diff --git a/arc/parser/adapters/orca.py b/arc/parser/adapters/orca.py index 2a93bd4be7..0d681f1a6c 100644 --- a/arc/parser/adapters/orca.py +++ b/arc/parser/adapters/orca.py @@ -7,10 +7,11 @@ import numpy as np import pandas as pd +import re from arc.common import SYMBOL_BY_NUMBER from arc.constants import E_h_kJmol, bohr_to_angstrom -from arc.species.converter import xyz_from_data +from arc.species.converter import str_to_xyz, xyz_from_data from arc.parser.adapter import ESSAdapter from arc.parser.factory import register_ess_adapter from arc.parser.parser import _get_lines_from_file @@ -238,8 +239,22 @@ def parse_1d_scan_energies(self) -> Tuple[Optional[List[float]], Optional[List[f Returns: Tuple[Optional[List[float]], Optional[List[float]]] The electronic energy in kJ/mol and the dihedral scan angle in degrees. """ - # Not implemented for Orca. - return None, None + cs, es = [], [] + with open(self.log_file_path, "r") as f: + flag_actual = False + for line in f.readlines(): + if "The Calculated Surface using the 'Actual Energy'" in line: + flag_actual = True + elif flag_actual: + if not line.strip(): + break + else: + c, e = line.split() + cs.append(float(c)) + es.append(float(e)) + if len(cs) != len(es) or not cs: + raise ValueError("Failed to parse 1D scan energies from Orca log file.") + return np.array(es), np.array(cs) def parse_1d_scan_coords(self) -> Optional[List[Dict[str, tuple]]]: """ @@ -248,8 +263,31 @@ def parse_1d_scan_coords(self) -> Optional[List[Dict[str, tuple]]]: Returns: List[Dict[str, tuple]] The Cartesian coordinates for each scan point. """ - # Not implemented for Orca. - return None + coords_list = [] + with open(self.log_file_path, "r") as f: + flag_hurray, flag_coords = False, False + pat = re.compile( + r'^\s*([A-Z][a-z]?)\s+' + r'([+-]?(?:\d+(?:\.\d*)?|\.\d+)(?:[eE][+-]?\d+)?)\s+' + r'([+-]?(?:\d+(?:\.\d*)?|\.\d+)(?:[eE][+-]?\d+)?)\s+' + r'([+-]?(?:\d+(?:\.\d*)?|\.\d+)(?:[eE][+-]?\d+)?)\s*$', + re.MULTILINE + ) + for line in f.readlines(): + if "HURRAY" in line: + coords = """""" + flag_hurray = True + if flag_hurray and "CARTESIAN COORDINATES (ANGSTROEM)" in line: + flag_coords = True + if flag_hurray and flag_coords: + if not line.strip(): + coords_list.append(str_to_xyz(coords)) + flag_hurray, flag_coords = False, False + if bool(pat.match(line)): + coords += line + if not coords_list: + raise ValueError("Failed to parse 1D scan coordinates from Orca log file.") + return coords_list def parse_irc_traj(self) -> Optional[List[Dict[str, tuple]]]: """ diff --git a/arc/parser/parser_test.py b/arc/parser/parser_test.py index 835e296a19..122d14e8ea 100644 --- a/arc/parser/parser_test.py +++ b/arc/parser/parser_test.py @@ -604,6 +604,24 @@ def test_parse_1d_scan_coords(self): self.assertEqual(traj_4[0]['symbols'], ('C', 'C', 'H', 'H', 'H', 'H', 'H', 'C', 'C', 'C', 'C', 'C', 'C', 'C', 'C', 'C', 'C', 'C', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H')) + + path_5 = os.path.join(ARC_PATH, 'arc', 'testing', 'rotor_scans', 'orca', 'cc.txt') + traj_5 = parser.parse_1d_scan_coords(path_5) + self.assertEqual(len(traj_5), 45) + self.assertEqual(traj_5[0]['symbols'], ('O', 'N', 'O', 'H')) + self.assertEqual(traj_5[10]['coords'], ((-0.799556, -0.234171, 0.251428), + (0.64986, -0.41193, -0.121131), + (0.909042, 0.203539, -1.074932), + (-0.759345, 0.442562, 0.944635))) + + path_6 = os.path.join(ARC_PATH, 'arc', 'testing', 'rotor_scans', 'orca', 'dft.txt') + traj_6 = parser.parse_1d_scan_coords(path_6) + self.assertEqual(len(traj_6), 40) + self.assertEqual(traj_6[0]['symbols'], ('N', 'O', 'O', 'H')) + self.assertEqual(traj_6[30]['coords'], ((0.002293, -0.673281, -0.26298), + (-0.138634, 0.590201, -0.397709), + (0.692562, 1.371759, 0.229642), + (-0.574929, -1.150836, 0.427339))) def test_parse_t1(self): """Test T1 diagnostic parsing""" @@ -712,6 +730,60 @@ def test_parse_1d_scan_energies(self): 104.0, 112.0, 120.0, 128.0, 136.0, 144.0, 152.0, 160.0, 168.0, 176.0, 184.0, 192.0, 200.0, 208.0, 216.0, 224.0, 232.0, 240.0, 248.0, 256.0, 264.0, 272.0, 280.0, 288.0, 296.0, 304.0, 312.0, 320.0, 328.0, 336.0, 344.0, 352.0]) + + path_4 = os.path.join(ARC_PATH, 'arc', 'testing', 'rotor_scans', 'orca', 'cc.txt') + energies_4, angles_4 = parser.parse_1d_scan_energies(log_file_path=path_4) + self.assertEqual(energies_4.shape, (45,)) + energies_4, angles_4 = energies_4.tolist(), angles_4.tolist() + self.assertEqual(angles_4, [-180. , -171.81818182, -163.63636364, -155.45454545, + -147.27272727, -139.09090909, -130.90909091, -122.72727273, + -114.54545455, -106.36363636, -98.18181818, -90. , + -81.81818182, -73.63636364, -65.45454545, -57.27272727, + -49.09090909, -40.90909091, -32.72727273, -24.54545455, + -16.36363636, -8.18181818, 0. , 8.18181818, + 16.36363636, 24.54545455, 32.72727273, 40.90909091, + 49.09090909, 57.27272727, 65.45454545, 73.63636364, + 81.81818182, 90. , 98.18181818, 106.36363636, + 114.54545455, 122.72727273, 130.90909091, 139.09090909, + 147.27272727, 155.45454545, 163.63636364, 171.81818182, + 180. ]) + self.assertEqual(energies_4, [-205.45224799, -205.45190811, -205.45091275, -205.44933274, + -205.44728671, -205.4449269 , -205.44243238, -205.43999284, + -205.43779528, -205.43600588, -205.434757 , -205.43414239, + -205.43420969, -205.43496112, -205.4363512 , -205.43828268, + -205.44061138, -205.44315299, -205.44569266, -205.44800238, + -205.4498563 , -205.4510646 , -205.45148293, -205.45106459, + -205.44985629, -205.44800238, -205.44569265, -205.44315298, + -205.44061136, -205.43828268, -205.43635116, -205.43496113, + -205.43420969, -205.43414239, -205.434757 , -205.43600587, + -205.43779528, -205.43999284, -205.44243239, -205.44492691, + -205.44728671, -205.44933274, -205.45091284, -205.45190811, + -205.45224799]) + + path_5 = os.path.join(ARC_PATH, 'arc', 'testing', 'rotor_scans', 'orca', 'dft.txt') + energies_5, angles_5 = parser.parse_1d_scan_energies(log_file_path=path_5) + self.assertEqual(energies_5.shape, (40,)) + energies_5, angles_5 = energies_5.tolist(), angles_5.tolist() + self.assertEqual(angles_5, [-180. , -170.76923077, -161.53846154, -152.30769231, + -143.07692308, -133.84615385, -124.61538462, -115.38461538, + -106.15384615, -96.92307692, -87.69230769, -78.46153846, + -69.23076923, -60. , -50.76923077, -41.53846154, + -32.30769231, -23.07692308, -13.84615385, -4.61538462, + 4.61538462, 13.84615385, 23.07692308, 32.30769231, + 41.53846154, 50.76923077, 60. , 69.23076923, + 78.46153846, 87.69230769, 96.92307692, 106.15384615, + 115.38461538, 124.61538462, 133.84615385, 143.07692308, + 152.30769231, 161.53846154, 170.76923077, 180. ]) + self.assertEqual(energies_5, [-205.56412863, -205.56304415, -205.55981277, -205.55449922, + -205.54721698, -205.53811775, -205.5274174 , -205.51539728, + -205.50245689, -205.49000818, -205.49181718, -205.50275068, + -205.51519265, -205.52710432, -205.53796901, -205.54748809, + -205.55543296, -205.56160894, -205.56584894, -205.5680131 , + -205.56801483, -205.56585336, -205.56161212, -205.55542977, + -205.54748298, -205.53796909, -205.52710778, -205.51519567, + -205.50275147, -205.49181828, -205.49000878, -205.50245773, + -205.51540006, -205.52742038, -205.53811826, -205.5472153 , + -205.55449977, -205.55981412, -205.56304759, -205.56413261]) def test_parse_nd_scan_energies(self): """Test parsing an ND scan output file""" diff --git a/arc/testing/rotor_scans/orca/cc.txt b/arc/testing/rotor_scans/orca/cc.txt new file mode 100644 index 0000000000..4e44830690 --- /dev/null +++ b/arc/testing/rotor_scans/orca/cc.txt @@ -0,0 +1,213801 @@ + + ***************** + * O R C A * + ***************** + + #, + ### + #### + ##### + ###### + ########, + ,,################,,,,, + ,,#################################,, + ,,##########################################,, + ,#########################################, ''#####, + ,#############################################,, '####, + ,##################################################,,,,####, + ,###########'''' ''''############################### + ,#####'' ,,,,##########,,,, '''####''' '#### + ,##' ,,,,###########################,,, '## + ' ,,###'''' '''############,,, + ,,##'' '''############,,,, ,,,,,,###'' + ,#'' '''#######################''' + ' ''''####'''' + ,#######, #######, ,#######, ## + ,#' '#, ## ## ,#' '#, #''# ###### ,####, + ## ## ## ,#' ## #' '# # #' '# + ## ## ####### ## ,######, #####, # # + '#, ,#' ## ## '#, ,#' ,# #, ## #, ,# + '#######' ## ## '#######' #' '# #####' # '####' + + + + ####################################################### + # -***- # + # Department of theory and spectroscopy # + # Directorship and core code : Frank Neese # + # Max Planck Institute fuer Kohlenforschung # + # Kaiser Wilhelm Platz 1 # + # D-45470 Muelheim/Ruhr # + # Germany # + # # + # All rights reserved # + # -***- # + ####################################################### + + + Program Version 5.0.4 - RELEASE - + + + With contributions from (in alphabetic order): + Daniel Aravena : Magnetic Suceptibility + Michael Atanasov : Ab Initio Ligand Field Theory (pilot matlab implementation) + Alexander A. Auer : GIAO ZORA, VPT2 properties, NMR spectrum + Ute Becker : Parallelization + Giovanni Bistoni : ED, misc. LED, open-shell LED, HFLD + Martin Brehm : Molecular dynamics + Dmytro Bykov : SCF Hessian + Vijay G. Chilkuri : MRCI spin determinant printing, contributions to CSF-ICE + Dipayan Datta : RHF DLPNO-CCSD density + Achintya Kumar Dutta : EOM-CC, STEOM-CC + Dmitry Ganyushin : Spin-Orbit,Spin-Spin,Magnetic field MRCI + Miquel Garcia : C-PCM and meta-GGA Hessian, CC/C-PCM, Gaussian charge scheme + Yang Guo : DLPNO-NEVPT2, F12-NEVPT2, CIM, IAO-localization + Andreas Hansen : Spin unrestricted coupled pair/coupled cluster methods + Benjamin Helmich-Paris : MC-RPA, TRAH-SCF, COSX integrals + Lee Huntington : MR-EOM, pCC + Robert Izsak : Overlap fitted RIJCOSX, COSX-SCS-MP3, EOM + Marcus Kettner : VPT2 + Christian Kollmar : KDIIS, OOCD, Brueckner-CCSD(T), CCSD density, CASPT2, CASPT2-K + Simone Kossmann : Meta GGA functionals, TD-DFT gradient, OOMP2, MP2 Hessian + Martin Krupicka : Initial AUTO-CI + Lucas Lang : DCDCAS + Marvin Lechner : AUTO-CI (C++ implementation), FIC-MRCC + Dagmar Lenk : GEPOL surface, SMD + Dimitrios Liakos : Extrapolation schemes; Compound Job, initial MDCI parallelization + Dimitrios Manganas : Further ROCIS development; embedding schemes + Dimitrios Pantazis : SARC Basis sets + Anastasios Papadopoulos: AUTO-CI, single reference methods and gradients + Taras Petrenko : DFT Hessian,TD-DFT gradient, ASA, ECA, R-Raman, ABS, FL, XAS/XES, NRVS + Peter Pinski : DLPNO-MP2, DLPNO-MP2 Gradient + Christoph Reimann : Effective Core Potentials + Marius Retegan : Local ZFS, SOC + Christoph Riplinger : Optimizer, TS searches, QM/MM, DLPNO-CCSD(T), (RO)-DLPNO pert. Triples + Tobias Risthaus : Range-separated hybrids, TD-DFT gradient, RPA, STAB + Michael Roemelt : Original ROCIS implementation + Masaaki Saitow : Open-shell DLPNO-CCSD energy and density + Barbara Sandhoefer : DKH picture change effects + Avijit Sen : IP-ROCIS + Kantharuban Sivalingam : CASSCF convergence, NEVPT2, FIC-MRCI + Bernardo de Souza : ESD, SOC TD-DFT + Georgi Stoychev : AutoAux, RI-MP2 NMR, DLPNO-MP2 response + Willem Van den Heuvel : Paramagnetic NMR + Boris Wezisla : Elementary symmetry handling + Frank Wennmohs : Technical directorship + + + We gratefully acknowledge several colleagues who have allowed us to + interface, adapt or use parts of their codes: + Stefan Grimme, W. Hujo, H. Kruse, P. Pracht, : VdW corrections, initial TS optimization, + C. Bannwarth, S. Ehlert DFT functionals, gCP, sTDA/sTD-DF + Ed Valeev, F. Pavosevic, A. Kumar : LibInt (2-el integral package), F12 methods + Garnet Chan, S. Sharma, J. Yang, R. Olivares : DMRG + Ulf Ekstrom : XCFun DFT Library + Mihaly Kallay : mrcc (arbitrary order and MRCC methods) + Jiri Pittner, Ondrej Demel : Mk-CCSD + Frank Weinhold : gennbo (NPA and NBO analysis) + Christopher J. Cramer and Donald G. Truhlar : smd solvation model + Lars Goerigk : TD-DFT with DH, B97 family of functionals + V. Asgeirsson, H. Jonsson : NEB implementation + FAccTs GmbH : IRC, NEB, NEB-TS, DLPNO-Multilevel, CI-OPT + MM, QMMM, 2- and 3-layer-ONIOM, Crystal-QMMM, + LR-CPCM, SF, NACMEs, symmetry and pop. for TD-DFT, + nearIR, NL-DFT gradient (VV10), updates on ESD, + ML-optimized integration grids + S Lehtola, MJT Oliveira, MAL Marques : LibXC Library + Liviu Ungur et al : ANISO software + + + Your calculation uses the libint2 library for the computation of 2-el integrals + For citations please refer to: http://libint.valeyev.net + + Your ORCA version has been built with support for libXC version: 5.1.0 + For citations please refer to: https://tddft.org/programs/libxc/ + + This ORCA versions uses: + CBLAS interface : Fast vector & matrix operations + LAPACKE interface : Fast linear algebra routines + SCALAPACK package : Parallel linear algebra routines + Shared memory : Shared parallel matrices + BLAS/LAPACK : OpenBLAS 0.3.15 USE64BITINT DYNAMIC_ARCH NO_AFFINITY Zen SINGLE_THREADED + Core in use : Zen + Copyright (c) 2011-2014, The OpenBLAS Project + + +================================================================================ + +----- Orbital basis set information ----- +Your calculation utilizes the basis: aug-cc-pVTZ + H, B-Ne : Obtained from the ccRepo (grant-hill.group.shef.ac.uk/ccrepo) Feb. 2017 + R. A. Kendall, T. H. Dunning, Jr., R. J. Harrison, J. Chem. Phys. 96, 6796 (1992) + He : Obtained from the ccRepo (grant-hill.group.shef.ac.uk/ccrepo) Feb. 2017 + D. E. Woon, T. H. Dunning, Jr., J. Chem. Phys. 100, 2975 (1994) + Li-Be, Na : Obtained from the ccRepo (grant-hill.group.shef.ac.uk/ccrepo) Feb. 2017 + B. P. Prascher, D. E. Woon, K. A. Peterson, T. H. Dunning, Jr., A. K. Wilson, Theor. Chem. Acc. 128, 69 (2011) + Mg : Obtained from the Peterson Research Group Website (tyr0.chem.wsu.edu/~kipeters) Feb. 2017 + B. P. Prascher, D. E. Woon, K. A. Peterson, T. H. Dunning, Jr., A. K. Wilson, Theor. Chem. Acc. 128, 69 (2011) + Al-Ar : Obtained from the ccRepo (grant-hill.group.shef.ac.uk/ccrepo) Feb. 2017 + D. E. Woon, T. H. Dunning, Jr., J. Chem. Phys. 98, 1358 (1993) + Sc-Zn : Obtained from the ccRepo (grant-hill.group.shef.ac.uk/ccrepo) Feb. 2017 + N. B. Balabanov, K. A. Peterson, J. Chem. Phys. 123, 064107 (2005) + N. B. Balabanov, K. A. Peterson, J. Chem. Phys. 125, 074110 (2006) + Ga-Kr : Obtained from the ccRepo (grant-hill.group.shef.ac.uk/ccrepo) Feb. 2017 + A. K. Wilson, D. E. Woon, K. A. Peterson, T. H. Dunning, Jr., J. Chem. Phys. 110, 7667 (1999) + Ag, Au : Obtained from the Peterson Research Group Website (tyr0.chem.wsu.edu/~kipeters) Feb. 2017 + K. A. Peterson, C. Puzzarini, Theor. Chem. Acc. 114, 283 (2005) + +================================================================================ + WARNINGS + Please study these warnings very carefully! +================================================================================ + + +WARNING: The environment variable RSH_COMMAND is not set! + ===> : All Displacements for the Numerical Hessian or Gradient calculation + will be started on localhost + +WARNING: Geometry Optimization + ===> : Switching off AutoStart + For restart on a previous wavefunction, please use MOREAD + +WARNING: Post HF methods need fully converged wavefunctions + ===> : Setting SCFConvForced true + You can overwrite this default with %scf ConvForced false + + +WARNING: MDCI localization with Augmented Hessian Foster-Boys + ===> : Switching off randomization! + +INFO : the flag for use of the SHARK integral package has been found! + +================================================================================ + INPUT FILE +================================================================================ +NAME = input.in +| 1> !uHF ccsd(t) aug-cc-pvtz tightscf numgrad +| 2> !Opt +| 3> +| 4> %maxcore 9900 +| 5> %pal # job parallelization settings +| 6> nprocs 30 +| 7> end +| 8> %scf # recommended SCF settings +| 9> MaxIter 1500 +| 10> AutoTRAH true +| 11> AutoTRAHTol 1.125 +| 12> AutoTRAHIter 20 +| 13> AutoTRAHNInter 10 +| 14> trah +| 15> tradius 0.8 +| 16> Randomize true +| 17> QuadRegionStart 1.e-3 +| 18> end +| 19> end +| 20> %mdci # recommended SCF settings +| 21> MaxIter 500 +| 22> end +| 23> %geom Scan +| 24> D 2 1 0 3 = -180.0, 180.0, 45.0 +| 25> end +| 26> Calc_Hess true # Request an exact Hessian (here analytical) in the first optimization step +| 27> Recalc_Hess 3 # Recalculate the exact Hessian every 2 steps. +| 28> NumHess true +| 29> end +| 30> +| 31> * xyz 0 1 +| 32> O -0.754572 0.071437 0.135009 +| 33> N 0.659894 -0.060849 -0.046614 +| 34> O 0.926378 -0.111472 -1.188780 +| 35> H -0.831699 0.100884 1.100385 +| 36> * +| 37> +| 38> ****END OF INPUT**** +================================================================================ + + ****************************** + * Relaxed Surface Scan * + ****************************** + + Dihedral ( 2, 1, 0, 3): range= -180.00000000 .. 180.00000000 steps = 45 + +There is 1 parameter to be scanned. +There will be 45 constrained geometry optimizations. + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 1 * + * * + * Dihedral ( 2, 1, 0, 3) : -180.00000000 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Almoef's Model + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000204498 RMS(Int)= 0.0000000000 + Iter 1: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4322 0.000000 + 2. B(O 2,N 1) 1.1739 0.000000 + 3. B(H 3,O 0) 0.9689 0.000000 + 4. A(N 1,O 0,H 3) 101.9921 0.000000 + 5. A(O 0,N 1,O 2) 110.5825 0.000000 + 6. D(O 2,N 1,O 0,H 3) -180.0000 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.754570 0.071455 0.135009 + N 0.659896 -0.060830 -0.046614 + O 0.926376 -0.111489 -1.188780 + H -0.831701 0.100864 1.100385 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.425931 0.135030 0.255129 + 1 N 7.0000 0 14.007 1.247022 -0.114951 -0.088089 + 2 O 8.0000 0 15.999 1.750598 -0.210684 -2.246468 + 3 H 1.0000 0 1.008 -1.571687 0.190605 2.079427 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.432201300475 0.00000000 0.00000000 + O 2 1 0 1.173933380538 110.58246747 0.00000000 + H 1 2 3 0.968899644604 101.99209941 180.00422844 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.706468226543 0.00000000 0.00000000 + O 2 1 0 2.218412588685 110.58246747 0.00000000 + H 1 2 3 1.830954979555 101.99209941 180.00422844 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.499001626865 Eh + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.4990016269 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 20 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.972e-04 +Time for diagonalization ... 0.013 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.003 sec +Total time needed ... 0.018 sec + +Time for model grid setup = 0.053 sec + +------------------------------ +INITIAL GUESS: MODEL POTENTIAL +------------------------------ +Loading Hartree-Fock densities ... done +Calculating cut-offs ... done +Initializing the effective Hamiltonian ... done +Setting up the integral package (SHARK) ... done +Starting the Coulomb interaction ... done ( 0.0 sec) +Reading the grid ... done +Mapping shells ... done +Starting the XC term evaluation ... done ( 0.0 sec) +Transforming the Hamiltonian ... done ( 0.0 sec) +Diagonalizing the Hamiltonian ... done ( 0.0 sec) +Back transforming the eigenvectors ... done ( 0.0 sec) +Now organizing SCF variables ... done + ------------------ + INITIAL GUESS DONE ( 0.1 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.6126493400 0.000000000000 0.01688516 0.00037119 0.1238706 0.7000 + 1 -204.6514185096 -0.038769169562 0.01219835 0.00026714 0.0729753 0.7000 + ***Turning on DIIS*** + 2 -204.6732852007 -0.021866691062 0.02621727 0.00059552 0.0548218 0.0000 + 3 -204.5966587294 0.076626471264 0.01116673 0.00019838 0.0242683 0.0000 + 4 -204.7516893784 -0.155030648989 0.00757127 0.00010705 0.0061127 0.0000 + 5 -204.7104502924 0.041239086028 0.00147375 0.00005790 0.0033444 0.0000 + 6 -204.7162301947 -0.005779902314 0.00114807 0.00004155 0.0019660 0.0000 + 7 -204.7245785125 -0.008348317779 0.00089337 0.00003367 0.0009277 0.0000 + 8 -204.7219452186 0.002633293856 0.00031430 0.00000984 0.0004057 0.0000 + 9 -204.7234034287 -0.001458210118 0.00011824 0.00000366 0.0003032 0.0000 + 10 -204.7237785324 -0.000375103672 0.00004118 0.00000093 0.0001121 0.0000 + 11 -204.7233942436 0.000384288789 0.00003005 0.00000082 0.0000696 0.0000 + 12 -204.7235955412 -0.000201297580 0.00000780 0.00000020 0.0000145 0.0000 + 13 -204.7235621241 0.000033417047 0.00000319 0.00000007 0.0000035 0.0000 + 14 -204.7235623664 -0.000000242306 0.00000114 0.00000003 0.0000022 0.0000 + 15 -204.7235788326 -0.000016466205 0.00000058 0.00000002 0.0000012 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 16 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72357242 Eh -5570.81162 eV + +Components: +Nuclear Repulsion : 69.49900163 Eh 1891.16398 eV +Electronic Energy : -274.22257404 Eh -7461.97560 eV +One Electron Energy: -418.70021607 Eh -11393.41211 eV +Two Electron Energy: 144.47764202 Eh 3931.43651 eV + +Virial components: +Potential Energy : -408.97169148 Eh -11128.68550 eV +Kinetic Energy : 204.24811906 Eh 5557.87388 eV +Virial Ratio : 2.00232782 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 6.4151e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.5877e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.9767e-09 Tolerance : 5.0000e-09 + Last DIIS Error ... 4.2492e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.666374 -562.3606 + 1 1.0000 -20.640631 -561.6601 + 2 1.0000 -15.799033 -429.9135 + 3 1.0000 -1.604956 -43.6731 + 4 1.0000 -1.401152 -38.1273 + 5 1.0000 -0.948457 -25.8088 + 6 1.0000 -0.784316 -21.3423 + 7 1.0000 -0.729953 -19.8630 + 8 1.0000 -0.681991 -18.5579 + 9 1.0000 -0.625766 -17.0280 + 10 1.0000 -0.528608 -14.3842 + 11 1.0000 -0.461227 -12.5506 + 12 0.0000 0.028186 0.7670 + 13 0.0000 0.080728 2.1967 + 14 0.0000 0.093798 2.5524 + 15 0.0000 0.097595 2.6557 + 16 0.0000 0.128966 3.5094 + 17 0.0000 0.144030 3.9193 + 18 0.0000 0.156806 4.2669 + 19 0.0000 0.172184 4.6854 + 20 0.0000 0.187308 5.0969 + 21 0.0000 0.196560 5.3487 + 22 0.0000 0.205557 5.5935 + 23 0.0000 0.233200 6.3457 + 24 0.0000 0.258296 7.0286 + 25 0.0000 0.296644 8.0721 + 26 0.0000 0.306323 8.3355 + 27 0.0000 0.329731 8.9724 + 28 0.0000 0.365079 9.9343 + 29 0.0000 0.382321 10.4035 + 30 0.0000 0.424684 11.5562 + 31 0.0000 0.525035 14.2869 + 32 0.0000 0.526380 14.3235 + 33 0.0000 0.547269 14.8919 + 34 0.0000 0.572958 15.5910 + 35 0.0000 0.613287 16.6884 + 36 0.0000 0.632441 17.2096 + 37 0.0000 0.648631 17.6502 + 38 0.0000 0.679572 18.4921 + 39 0.0000 0.714224 19.4350 + 40 0.0000 0.717727 19.5303 + 41 0.0000 0.748448 20.3663 + 42 0.0000 0.775021 21.0894 + 43 0.0000 0.782002 21.2794 + 44 0.0000 0.811611 22.0851 + 45 0.0000 0.811813 22.0906 + 46 0.0000 0.861048 23.4303 + 47 0.0000 0.878342 23.9009 + 48 0.0000 0.926303 25.2060 + 49 0.0000 0.939421 25.5629 + 50 0.0000 0.946035 25.7429 + 51 0.0000 0.995906 27.1000 + 52 0.0000 1.049086 28.5471 + 53 0.0000 1.062877 28.9224 + 54 0.0000 1.081216 29.4214 + 55 0.0000 1.105813 30.0907 + 56 0.0000 1.160613 31.5819 + 57 0.0000 1.195090 32.5200 + 58 0.0000 1.253616 34.1126 + 59 0.0000 1.267957 34.5029 + 60 0.0000 1.363209 37.0948 + 61 0.0000 1.434927 39.0464 + 62 0.0000 1.490479 40.5580 + 63 0.0000 1.522698 41.4347 + 64 0.0000 1.524489 41.4835 + 65 0.0000 1.544005 42.0145 + 66 0.0000 1.555311 42.3222 + 67 0.0000 1.608982 43.7826 + 68 0.0000 1.658104 45.1193 + 69 0.0000 1.728116 47.0244 + 70 0.0000 1.753346 47.7110 + 71 0.0000 1.822075 49.5812 + 72 0.0000 1.854630 50.4670 + 73 0.0000 1.962140 53.3926 + 74 0.0000 1.975512 53.7564 + 75 0.0000 1.995623 54.3037 + 76 0.0000 2.072981 56.4087 + 77 0.0000 2.132985 58.0415 + 78 0.0000 2.133028 58.0426 + 79 0.0000 2.186682 59.5026 + 80 0.0000 2.270895 61.7942 + 81 0.0000 2.309560 62.8463 + 82 0.0000 2.328835 63.3708 + 83 0.0000 2.381951 64.8162 + 84 0.0000 2.450733 66.6878 + 85 0.0000 2.468720 67.1773 + 86 0.0000 2.499690 68.0200 + 87 0.0000 2.502254 68.0898 + 88 0.0000 2.522190 68.6323 + 89 0.0000 2.543823 69.2209 + 90 0.0000 2.569374 69.9162 + 91 0.0000 2.607705 70.9593 + 92 0.0000 2.608580 70.9831 + 93 0.0000 2.663985 72.4907 + 94 0.0000 2.772406 75.4410 + 95 0.0000 2.779627 75.6375 + 96 0.0000 2.835408 77.1554 + 97 0.0000 2.938139 79.9508 + 98 0.0000 2.946690 80.1835 + 99 0.0000 3.113794 84.7307 + 100 0.0000 3.148543 85.6762 + 101 0.0000 3.183685 86.6325 + 102 0.0000 3.247018 88.3558 + 103 0.0000 3.457521 94.0839 + 104 0.0000 3.833932 104.3266 + 105 0.0000 3.852432 104.8300 + 106 0.0000 4.030589 109.6779 + 107 0.0000 4.172691 113.5447 + 108 0.0000 4.186401 113.9178 + 109 0.0000 4.212854 114.6376 + 110 0.0000 4.367968 118.8585 + 111 0.0000 4.373793 119.0170 + 112 0.0000 4.579770 124.6219 + 113 0.0000 4.634529 126.1120 + 114 0.0000 4.750153 129.2582 + 115 0.0000 4.814628 131.0127 + 116 0.0000 4.872016 132.5743 + 117 0.0000 4.887346 132.9914 + 118 0.0000 4.984412 135.6328 + 119 0.0000 5.001438 136.0960 + 120 0.0000 5.073903 138.0679 + 121 0.0000 5.089808 138.5007 + 122 0.0000 5.169947 140.6814 + 123 0.0000 5.248402 142.8163 + 124 0.0000 5.256924 143.0482 + 125 0.0000 5.336164 145.2044 + 126 0.0000 5.368995 146.0978 + 127 0.0000 5.374919 146.2590 + 128 0.0000 5.574875 151.7001 + 129 0.0000 5.672083 154.3452 + 130 0.0000 5.796892 157.7414 + 131 0.0000 5.992307 163.0590 + 132 0.0000 6.111650 166.3064 + 133 0.0000 6.433807 175.0728 + 134 0.0000 6.506423 177.0488 + 135 0.0000 6.509661 177.1369 + 136 0.0000 6.674513 181.6227 + 137 0.0000 6.716520 182.7658 + 138 0.0000 6.744903 183.5381 + 139 0.0000 6.848282 186.3512 + 140 0.0000 6.915124 188.1701 + 141 0.0000 7.070627 192.4015 + 142 0.0000 7.119682 193.7364 + 143 0.0000 7.183344 195.4687 + 144 0.0000 7.233744 196.8402 + 145 0.0000 7.256463 197.4584 + 146 0.0000 7.259774 197.5485 + 147 0.0000 7.337757 199.6705 + 148 0.0000 7.383245 200.9083 + 149 0.0000 7.432623 202.2519 + 150 0.0000 7.478325 203.4956 + 151 0.0000 7.611066 207.1076 + 152 0.0000 7.647574 208.1011 + 153 0.0000 7.701910 209.5796 + 154 0.0000 7.788453 211.9346 + 155 0.0000 7.975878 217.0347 + 156 0.0000 8.069495 219.5821 + 157 0.0000 8.427282 229.3180 + 158 0.0000 14.212783 386.7495 + 159 0.0000 15.130630 411.7254 + 160 0.0000 16.046156 436.6381 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.666374 -562.3606 + 1 1.0000 -20.640631 -561.6601 + 2 1.0000 -15.799033 -429.9135 + 3 1.0000 -1.604956 -43.6731 + 4 1.0000 -1.401152 -38.1273 + 5 1.0000 -0.948457 -25.8088 + 6 1.0000 -0.784316 -21.3423 + 7 1.0000 -0.729953 -19.8630 + 8 1.0000 -0.681991 -18.5579 + 9 1.0000 -0.625766 -17.0280 + 10 1.0000 -0.528608 -14.3842 + 11 1.0000 -0.461227 -12.5506 + 12 0.0000 0.028186 0.7670 + 13 0.0000 0.080728 2.1967 + 14 0.0000 0.093798 2.5524 + 15 0.0000 0.097595 2.6557 + 16 0.0000 0.128966 3.5094 + 17 0.0000 0.144030 3.9193 + 18 0.0000 0.156806 4.2669 + 19 0.0000 0.172184 4.6854 + 20 0.0000 0.187308 5.0969 + 21 0.0000 0.196560 5.3487 + 22 0.0000 0.205557 5.5935 + 23 0.0000 0.233200 6.3457 + 24 0.0000 0.258296 7.0286 + 25 0.0000 0.296644 8.0721 + 26 0.0000 0.306323 8.3355 + 27 0.0000 0.329731 8.9724 + 28 0.0000 0.365079 9.9343 + 29 0.0000 0.382321 10.4035 + 30 0.0000 0.424684 11.5562 + 31 0.0000 0.525035 14.2869 + 32 0.0000 0.526380 14.3235 + 33 0.0000 0.547269 14.8919 + 34 0.0000 0.572958 15.5910 + 35 0.0000 0.613287 16.6884 + 36 0.0000 0.632441 17.2096 + 37 0.0000 0.648631 17.6502 + 38 0.0000 0.679572 18.4921 + 39 0.0000 0.714224 19.4350 + 40 0.0000 0.717727 19.5303 + 41 0.0000 0.748448 20.3663 + 42 0.0000 0.775021 21.0894 + 43 0.0000 0.782002 21.2794 + 44 0.0000 0.811611 22.0851 + 45 0.0000 0.811813 22.0906 + 46 0.0000 0.861048 23.4303 + 47 0.0000 0.878342 23.9009 + 48 0.0000 0.926303 25.2060 + 49 0.0000 0.939421 25.5629 + 50 0.0000 0.946035 25.7429 + 51 0.0000 0.995906 27.1000 + 52 0.0000 1.049086 28.5471 + 53 0.0000 1.062877 28.9224 + 54 0.0000 1.081216 29.4214 + 55 0.0000 1.105813 30.0907 + 56 0.0000 1.160613 31.5819 + 57 0.0000 1.195090 32.5200 + 58 0.0000 1.253616 34.1126 + 59 0.0000 1.267957 34.5029 + 60 0.0000 1.363209 37.0948 + 61 0.0000 1.434927 39.0464 + 62 0.0000 1.490479 40.5580 + 63 0.0000 1.522698 41.4347 + 64 0.0000 1.524489 41.4835 + 65 0.0000 1.544005 42.0145 + 66 0.0000 1.555311 42.3222 + 67 0.0000 1.608982 43.7826 + 68 0.0000 1.658104 45.1193 + 69 0.0000 1.728116 47.0244 + 70 0.0000 1.753346 47.7110 + 71 0.0000 1.822075 49.5812 + 72 0.0000 1.854630 50.4670 + 73 0.0000 1.962140 53.3926 + 74 0.0000 1.975512 53.7564 + 75 0.0000 1.995623 54.3037 + 76 0.0000 2.072981 56.4087 + 77 0.0000 2.132985 58.0415 + 78 0.0000 2.133028 58.0426 + 79 0.0000 2.186682 59.5026 + 80 0.0000 2.270895 61.7942 + 81 0.0000 2.309560 62.8463 + 82 0.0000 2.328835 63.3708 + 83 0.0000 2.381951 64.8162 + 84 0.0000 2.450733 66.6878 + 85 0.0000 2.468720 67.1773 + 86 0.0000 2.499690 68.0200 + 87 0.0000 2.502254 68.0898 + 88 0.0000 2.522190 68.6323 + 89 0.0000 2.543823 69.2209 + 90 0.0000 2.569374 69.9162 + 91 0.0000 2.607705 70.9593 + 92 0.0000 2.608580 70.9831 + 93 0.0000 2.663985 72.4907 + 94 0.0000 2.772406 75.4410 + 95 0.0000 2.779627 75.6375 + 96 0.0000 2.835408 77.1554 + 97 0.0000 2.938139 79.9508 + 98 0.0000 2.946690 80.1835 + 99 0.0000 3.113794 84.7307 + 100 0.0000 3.148543 85.6762 + 101 0.0000 3.183685 86.6325 + 102 0.0000 3.247018 88.3558 + 103 0.0000 3.457521 94.0839 + 104 0.0000 3.833932 104.3266 + 105 0.0000 3.852432 104.8300 + 106 0.0000 4.030589 109.6779 + 107 0.0000 4.172691 113.5447 + 108 0.0000 4.186401 113.9178 + 109 0.0000 4.212854 114.6376 + 110 0.0000 4.367968 118.8585 + 111 0.0000 4.373793 119.0170 + 112 0.0000 4.579770 124.6219 + 113 0.0000 4.634529 126.1120 + 114 0.0000 4.750153 129.2582 + 115 0.0000 4.814628 131.0127 + 116 0.0000 4.872016 132.5743 + 117 0.0000 4.887346 132.9914 + 118 0.0000 4.984412 135.6328 + 119 0.0000 5.001438 136.0960 + 120 0.0000 5.073903 138.0679 + 121 0.0000 5.089808 138.5007 + 122 0.0000 5.169947 140.6814 + 123 0.0000 5.248402 142.8163 + 124 0.0000 5.256924 143.0482 + 125 0.0000 5.336164 145.2044 + 126 0.0000 5.368995 146.0978 + 127 0.0000 5.374919 146.2590 + 128 0.0000 5.574875 151.7001 + 129 0.0000 5.672083 154.3452 + 130 0.0000 5.796892 157.7414 + 131 0.0000 5.992307 163.0590 + 132 0.0000 6.111650 166.3064 + 133 0.0000 6.433807 175.0728 + 134 0.0000 6.506423 177.0488 + 135 0.0000 6.509661 177.1369 + 136 0.0000 6.674513 181.6227 + 137 0.0000 6.716520 182.7658 + 138 0.0000 6.744903 183.5381 + 139 0.0000 6.848282 186.3512 + 140 0.0000 6.915124 188.1701 + 141 0.0000 7.070627 192.4015 + 142 0.0000 7.119682 193.7364 + 143 0.0000 7.183344 195.4687 + 144 0.0000 7.233744 196.8402 + 145 0.0000 7.256463 197.4584 + 146 0.0000 7.259774 197.5485 + 147 0.0000 7.337757 199.6705 + 148 0.0000 7.383245 200.9083 + 149 0.0000 7.432623 202.2519 + 150 0.0000 7.478325 203.4956 + 151 0.0000 7.611066 207.1076 + 152 0.0000 7.647574 208.1011 + 153 0.0000 7.701910 209.5796 + 154 0.0000 7.788453 211.9346 + 155 0.0000 7.975878 217.0347 + 156 0.0000 8.069495 219.5821 + 157 0.0000 8.427282 229.3180 + 158 0.0000 14.212783 386.7495 + 159 0.0000 15.130630 411.7254 + 160 0.0000 16.046156 436.6381 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.343814 0.000000 + 1 N : 0.343829 0.000000 + 2 O : -0.278290 0.000000 + 3 H : 0.278275 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.866646 s : 3.866646 + pz : 1.377087 p : 4.448634 + px : 1.239945 + py : 1.831601 + dz2 : 0.012070 d : 0.023873 + dxz : -0.002951 + dyz : 0.000805 + dx2y2 : 0.006041 + dxy : 0.007909 + f0 : 0.000572 f : 0.004661 + f+1 : 0.001056 + f-1 : 0.000067 + f+2 : 0.000668 + f-2 : -0.000149 + f+3 : 0.001048 + f-3 : 0.001398 + 1 N s : 3.829964 s : 3.829964 + pz : 1.084856 p : 2.651221 + px : 0.833260 + py : 0.733106 + dz2 : 0.031703 d : 0.145290 + dxz : 0.035177 + dyz : 0.032310 + dx2y2 : 0.023838 + dxy : 0.022263 + f0 : 0.005277 f : 0.029696 + f+1 : 0.009176 + f-1 : 0.005949 + f+2 : 0.002046 + f-2 : 0.000323 + f+3 : 0.001900 + f-3 : 0.005024 + 2 O s : 3.876828 s : 3.876828 + pz : 1.202296 p : 4.330176 + px : 1.858925 + py : 1.268955 + dz2 : 0.013917 d : 0.063436 + dxz : 0.017258 + dyz : 0.030667 + dx2y2 : -0.000131 + dxy : 0.001726 + f0 : 0.002181 f : 0.007849 + f+1 : 0.002451 + f-1 : 0.002845 + f+2 : 0.000049 + f-2 : 0.000465 + f+3 : -0.000044 + f-3 : -0.000098 + 3 H s : 0.621480 s : 0.621480 + pz : 0.015374 p : 0.077553 + px : 0.020126 + py : 0.042053 + dz2 : 0.000760 d : 0.022691 + dxz : 0.011650 + dyz : 0.011012 + dx2y2 : -0.000336 + dxy : -0.000395 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.605103 0.000000 + 1 N : -0.268722 0.000000 + 2 O : 0.234778 0.000000 + 3 H : -0.571159 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.112836 s : 3.112836 + pz : 1.284577 p : 3.900254 + px : 1.179134 + py : 1.436543 + dz2 : 0.076007 d : 0.293053 + dxz : 0.073969 + dyz : 0.005076 + dx2y2 : 0.091888 + dxy : 0.046113 + f0 : 0.018117 f : 0.088754 + f+1 : 0.015792 + f-1 : 0.001082 + f+2 : 0.017661 + f-2 : 0.003187 + f+3 : 0.018552 + f-3 : 0.014363 + 1 N s : 3.001518 s : 3.001518 + pz : 1.235340 p : 2.833138 + px : 0.912972 + py : 0.684827 + dz2 : 0.278630 d : 0.973571 + dxz : 0.309443 + dyz : 0.114133 + dx2y2 : 0.146084 + dxy : 0.125281 + f0 : 0.110553 f : 0.460494 + f+1 : 0.137900 + f-1 : 0.063178 + f+2 : 0.048935 + f-2 : 0.008778 + f+3 : 0.036395 + f-3 : 0.054756 + 2 O s : 3.315119 s : 3.315119 + pz : 1.405515 p : 4.007126 + px : 1.515046 + py : 1.086565 + dz2 : 0.154349 d : 0.324903 + dxz : 0.098597 + dyz : 0.048604 + dx2y2 : 0.015524 + dxy : 0.007829 + f0 : 0.049581 f : 0.118073 + f+1 : 0.032067 + f-1 : 0.020265 + f+2 : 0.010218 + f-2 : 0.004860 + f+3 : 0.000782 + f-3 : 0.000301 + 3 H s : 0.621336 s : 0.621336 + pz : 0.264553 p : 0.554298 + px : 0.131291 + py : 0.158453 + dz2 : 0.131783 d : 0.395525 + dxz : 0.119141 + dyz : 0.123726 + dx2y2 : 0.017316 + dxy : 0.003559 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3438 8.0000 -0.3438 1.9472 1.9472 -0.0000 + 1 N 6.6562 7.0000 0.3438 2.5335 2.5335 0.0000 + 2 O 8.2783 8.0000 -0.2783 1.7240 1.7240 0.0000 + 3 H 0.7217 1.0000 0.2783 0.9374 0.9374 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.9269 B( 0-O , 3-H ) : 0.9638 B( 1-N , 2-O ) : 1.6502 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 5 sec + +Total time .... 5.769 sec +Sum of individual times .... 5.444 sec ( 94.4%) + +Fock matrix formation .... 4.763 sec ( 82.6%) +Diagonalization .... 0.280 sec ( 4.9%) +Density matrix formation .... 0.024 sec ( 0.4%) +Population analysis .... 0.019 sec ( 0.3%) +Initial guess .... 0.061 sec ( 1.1%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.244 sec ( 4.2%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.704 sec +Reference energy ... -204.723572229 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 10.022 sec +AO-integral generation ... 0.359 sec +Half transformation ... 0.164 sec +K-integral sorting ... 7.494 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.061 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.065 s ( 0.000 ms/b) + 277134 b 0 skpd 0.070 s ( 0.000 ms/b) +: : 151164 b 0 skpd 0.074 s ( 0.000 ms/b) + 159120 b 0 skpd 0.037 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.079 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.075 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.060 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.102 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.053 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.793 sec +AO-integral generation ... 0.615 sec +Half transformation ... 0.065 sec +J-integral sorting ... 0.074 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.244 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.340 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090624542 +EMP2(bb)= -0.090624542 +EMP2(ab)= -0.516513955 + +Initial guess performed in 0.167 sec +E(0) ... -204.723572229 +E(MP2) ... -0.697763039 +Initial E(tot) ... -205.421335268 + ... 0.187994192 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.421335268 -0.697763039 -0.000000000 0.027383982 6.16 0.000000409 + *** Turning on DIIS *** + 1 -205.391990128 -0.668417899 0.029345140 0.012033897 4.92 0.058113227 + 2 -205.411496099 -0.687923870 -0.019505971 0.006058379 5.82 0.061002179 + 3 -205.415186525 -0.691614296 -0.003690426 0.002487962 5.15 0.075437301 + 4 -205.416755054 -0.693182825 -0.001568529 0.001610328 5.51 0.082320119 + 5 -205.417313976 -0.693741747 -0.000558922 0.000850287 5.71 0.088076293 + 6 -205.417425587 -0.693853358 -0.000111611 0.000498841 4.61 0.090876778 + 7 -205.417469380 -0.693897152 -0.000043794 0.000190475 4.93 0.092090001 + 8 -205.417480870 -0.693908641 -0.000011489 0.000098421 4.55 0.092521443 + 9 -205.417476777 -0.693904548 0.000004093 0.000025370 4.92 0.092644701 + 10 -205.417481012 -0.693908783 -0.000004235 0.000008820 5.17 0.092677975 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.723572229 +E(CORR) ... -0.693908783 +E(TOT) ... -205.417481012 +Singles norm **1/2 ... 0.092677975 ( 0.046338988, 0.046338988) +T1 diagnostic ... 0.021844408 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.066658 + 10a-> 13a 10b-> 13b 0.054280 + 8b-> 13b -1b-> -1b 0.045584 + 8a-> 13a -1a-> -1a 0.045584 + 10a-> 13a 8b-> 13b 0.036997 + 8a-> 13a 10b-> 13b 0.036997 + 10a-> 13a -1a-> -1a 0.033154 + 10b-> 13b -1b-> -1b 0.033154 + 11a-> 26a 11b-> 26b 0.031674 + 11a-> 26a -1a-> -1a 0.030160 + 11b-> 26b -1b-> -1b 0.030160 + 11a-> 13a 11b-> 13b 0.027957 + 5a-> 13a 5b-> 13b 0.025414 + 11a-> 26a 10b-> 13b 0.025175 + 10a-> 13a 11b-> 26b 0.025175 + 8a-> 22a 8b-> 13b 0.024607 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034766973 + alpha-alpha-alpha ... -0.000901677 ( 2.6%) + alpha-alpha-beta ... -0.016481810 ( 47.4%) + alpha-beta -beta ... -0.016481810 ( 47.4%) + beta -beta -beta ... -0.000901677 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034766973 + +Final correlation energy ... -0.728675757 +E(CCSD) ... -205.417481012 +E(CCSD(T)) ... -205.452247985 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209492550 sqrt= 1.099769317 +W(HF) = 0.826793021 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.254542 0.000000 + 1 N : 0.153566 -0.000000 + 2 O : -0.164582 -0.000000 + 3 H : 0.265559 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.846965 s : 3.846965 + pz : 1.359653 p : 4.342840 + px : 1.236711 + py : 1.746476 + dz2 : 0.016494 d : 0.056259 + dxz : 0.005370 + dyz : 0.007895 + dx2y2 : 0.011213 + dxy : 0.015287 + f0 : 0.001289 f : 0.008478 + f+1 : 0.001495 + f-1 : 0.000695 + f+2 : 0.001209 + f-2 : 0.000533 + f+3 : 0.001313 + f-3 : 0.001944 + 1 N s : 3.879614 s : 3.879614 + pz : 1.048969 p : 2.762244 + px : 0.868735 + py : 0.844539 + dz2 : 0.036066 d : 0.175434 + dxz : 0.046687 + dyz : 0.032276 + dx2y2 : 0.029169 + dxy : 0.031236 + f0 : 0.004858 f : 0.029143 + f+1 : 0.008884 + f-1 : 0.004746 + f+2 : 0.002509 + f-2 : 0.000948 + f+3 : 0.002042 + f-3 : 0.005155 + 2 O s : 3.866794 s : 3.866794 + pz : 1.190891 p : 4.202119 + px : 1.777694 + py : 1.233534 + dz2 : 0.016620 d : 0.085232 + dxz : 0.024233 + dyz : 0.030169 + dx2y2 : 0.006282 + dxy : 0.007928 + f0 : 0.002272 f : 0.010437 + f+1 : 0.002864 + f-1 : 0.002589 + f+2 : 0.000678 + f-2 : 0.001025 + f+3 : 0.000533 + f-3 : 0.000476 + 3 H s : 0.633578 s : 0.633578 + pz : 0.009208 p : 0.081405 + px : 0.023910 + py : 0.048287 + dz2 : -0.000314 d : 0.019458 + dxz : 0.010462 + dyz : 0.009253 + dx2y2 : 0.000199 + dxy : -0.000141 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.622295 0.000000 + 1 N : -0.319272 -0.000000 + 2 O : 0.267846 -0.000000 + 3 H : -0.570869 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.120299 s : 3.120299 + pz : 1.273323 p : 3.837397 + px : 1.188129 + py : 1.375944 + dz2 : 0.082877 d : 0.324298 + dxz : 0.079046 + dyz : 0.010718 + dx2y2 : 0.098630 + dxy : 0.053027 + f0 : 0.019143 f : 0.095711 + f+1 : 0.016630 + f-1 : 0.001894 + f+2 : 0.017899 + f-2 : 0.003626 + f+3 : 0.019881 + f-3 : 0.016639 + 1 N s : 3.006717 s : 3.006717 + pz : 1.204580 p : 2.882009 + px : 0.923589 + py : 0.753840 + dz2 : 0.284804 d : 0.982295 + dxz : 0.306427 + dyz : 0.111045 + dx2y2 : 0.153553 + dxy : 0.126467 + f0 : 0.107594 f : 0.448251 + f+1 : 0.134712 + f-1 : 0.062571 + f+2 : 0.046807 + f-2 : 0.009158 + f+3 : 0.037291 + f-3 : 0.050119 + 2 O s : 3.316909 s : 3.316909 + pz : 1.396324 p : 3.931874 + px : 1.463145 + py : 1.072405 + dz2 : 0.158317 d : 0.356595 + dxz : 0.101514 + dyz : 0.060824 + dx2y2 : 0.021150 + dxy : 0.014791 + f0 : 0.049282 f : 0.126776 + f+1 : 0.033104 + f-1 : 0.025313 + f+2 : 0.010504 + f-2 : 0.006357 + f+3 : 0.001326 + f-3 : 0.000889 + 3 H s : 0.623609 s : 0.623609 + pz : 0.267400 p : 0.562214 + px : 0.132263 + py : 0.162551 + dz2 : 0.131611 d : 0.385045 + dxz : 0.115207 + dyz : 0.116162 + dx2y2 : 0.017631 + dxy : 0.004434 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2545 8.0000 -0.2545 2.3137 1.8527 0.4610 + 1 N 6.8464 7.0000 0.1536 2.8246 2.3501 0.4745 + 2 O 8.1646 8.0000 -0.1646 2.1271 1.6311 0.4960 + 3 H 0.7344 1.0000 0.2656 0.9589 0.8890 0.0699 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8623 B( 0-O , 3-H ) : 0.8904 B( 1-N , 2-O ) : 1.5102 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 86.050 sec + +Fock Matrix Formation ... 0.704 sec ( 0.8%) +Initial Guess ... 0.167 sec ( 0.2%) +DIIS Solver ... 3.015 sec ( 3.5%) +State Vector Update ... 0.155 sec ( 0.2%) +Sigma-vector construction ... 54.301 sec ( 63.1%) + <0|H|D> ... 0.007 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.026 sec ( 0.0% of sigma) + (0-ext) ... 0.077 sec ( 0.1% of sigma) + (2-ext Fock) ... 0.029 sec ( 0.1% of sigma) + (2-ext) ... 1.035 sec ( 1.9% of sigma) + (4-ext) ... 31.234 sec ( 57.5% of sigma) + ... 2.935 sec ( 5.4% of sigma) + ... 0.004 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.147 sec ( 0.3% of sigma) + Fock-dressing ... 3.681 sec ( 6.8% of sigma) + (ik|jl)-dressing ... 0.091 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 12.173 sec ( 22.4% of sigma) + Pair energies ... 0.022 sec ( 0.0% of sigma) +Total Time for computing (T) ... 14.969 sec ( 17.4% of ALL) + I/O of integral and amplitudes ... 2.234 sec ( 14.9% of (T)) + External N**7 contributions ... 8.435 sec ( 56.4% of (T)) + Internal N**7 contributions ... 0.904 sec ( 6.0% of (T)) + N**6 triples energy contributions ... 3.235 sec ( 21.6% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.452247985410 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.000051550 0.000004948 -0.000016711 + 2 N : 0.000054303 -0.000005621 -0.000015296 + 3 O : -0.000018915 0.000002069 0.000034037 + 4 H : 0.000016163 -0.000001395 -0.000002031 + +Norm of the cartesian gradient ... 0.000089238 +RMS gradient ... 0.000025761 +MAX gradient ... 0.000054303 + +------- +TIMINGS +------- + +Total numerical gradient time ... 528.077 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 565.78 cm**-1 + 7: 617.77 cm**-1 + 8: 814.72 cm**-1 + 9: 1306.40 cm**-1 + 10: 1714.74 cm**-1 + 11: 3744.62 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 -0.005371 -0.535620 0.202137 0.048403 0.101976 0.005949 + 1 -0.055619 0.056537 -0.016290 -0.002680 -0.008257 -0.002027 + 2 0.001508 0.333255 0.087656 0.073588 0.042383 -0.062503 + 3 -0.006148 0.111307 -0.522105 -0.043677 0.026578 -0.000296 + 4 -0.069160 -0.016096 0.045278 0.003950 -0.017059 -0.000059 + 5 0.001469 -0.275133 -0.084480 0.000197 -0.630313 -0.001762 + 6 0.005084 0.413941 0.206004 0.052018 -0.089936 -0.000361 + 7 0.053782 -0.040526 -0.019141 -0.006392 0.020051 0.000101 + 8 -0.001316 -0.118703 -0.022106 -0.072737 0.512258 0.001424 + 9 0.089993 0.384588 0.777066 -0.986950 -0.560425 -0.084575 + 10 0.990193 -0.030461 -0.066808 0.089111 0.049852 0.031386 + 11 -0.023468 0.417845 0.133506 -0.016239 -0.044545 0.993937 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 565.78 0.019417 98.13 0.010710 ( 0.009525 0.103015 -0.002617) + 7: 617.77 0.024144 122.01 0.012196 ( 0.094879 -0.010065 -0.055614) + 8: 814.72 0.027645 139.71 0.010589 (-0.087521 0.009180 0.053336) + 9: 1306.40 0.031501 159.19 0.007525 (-0.081318 0.008054 0.029107) + 10: 1714.74 0.022950 115.98 0.004177 ( 0.045344 -0.005166 -0.045760) + 11: 3744.62 0.014377 72.66 0.001198 (-0.015618 0.002158 0.030815) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 565.78 E(vib) ... 0.11 +freq. 617.77 E(vib) ... 0.09 +freq. 814.72 E(vib) ... 0.05 +freq. 1306.40 E(vib) ... 0.01 +freq. 1714.74 E(vib) ... 0.00 +freq. 3744.62 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.45224799 Eh +Zero point energy ... 0.01996592 Eh 12.53 kcal/mol +Thermal vibrational correction ... 0.00041743 Eh 0.26 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42903209 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00324998 Eh 2.04 kcal/mol +Non-thermal (ZPE) correction 0.01996592 Eh 12.53 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02321589 Eh 14.57 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42903209 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.42808788 Eh + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: Cs, Symmetry Number: 1 +Rotational constants in cm-1: 3.083601 0.418783 0.368709 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00055148 Eh 0.35 kcal/mol +Rotational entropy ... 0.00986113 Eh 6.19 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02821492 Eh 17.71 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00986113 Eh 6.19 kcal/mol| +| sn= 2 | S(rot)= 0.00920667 Eh 5.78 kcal/mol| +| sn= 3 | S(rot)= 0.00882384 Eh 5.54 kcal/mol| +| sn= 4 | S(rot)= 0.00855221 Eh 5.37 kcal/mol| +| sn= 5 | S(rot)= 0.00834153 Eh 5.23 kcal/mol| +| sn= 6 | S(rot)= 0.00816938 Eh 5.13 kcal/mol| +| sn= 7 | S(rot)= 0.00802384 Eh 5.04 kcal/mol| +| sn= 8 | S(rot)= 0.00789776 Eh 4.96 kcal/mol| +| sn= 9 | S(rot)= 0.00778655 Eh 4.89 kcal/mol| +| sn=10 | S(rot)= 0.00768707 Eh 4.82 kcal/mol| +| sn=11 | S(rot)= 0.00759708 Eh 4.77 kcal/mol| +| sn=12 | S(rot)= 0.00751493 Eh 4.72 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.42808788 Eh +Total entropy correction ... -0.02821492 Eh -17.71 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.45630281 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00405482 Eh -2.54 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.452247985 Eh +Current gradient norm .... 0.000089238 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.033501849 0.136018999 0.189728312 0.495633776 0.529047339 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999935 +Lowest eigenvalues of augmented Hessian: + -0.000000020 0.136019016 0.189728312 0.495633765 0.529047299 +Length of the computed step .... 0.000360941 +The final length of the internal step .... 0.000360941 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0001473535 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0000746299 RMS(Int)= 0.0001473539 + Iter 1: RMS(Cart)= 0.0000000069 RMS(Int)= 0.0000000113 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0000260715 0.0001000000 YES + MAX gradient 0.0000368909 0.0003000000 YES + RMS step 0.0001473535 0.0020000000 YES + MAX step 0.0002898846 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0002 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4322 0.000032 -0.0002 1.4320 + 2. B(O 2,N 1) 1.1739 -0.000037 0.0000 1.1740 + 3. B(H 3,O 0) 0.9689 -0.000003 0.0000 0.9689 + 4. A(N 1,O 0,H 3) 101.99 -0.000031 0.01 102.00 + 5. A(O 0,N 1,O 2) 110.58 -0.000027 0.00 110.59 + 6. D(O 2,N 1,O 0,H 3) -180.00 -0.000000 -0.00 -180.00 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 1 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.754460 0.071445 0.135025 + N 0.659850 -0.060825 -0.046608 + O 0.926369 -0.111489 -1.188807 + H -0.831758 0.100869 1.100389 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.425724 0.135012 0.255161 + 1 N 7.0000 0 14.007 1.246937 -0.114943 -0.088075 + 2 O 8.0000 0 15.999 1.750583 -0.210684 -2.246520 + 3 H 1.0000 0 1.008 -1.571795 0.190615 2.079434 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.432047900131 0.00000000 0.00000000 + O 2 1 0 1.173975680938 110.58507065 0.00000000 + H 1 2 3 0.968900289541 102.00323747 180.00000000 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.706178341905 0.00000000 0.00000000 + O 2 1 0 2.218492524857 110.58507065 0.00000000 + H 1 2 3 1.830956198309 102.00323747 180.00000000 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2692 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.500750606749 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.5007506067 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.972e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7235809867 0.000000000000 0.00000518 0.00000013 0.0000295 0.7000 + 1 -204.7235809912 -0.000000004518 0.00000428 0.00000011 0.0000234 0.7000 + ***Turning on DIIS*** + 2 -204.7235809949 -0.000000003739 0.00001114 0.00000029 0.0000184 0.0000 + 3 -204.7235840088 -0.000003013839 0.00000399 0.00000013 0.0000052 0.0000 + 4 -204.7235800304 0.000003978413 0.00000153 0.00000004 0.0000015 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72358091 Eh -5570.81185 eV + +Components: +Nuclear Repulsion : 69.50075061 Eh 1891.21157 eV +Electronic Energy : -274.22433152 Eh -7462.02342 eV +One Electron Energy: -418.70371393 Eh -11393.50729 eV +Two Electron Energy: 144.47938241 Eh 3931.48387 eV + +Virial components: +Potential Energy : -408.97172395 Eh -11128.68638 eV +Kinetic Energy : 204.24814304 Eh 5557.87453 eV +Virial Ratio : 2.00232775 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -8.8250e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.1271e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.3133e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.6675e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.666339 -562.3597 + 1 1.0000 -20.640664 -561.6610 + 2 1.0000 -15.799017 -429.9131 + 3 1.0000 -1.604926 -43.6722 + 4 1.0000 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2.133041 58.0430 + 79 0.0000 2.186644 59.5016 + 80 0.0000 2.270903 61.7944 + 81 0.0000 2.309574 62.8467 + 82 0.0000 2.328855 63.3714 + 83 0.0000 2.381919 64.8153 + 84 0.0000 2.450760 66.6886 + 85 0.0000 2.468719 67.1772 + 86 0.0000 2.499710 68.0206 + 87 0.0000 2.502266 68.0901 + 88 0.0000 2.522200 68.6326 + 89 0.0000 2.543843 69.2215 + 90 0.0000 2.569324 69.9148 + 91 0.0000 2.607703 70.9592 + 92 0.0000 2.608579 70.9830 + 93 0.0000 2.663981 72.4906 + 94 0.0000 2.772390 75.4406 + 95 0.0000 2.779699 75.6395 + 96 0.0000 2.835487 77.1575 + 97 0.0000 2.938176 79.9518 + 98 0.0000 2.946870 80.1884 + 99 0.0000 3.113868 84.7327 + 100 0.0000 3.148670 85.6797 + 101 0.0000 3.183685 86.6325 + 102 0.0000 3.247006 88.3555 + 103 0.0000 3.457522 94.0840 + 104 0.0000 3.833988 104.3281 + 105 0.0000 3.852477 104.8312 + 106 0.0000 4.030603 109.6783 + 107 0.0000 4.172714 113.5453 + 108 0.0000 4.186311 113.9153 + 109 0.0000 4.212904 114.6390 + 110 0.0000 4.368030 118.8601 + 111 0.0000 4.373794 119.0170 + 112 0.0000 4.579755 124.6215 + 113 0.0000 4.634495 126.1110 + 114 0.0000 4.750140 129.2579 + 115 0.0000 4.814755 131.0161 + 116 0.0000 4.871992 132.5737 + 117 0.0000 4.887358 132.9918 + 118 0.0000 4.984512 135.6355 + 119 0.0000 5.001490 136.0975 + 120 0.0000 5.073946 138.0691 + 121 0.0000 5.089797 138.5004 + 122 0.0000 5.169988 140.6825 + 123 0.0000 5.248388 142.8159 + 124 0.0000 5.256910 143.0478 + 125 0.0000 5.336123 145.2033 + 126 0.0000 5.369059 146.0995 + 127 0.0000 5.374962 146.2602 + 128 0.0000 5.575005 151.7036 + 129 0.0000 5.672036 154.3440 + 130 0.0000 5.796836 157.7399 + 131 0.0000 5.992232 163.0569 + 132 0.0000 6.111689 166.3075 + 133 0.0000 6.433938 175.0764 + 134 0.0000 6.506462 177.0498 + 135 0.0000 6.509691 177.1377 + 136 0.0000 6.674500 181.6224 + 137 0.0000 6.716543 182.7664 + 138 0.0000 6.744872 183.5373 + 139 0.0000 6.848288 186.3514 + 140 0.0000 6.915196 188.1721 + 141 0.0000 7.070746 192.4048 + 142 0.0000 7.119687 193.7365 + 143 0.0000 7.183325 195.4682 + 144 0.0000 7.233828 196.8425 + 145 0.0000 7.256454 197.4582 + 146 0.0000 7.259750 197.5478 + 147 0.0000 7.337689 199.6687 + 148 0.0000 7.383194 200.9069 + 149 0.0000 7.432719 202.2546 + 150 0.0000 7.478340 203.4960 + 151 0.0000 7.611059 207.1074 + 152 0.0000 7.647592 208.1016 + 153 0.0000 7.701994 209.5819 + 154 0.0000 7.788493 211.9357 + 155 0.0000 7.976034 217.0389 + 156 0.0000 8.069729 219.5885 + 157 0.0000 8.427344 229.3197 + 158 0.0000 14.212818 386.7505 + 159 0.0000 15.131450 411.7477 + 160 0.0000 16.045145 436.6106 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.343716 0.000000 + 1 N : 0.343802 0.000000 + 2 O : -0.278354 0.000000 + 3 H : 0.278268 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.866599 s : 3.866599 + pz : 1.377113 p : 4.448580 + px : 1.239919 + py : 1.831548 + dz2 : 0.012066 d : 0.023874 + dxz : -0.002952 + dyz : 0.000805 + dx2y2 : 0.006040 + dxy : 0.007914 + f0 : 0.000572 f : 0.004662 + f+1 : 0.001056 + f-1 : 0.000067 + f+2 : 0.000668 + f-2 : -0.000149 + f+3 : 0.001048 + f-3 : 0.001399 + 1 N s : 3.829949 s : 3.829949 + pz : 1.084861 p : 2.651249 + px : 0.833284 + py : 0.733104 + dz2 : 0.031705 d : 0.145304 + dxz : 0.035178 + dyz : 0.032313 + dx2y2 : 0.023837 + dxy : 0.022271 + f0 : 0.005277 f : 0.029697 + f+1 : 0.009176 + f-1 : 0.005949 + f+2 : 0.002046 + f-2 : 0.000323 + f+3 : 0.001900 + f-3 : 0.005025 + 2 O s : 3.876841 s : 3.876841 + pz : 1.202283 p : 4.330239 + px : 1.858958 + py : 1.268997 + dz2 : 0.013916 d : 0.063425 + dxz : 0.017251 + dyz : 0.030663 + dx2y2 : -0.000131 + dxy : 0.001726 + f0 : 0.002181 f : 0.007849 + f+1 : 0.002450 + f-1 : 0.002845 + f+2 : 0.000049 + f-2 : 0.000465 + f+3 : -0.000044 + f-3 : -0.000098 + 3 H s : 0.621480 s : 0.621480 + pz : 0.015375 p : 0.077557 + px : 0.020131 + py : 0.042051 + dz2 : 0.000761 d : 0.022695 + dxz : 0.011652 + dyz : 0.011012 + dx2y2 : -0.000335 + dxy : -0.000395 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.605123 0.000000 + 1 N : -0.268816 0.000000 + 2 O : 0.234751 0.000000 + 3 H : -0.571058 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.112768 s : 3.112768 + pz : 1.284560 p : 3.900196 + px : 1.179165 + py : 1.436471 + dz2 : 0.076018 d : 0.293131 + dxz : 0.074002 + dyz : 0.005079 + dx2y2 : 0.091903 + dxy : 0.046129 + f0 : 0.018120 f : 0.088782 + f+1 : 0.015797 + f-1 : 0.001082 + f+2 : 0.017670 + f-2 : 0.003189 + f+3 : 0.018555 + f-3 : 0.014369 + 1 N s : 3.001470 s : 3.001470 + pz : 1.235291 p : 2.833156 + px : 0.913057 + py : 0.684808 + dz2 : 0.278635 d : 0.973658 + dxz : 0.309468 + dyz : 0.114142 + dx2y2 : 0.146099 + dxy : 0.125314 + f0 : 0.110558 f : 0.460532 + f+1 : 0.137899 + f-1 : 0.063181 + f+2 : 0.048945 + f-2 : 0.008780 + f+3 : 0.036400 + f-3 : 0.054769 + 2 O s : 3.315136 s : 3.315136 + pz : 1.405478 p : 4.007165 + px : 1.515086 + py : 1.086600 + dz2 : 0.154338 d : 0.324879 + dxz : 0.098589 + dyz : 0.048599 + dx2y2 : 0.015523 + dxy : 0.007830 + f0 : 0.049577 f : 0.118069 + f+1 : 0.032067 + f-1 : 0.020262 + f+2 : 0.010219 + f-2 : 0.004861 + f+3 : 0.000782 + f-3 : 0.000301 + 3 H s : 0.621319 s : 0.621319 + pz : 0.264543 p : 0.554247 + px : 0.131268 + py : 0.158436 + dz2 : 0.131779 d : 0.395491 + dxz : 0.119119 + dyz : 0.123715 + dx2y2 : 0.017316 + dxy : 0.003562 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3437 8.0000 -0.3437 1.9473 1.9473 -0.0000 + 1 N 6.6562 7.0000 0.3438 2.5335 2.5335 -0.0000 + 2 O 8.2784 8.0000 -0.2784 1.7239 1.7239 0.0000 + 3 H 0.7217 1.0000 0.2783 0.9374 0.9374 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.9269 B( 0-O , 3-H ) : 0.9638 B( 1-N , 2-O ) : 1.6501 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.911 sec +Sum of individual times .... 0.759 sec ( 83.4%) + +Fock matrix formation .... 0.623 sec ( 68.4%) +Diagonalization .... 0.065 sec ( 7.1%) +Density matrix formation .... 0.005 sec ( 0.5%) +Population analysis .... 0.012 sec ( 1.3%) +Initial guess .... 0.009 sec ( 1.0%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.5%) +DIIS solution .... 0.045 sec ( 5.0%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.202 sec +Reference energy ... -204.723581007 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.370 sec +AO-integral generation ... 0.143 sec +Half transformation ... 0.079 sec +K-integral sorting ... 5.379 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.026 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.032 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.035 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.040 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.029 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.375 sec +AO-integral generation ... 0.263 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.053 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.146 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.249 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090623631 +EMP2(bb)= -0.090623631 +EMP2(ab)= -0.516507263 + +Initial guess performed in 0.133 sec +E(0) ... -204.723581007 +E(MP2) ... -0.697754524 +Initial E(tot) ... -205.421335531 + ... 0.187986245 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.421335531 -0.697754524 -0.000000000 0.027389609 2.69 0.000000801 + *** Turning on DIIS *** + 1 -205.391994183 -0.668413176 0.029341348 0.012035892 2.70 0.058109339 + 2 -205.411498778 -0.687917771 -0.019504595 0.006059982 2.88 0.060999000 + 3 -205.415188928 -0.691607922 -0.003690150 0.002488042 2.84 0.075432328 + 4 -205.416757299 -0.693176292 -0.001568370 0.001608921 2.81 0.082314094 + 5 -205.417316054 -0.693735048 -0.000558756 0.000849631 2.89 0.088068025 + 6 -205.417427602 -0.693846596 -0.000111548 0.000498456 2.78 0.090866643 + 7 -205.417471358 -0.693890351 -0.000043755 0.000190408 2.82 0.092078574 + 8 -205.417482832 -0.693901826 -0.000011475 0.000098388 2.89 0.092509566 + 9 -205.417478742 -0.693897735 0.000004091 0.000025370 2.77 0.092632704 + 10 -205.417482974 -0.693901967 -0.000004232 0.000008817 2.72 0.092665947 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.723581007 +E(CORR) ... -0.693901967 +E(TOT) ... -205.417482974 +Singles norm **1/2 ... 0.092665947 ( 0.046332973, 0.046332973) +T1 diagnostic ... 0.021841573 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.066636 + 10a-> 13a 10b-> 13b 0.054311 + 8b-> 13b -1b-> -1b 0.045596 + 8a-> 13a -1a-> -1a 0.045596 + 8a-> 13a 10b-> 13b 0.037000 + 10a-> 13a 8b-> 13b 0.037000 + 10a-> 13a -1a-> -1a 0.033121 + 10b-> 13b -1b-> -1b 0.033121 + 11a-> 26a 11b-> 26b 0.031625 + 11a-> 26a -1a-> -1a 0.030149 + 11b-> 26b -1b-> -1b 0.030149 + 11a-> 13a 11b-> 13b 0.027962 + 5a-> 13a 5b-> 13b 0.025408 + 11a-> 26a 10b-> 13b 0.025159 + 10a-> 13a 11b-> 26b 0.025159 + 8a-> 22a 8b-> 13b 0.024596 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034765020 + alpha-alpha-alpha ... -0.000901649 ( 2.6%) + alpha-alpha-beta ... -0.016480861 ( 47.4%) + alpha-beta -beta ... -0.016480861 ( 47.4%) + beta -beta -beta ... -0.000901649 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034765020 + +Final correlation energy ... -0.728666987 +E(CCSD) ... -205.417482974 +E(CCSD(T)) ... -205.452247993 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209480134 sqrt= 1.099763672 +W(HF) = 0.826801509 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.254444 0.000000 + 1 N : 0.153533 -0.000000 + 2 O : -0.164645 0.000000 + 3 H : 0.265555 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.846917 s : 3.846917 + pz : 1.359677 p : 4.342788 + px : 1.236680 + py : 1.746430 + dz2 : 0.016491 d : 0.056259 + dxz : 0.005370 + dyz : 0.007895 + dx2y2 : 0.011212 + dxy : 0.015291 + f0 : 0.001289 f : 0.008479 + f+1 : 0.001496 + f-1 : 0.000695 + f+2 : 0.001209 + f-2 : 0.000533 + f+3 : 0.001313 + f-3 : 0.001944 + 1 N s : 3.879609 s : 3.879609 + pz : 1.048977 p : 2.762266 + px : 0.868729 + py : 0.844560 + dz2 : 0.036069 d : 0.175448 + dxz : 0.046689 + dyz : 0.032279 + dx2y2 : 0.029168 + dxy : 0.031242 + f0 : 0.004858 f : 0.029144 + f+1 : 0.008884 + f-1 : 0.004747 + f+2 : 0.002509 + f-2 : 0.000948 + f+3 : 0.002041 + f-3 : 0.005156 + 2 O s : 3.866804 s : 3.866804 + pz : 1.190883 p : 4.202181 + px : 1.777749 + py : 1.233549 + dz2 : 0.016619 d : 0.085223 + dxz : 0.024227 + dyz : 0.030166 + dx2y2 : 0.006282 + dxy : 0.007928 + f0 : 0.002272 f : 0.010437 + f+1 : 0.002863 + f-1 : 0.002589 + f+2 : 0.000678 + f-2 : 0.001025 + f+3 : 0.000533 + f-3 : 0.000476 + 3 H s : 0.633576 s : 0.633576 + pz : 0.009210 p : 0.081406 + px : 0.023914 + py : 0.048282 + dz2 : -0.000313 d : 0.019462 + dxz : 0.010464 + dyz : 0.009253 + dx2y2 : 0.000199 + dxy : -0.000140 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.622312 0.000000 + 1 N : -0.319362 -0.000000 + 2 O : 0.267821 -0.000000 + 3 H : -0.570771 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.120232 s : 3.120232 + pz : 1.273306 p : 3.837341 + px : 1.188152 + py : 1.375883 + dz2 : 0.082888 d : 0.324376 + dxz : 0.079079 + dyz : 0.010720 + dx2y2 : 0.098643 + dxy : 0.053045 + f0 : 0.019146 f : 0.095739 + f+1 : 0.016635 + f-1 : 0.001895 + f+2 : 0.017907 + f-2 : 0.003628 + f+3 : 0.019884 + f-3 : 0.016645 + 1 N s : 3.006671 s : 3.006671 + pz : 1.204533 p : 2.882023 + px : 0.923652 + py : 0.753839 + dz2 : 0.284810 d : 0.982381 + dxz : 0.306456 + dyz : 0.111049 + dx2y2 : 0.153570 + dxy : 0.126496 + f0 : 0.107598 f : 0.448286 + f+1 : 0.134712 + f-1 : 0.062572 + f+2 : 0.046817 + f-2 : 0.009159 + f+3 : 0.037296 + f-3 : 0.050132 + 2 O s : 3.316927 s : 3.316927 + pz : 1.396289 p : 3.931908 + px : 1.463198 + py : 1.072421 + dz2 : 0.158306 d : 0.356573 + dxz : 0.101506 + dyz : 0.060819 + dx2y2 : 0.021149 + dxy : 0.014792 + f0 : 0.049278 f : 0.126772 + f+1 : 0.033103 + f-1 : 0.025310 + f+2 : 0.010506 + f-2 : 0.006359 + f+3 : 0.001327 + f-3 : 0.000889 + 3 H s : 0.623594 s : 0.623594 + pz : 0.267389 p : 0.562163 + px : 0.132242 + py : 0.162531 + dz2 : 0.131606 d : 0.385014 + dxz : 0.115188 + dyz : 0.116152 + dx2y2 : 0.017631 + dxy : 0.004438 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2544 8.0000 -0.2544 2.3137 1.8527 0.4610 + 1 N 6.8465 7.0000 0.1535 2.8246 2.3500 0.4745 + 2 O 8.1646 8.0000 -0.1646 2.1270 1.6310 0.4960 + 3 H 0.7344 1.0000 0.2656 0.9589 0.8890 0.0699 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8624 B( 0-O , 3-H ) : 0.8904 B( 1-N , 2-O ) : 1.5101 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 45.796 sec + +Fock Matrix Formation ... 0.202 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.3%) +DIIS Solver ... 1.430 sec ( 3.1%) +State Vector Update ... 0.070 sec ( 0.2%) +Sigma-vector construction ... 29.305 sec ( 64.0%) + <0|H|D> ... 0.003 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (0-ext) ... 0.057 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (2-ext) ... 0.739 sec ( 2.5% of sigma) + (4-ext) ... 15.866 sec ( 54.1% of sigma) + ... 1.081 sec ( 3.7% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.086 sec ( 0.3% of sigma) + Fock-dressing ... 1.654 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.060 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 7.638 sec ( 26.1% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.851 sec ( 15.0% of ALL) + I/O of integral and amplitudes ... 0.814 sec ( 11.9% of (T)) + External N**7 contributions ... 3.920 sec ( 57.2% of (T)) + Internal N**7 contributions ... 0.316 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.725 sec ( 25.2% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.452247993461 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.001.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.001.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.448363, -0.055911 -0.659336) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.86729 -0.08968 -0.48010 +Nuclear contribution : -1.00508 0.12250 1.35609 + ----------------------------------------- +Total Dipole Moment : -0.13779 0.03283 0.87599 + ----------------------------------------- +Magnitude (a.u.) : 0.88737 +Magnitude (Debye) : 2.25551 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.084008 0.418807 0.368733 +Rotational constants in MHz : 92456.236174 12555.512036 11054.338261 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.646134 0.608223 0.000000 +x,y,z [Debye]: -1.642343 1.545980 0.000000 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.448363, -0.055911 -0.659336) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.84284 -0.09159 -0.65771 +Nuclear contribution : -1.00508 0.12250 1.35609 + ----------------------------------------- +Total Dipole Moment : -0.16223 0.03091 0.69839 + ----------------------------------------- +Magnitude (a.u.) : 0.71765 +Magnitude (Debye) : 1.82412 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.084008 0.418807 0.368733 +Rotational constants in MHz : 92456.236174 12555.512036 11054.338261 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.556779 0.452788 0.000000 +x,y,z [Debye]: -1.415220 1.150895 0.000000 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 2 * + * * + * Dihedral ( 2, 1, 0, 3) : -171.81818182 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0395707886 RMS(Int)= 0.0002469552 + Iter 1: RMS(Cart)= 0.0000684330 RMS(Int)= 0.0000012807 + Iter 2: RMS(Cart)= 0.0000003549 RMS(Int)= 0.0000000067 + Iter 3: RMS(Cart)= 0.0000000018 RMS(Int)= 0.0000000000 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4321 0.000000 + 2. B(O 2,N 1) 1.1761 0.000000 + 3. B(H 3,O 0) 0.9717 0.000000 + 4. A(N 1,O 0,H 3) 101.9776 0.000000 + 5. A(O 0,N 1,O 2) 110.5375 0.000000 + 6. D(O 2,N 1,O 0,H 3) -171.8182 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.757593 0.036849 0.135829 + N 0.656444 -0.098447 -0.045734 + O 0.929396 -0.078049 -1.189584 + H -0.828247 0.139648 1.099488 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.431643 0.069634 0.256680 + 1 N 7.0000 0 14.007 1.240500 -0.186039 -0.086424 + 2 O 8.0000 0 15.999 1.756305 -0.147492 -2.247988 + 3 H 1.0000 0 1.008 -1.565160 0.263896 2.077732 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.432047900131 0.00000000 0.00000000 + O 2 1 0 1.173975680938 110.58507065 0.00000000 + H 1 2 3 0.968900289541 102.00323747 180.00000085 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.706178341905 0.00000000 0.00000000 + O 2 1 0 2.218492524857 110.58507065 0.00000000 + H 1 2 3 1.830956198309 102.00323747 180.00000085 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2692 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.432001718131 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.4320017181 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.978e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7183939568 0.000000000000 0.00184870 0.00005272 0.0197431 0.7000 + 1 -204.7192940277 -0.000900070899 0.00175158 0.00004754 0.0163415 0.7000 + ***Turning on DIIS*** + 2 -204.7200603635 -0.000766335805 0.00476320 0.00012838 0.0132771 0.0000 + 3 -204.7238006956 -0.003740332057 0.00195303 0.00005155 0.0053369 0.0000 + 4 -204.7218493936 0.001951301966 0.00088208 0.00002260 0.0021084 0.0000 + 5 -204.7233688951 -0.001519501530 0.00058405 0.00001714 0.0010279 0.0000 + 6 -204.7226921366 0.000676758568 0.00061461 0.00002021 0.0006000 0.0000 + 7 -204.7223427306 0.000349405928 0.00032297 0.00001066 0.0002643 0.0000 + 8 -204.7230491240 -0.000706393410 0.00017641 0.00000665 0.0001916 0.0000 + 9 -204.7226528304 0.000396293647 0.00014447 0.00000464 0.0001278 0.0000 + 10 -204.7227816963 -0.000128865904 0.00006836 0.00000195 0.0000573 0.0000 + 11 -204.7228971799 -0.000115483640 0.00002940 0.00000078 0.0000229 0.0000 + 12 -204.7228040921 0.000093087882 0.00000745 0.00000019 0.0000070 0.0000 + 13 -204.7228273788 -0.000023286737 0.00000189 0.00000005 0.0000023 0.0000 + 14 -204.7228198430 0.000007535763 0.00000074 0.00000002 0.0000013 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 15 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72282153 Eh -5570.79119 eV + +Components: +Nuclear Repulsion : 69.43200172 Eh 1889.34082 eV +Electronic Energy : -274.15482325 Eh -7460.13201 eV +One Electron Energy: -418.57375879 Eh -11389.97103 eV +Two Electron Energy: 144.41893554 Eh 3929.83903 eV + +Virial components: +Potential Energy : -408.95676386 Eh -11128.27930 eV +Kinetic Energy : 204.23394232 Eh 5557.48811 eV +Virial Ratio : 2.00239372 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.6914e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.1464e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.3927e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.8983e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.666426 -562.3620 + 1 1.0000 -20.641103 -561.6730 + 2 1.0000 -15.799208 -429.9183 + 3 1.0000 -1.603161 -43.6242 + 4 1.0000 -1.400441 -38.1079 + 5 1.0000 -0.948595 -25.8126 + 6 1.0000 -0.783308 -21.3149 + 7 1.0000 -0.729377 -19.8474 + 8 1.0000 -0.681783 -18.5523 + 9 1.0000 -0.624414 -16.9912 + 10 1.0000 -0.528444 -14.3797 + 11 1.0000 -0.461685 -12.5631 + 12 0.0000 0.028086 0.7643 + 13 0.0000 0.079982 2.1764 + 14 0.0000 0.093867 2.5543 + 15 0.0000 0.097686 2.6582 + 16 0.0000 0.128434 3.4949 + 17 0.0000 0.144101 3.9212 + 18 0.0000 0.156884 4.2690 + 19 0.0000 0.172169 4.6850 + 20 0.0000 0.187233 5.0949 + 21 0.0000 0.196531 5.3479 + 22 0.0000 0.205373 5.5885 + 23 0.0000 0.233494 6.3537 + 24 0.0000 0.258470 7.0333 + 25 0.0000 0.295700 8.0464 + 26 0.0000 0.307228 8.3601 + 27 0.0000 0.329733 8.9725 + 28 0.0000 0.364708 9.9242 + 29 0.0000 0.381257 10.3745 + 30 0.0000 0.423668 11.5286 + 31 0.0000 0.520783 14.1712 + 32 0.0000 0.529111 14.3979 + 33 0.0000 0.547686 14.9033 + 34 0.0000 0.572116 15.5681 + 35 0.0000 0.613573 16.6962 + 36 0.0000 0.631551 17.1854 + 37 0.0000 0.647936 17.6312 + 38 0.0000 0.681943 18.5566 + 39 0.0000 0.715468 19.4689 + 40 0.0000 0.717897 19.5350 + 41 0.0000 0.747740 20.3470 + 42 0.0000 0.773896 21.0588 + 43 0.0000 0.783319 21.3152 + 44 0.0000 0.808845 22.0098 + 45 0.0000 0.814348 22.1595 + 46 0.0000 0.860299 23.4099 + 47 0.0000 0.876505 23.8509 + 48 0.0000 0.926108 25.2007 + 49 0.0000 0.938555 25.5394 + 50 0.0000 0.946825 25.7644 + 51 0.0000 0.996426 27.1141 + 52 0.0000 1.047865 28.5139 + 53 0.0000 1.061455 28.8837 + 54 0.0000 1.077248 29.3134 + 55 0.0000 1.103792 30.0357 + 56 0.0000 1.160484 31.5784 + 57 0.0000 1.194313 32.4989 + 58 0.0000 1.252052 34.0701 + 59 0.0000 1.273395 34.6508 + 60 0.0000 1.363619 37.1060 + 61 0.0000 1.431180 38.9444 + 62 0.0000 1.491102 40.5749 + 63 0.0000 1.521302 41.3967 + 64 0.0000 1.525052 41.4988 + 65 0.0000 1.546439 42.0807 + 66 0.0000 1.553006 42.2595 + 67 0.0000 1.606662 43.7195 + 68 0.0000 1.660321 45.1796 + 69 0.0000 1.729181 47.0534 + 70 0.0000 1.755468 47.7687 + 71 0.0000 1.820019 49.5252 + 72 0.0000 1.857077 50.5336 + 73 0.0000 1.959805 53.3290 + 74 0.0000 1.969076 53.5813 + 75 0.0000 2.001325 54.4588 + 76 0.0000 2.075165 56.4681 + 77 0.0000 2.116734 57.5993 + 78 0.0000 2.148160 58.4544 + 79 0.0000 2.181486 59.3613 + 80 0.0000 2.275362 61.9158 + 81 0.0000 2.307112 62.7797 + 82 0.0000 2.327074 63.3229 + 83 0.0000 2.379796 64.7575 + 84 0.0000 2.449285 66.6484 + 85 0.0000 2.469078 67.1870 + 86 0.0000 2.498402 67.9850 + 87 0.0000 2.502527 68.0972 + 88 0.0000 2.520107 68.5756 + 89 0.0000 2.543341 69.2078 + 90 0.0000 2.568987 69.9057 + 91 0.0000 2.602706 70.8232 + 92 0.0000 2.620499 71.3074 + 93 0.0000 2.664403 72.5021 + 94 0.0000 2.765479 75.2525 + 95 0.0000 2.773860 75.4806 + 96 0.0000 2.845865 77.4399 + 97 0.0000 2.928618 79.6917 + 98 0.0000 2.948222 80.2252 + 99 0.0000 3.111236 84.6610 + 100 0.0000 3.149795 85.7103 + 101 0.0000 3.183599 86.6301 + 102 0.0000 3.247926 88.3806 + 103 0.0000 3.458028 94.0977 + 104 0.0000 3.816795 103.8603 + 105 0.0000 3.863011 105.1179 + 106 0.0000 4.028803 109.6293 + 107 0.0000 4.171125 113.5021 + 108 0.0000 4.175942 113.6331 + 109 0.0000 4.221079 114.8614 + 110 0.0000 4.363017 118.7237 + 111 0.0000 4.377089 119.1067 + 112 0.0000 4.577248 124.5532 + 113 0.0000 4.627062 125.9088 + 114 0.0000 4.746378 129.1555 + 115 0.0000 4.814963 131.0218 + 116 0.0000 4.862017 132.3022 + 117 0.0000 4.891229 133.0971 + 118 0.0000 4.978063 135.4600 + 119 0.0000 5.002569 136.1268 + 120 0.0000 5.072017 138.0166 + 121 0.0000 5.088341 138.4608 + 122 0.0000 5.167883 140.6252 + 123 0.0000 5.246443 142.7630 + 124 0.0000 5.256399 143.0339 + 125 0.0000 5.329864 145.0330 + 126 0.0000 5.349211 145.5594 + 127 0.0000 5.387184 146.5927 + 128 0.0000 5.575634 151.7207 + 129 0.0000 5.670205 154.2941 + 130 0.0000 5.793712 157.6549 + 131 0.0000 5.991136 163.0271 + 132 0.0000 6.113563 166.3585 + 133 0.0000 6.431237 175.0029 + 134 0.0000 6.507402 177.0754 + 135 0.0000 6.509156 177.1231 + 136 0.0000 6.675653 181.6538 + 137 0.0000 6.714377 182.7075 + 138 0.0000 6.743750 183.5068 + 139 0.0000 6.847165 186.3208 + 140 0.0000 6.914919 188.1645 + 141 0.0000 7.067878 192.3267 + 142 0.0000 7.120596 193.7613 + 143 0.0000 7.176476 195.2818 + 144 0.0000 7.228014 196.6842 + 145 0.0000 7.250571 197.2981 + 146 0.0000 7.257614 197.4897 + 147 0.0000 7.333209 199.5467 + 148 0.0000 7.380038 200.8210 + 149 0.0000 7.433534 202.2767 + 150 0.0000 7.477843 203.4825 + 151 0.0000 7.606588 206.9858 + 152 0.0000 7.644800 208.0256 + 153 0.0000 7.698563 209.4885 + 154 0.0000 7.788230 211.9285 + 155 0.0000 7.970548 216.8896 + 156 0.0000 8.067810 219.5363 + 157 0.0000 8.417965 229.0645 + 158 0.0000 14.177917 385.8007 + 159 0.0000 15.082333 410.4112 + 160 0.0000 15.983299 434.9277 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.666426 -562.3620 + 1 1.0000 -20.641103 -561.6730 + 2 1.0000 -15.799208 -429.9183 + 3 1.0000 -1.603161 -43.6242 + 4 1.0000 -1.400441 -38.1079 + 5 1.0000 -0.948595 -25.8126 + 6 1.0000 -0.783308 -21.3149 + 7 1.0000 -0.729377 -19.8474 + 8 1.0000 -0.681783 -18.5523 + 9 1.0000 -0.624414 -16.9912 + 10 1.0000 -0.528444 -14.3797 + 11 1.0000 -0.461685 -12.5631 + 12 0.0000 0.028086 0.7643 + 13 0.0000 0.079982 2.1764 + 14 0.0000 0.093867 2.5543 + 15 0.0000 0.097686 2.6582 + 16 0.0000 0.128434 3.4949 + 17 0.0000 0.144101 3.9212 + 18 0.0000 0.156884 4.2690 + 19 0.0000 0.172169 4.6850 + 20 0.0000 0.187233 5.0949 + 21 0.0000 0.196531 5.3479 + 22 0.0000 0.205373 5.5885 + 23 0.0000 0.233494 6.3537 + 24 0.0000 0.258470 7.0333 + 25 0.0000 0.295700 8.0464 + 26 0.0000 0.307228 8.3601 + 27 0.0000 0.329733 8.9725 + 28 0.0000 0.364708 9.9242 + 29 0.0000 0.381257 10.3745 + 30 0.0000 0.423668 11.5286 + 31 0.0000 0.520783 14.1712 + 32 0.0000 0.529111 14.3979 + 33 0.0000 0.547686 14.9033 + 34 0.0000 0.572116 15.5681 + 35 0.0000 0.613573 16.6962 + 36 0.0000 0.631551 17.1854 + 37 0.0000 0.647936 17.6312 + 38 0.0000 0.681943 18.5566 + 39 0.0000 0.715468 19.4689 + 40 0.0000 0.717897 19.5350 + 41 0.0000 0.747740 20.3470 + 42 0.0000 0.773896 21.0588 + 43 0.0000 0.783319 21.3152 + 44 0.0000 0.808845 22.0098 + 45 0.0000 0.814348 22.1595 + 46 0.0000 0.860299 23.4099 + 47 0.0000 0.876505 23.8509 + 48 0.0000 0.926108 25.2007 + 49 0.0000 0.938555 25.5394 + 50 0.0000 0.946825 25.7644 + 51 0.0000 0.996426 27.1141 + 52 0.0000 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67.9850 + 87 0.0000 2.502527 68.0972 + 88 0.0000 2.520107 68.5756 + 89 0.0000 2.543341 69.2078 + 90 0.0000 2.568987 69.9057 + 91 0.0000 2.602706 70.8232 + 92 0.0000 2.620499 71.3074 + 93 0.0000 2.664403 72.5021 + 94 0.0000 2.765479 75.2525 + 95 0.0000 2.773860 75.4806 + 96 0.0000 2.845865 77.4399 + 97 0.0000 2.928618 79.6917 + 98 0.0000 2.948222 80.2252 + 99 0.0000 3.111236 84.6610 + 100 0.0000 3.149795 85.7103 + 101 0.0000 3.183599 86.6301 + 102 0.0000 3.247926 88.3806 + 103 0.0000 3.458028 94.0977 + 104 0.0000 3.816795 103.8603 + 105 0.0000 3.863011 105.1179 + 106 0.0000 4.028803 109.6293 + 107 0.0000 4.171125 113.5021 + 108 0.0000 4.175942 113.6331 + 109 0.0000 4.221079 114.8614 + 110 0.0000 4.363017 118.7237 + 111 0.0000 4.377089 119.1067 + 112 0.0000 4.577248 124.5532 + 113 0.0000 4.627062 125.9088 + 114 0.0000 4.746378 129.1555 + 115 0.0000 4.814963 131.0218 + 116 0.0000 4.862017 132.3022 + 117 0.0000 4.891229 133.0971 + 118 0.0000 4.978063 135.4600 + 119 0.0000 5.002569 136.1268 + 120 0.0000 5.072017 138.0166 + 121 0.0000 5.088341 138.4608 + 122 0.0000 5.167883 140.6252 + 123 0.0000 5.246443 142.7630 + 124 0.0000 5.256399 143.0339 + 125 0.0000 5.329864 145.0330 + 126 0.0000 5.349211 145.5594 + 127 0.0000 5.387184 146.5927 + 128 0.0000 5.575634 151.7207 + 129 0.0000 5.670205 154.2941 + 130 0.0000 5.793712 157.6549 + 131 0.0000 5.991136 163.0271 + 132 0.0000 6.113563 166.3585 + 133 0.0000 6.431237 175.0029 + 134 0.0000 6.507402 177.0754 + 135 0.0000 6.509156 177.1231 + 136 0.0000 6.675653 181.6538 + 137 0.0000 6.714377 182.7075 + 138 0.0000 6.743750 183.5068 + 139 0.0000 6.847165 186.3208 + 140 0.0000 6.914919 188.1645 + 141 0.0000 7.067878 192.3267 + 142 0.0000 7.120596 193.7613 + 143 0.0000 7.176476 195.2818 + 144 0.0000 7.228014 196.6842 + 145 0.0000 7.250571 197.2981 + 146 0.0000 7.257614 197.4897 + 147 0.0000 7.333209 199.5467 + 148 0.0000 7.380038 200.8210 + 149 0.0000 7.433534 202.2767 + 150 0.0000 7.477843 203.4825 + 151 0.0000 7.606588 206.9858 + 152 0.0000 7.644800 208.0256 + 153 0.0000 7.698563 209.4885 + 154 0.0000 7.788230 211.9285 + 155 0.0000 7.970548 216.8896 + 156 0.0000 8.067810 219.5363 + 157 0.0000 8.417965 229.0645 + 158 0.0000 14.177917 385.8007 + 159 0.0000 15.082333 410.4112 + 160 0.0000 15.983299 434.9277 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.345404 0.000000 + 1 N : 0.343499 0.000000 + 2 O : -0.278639 0.000000 + 3 H : 0.280544 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.866946 s : 3.866946 + pz : 1.383068 p : 4.449680 + px : 1.239073 + py : 1.827538 + dz2 : 0.012106 d : 0.024091 + dxz : -0.002823 + dyz : 0.000850 + dx2y2 : 0.006027 + dxy : 0.007931 + f0 : 0.000564 f : 0.004687 + f+1 : 0.001056 + f-1 : 0.000097 + f+2 : 0.000644 + f-2 : -0.000127 + f+3 : 0.001033 + f-3 : 0.001421 + 1 N s : 3.829637 s : 3.829637 + pz : 1.083634 p : 2.652310 + px : 0.831820 + py : 0.736856 + dz2 : 0.031677 d : 0.144792 + dxz : 0.035041 + dyz : 0.032062 + dx2y2 : 0.023531 + dxy : 0.022480 + f0 : 0.005272 f : 0.029762 + f+1 : 0.009146 + f-1 : 0.005963 + f+2 : 0.002147 + f-2 : 0.000307 + f+3 : 0.001951 + f-3 : 0.004976 + 2 O s : 3.877777 s : 3.877777 + pz : 1.201894 p : 4.329967 + px : 1.855532 + py : 1.272541 + dz2 : 0.013939 d : 0.063074 + dxz : 0.017043 + dyz : 0.030525 + dx2y2 : -0.000225 + dxy : 0.001792 + f0 : 0.002180 f : 0.007821 + f+1 : 0.002424 + f-1 : 0.002844 + f+2 : 0.000029 + f-2 : 0.000479 + f+3 : -0.000041 + f-3 : -0.000095 + 3 H s : 0.619967 s : 0.619967 + pz : 0.015770 p : 0.077057 + px : 0.019912 + py : 0.041376 + dz2 : 0.001006 d : 0.022431 + dxz : 0.011495 + dyz : 0.010463 + dx2y2 : -0.000275 + dxy : -0.000258 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.601429 0.000000 + 1 N : -0.268930 0.000000 + 2 O : 0.233459 0.000000 + 3 H : -0.565958 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.114212 s : 3.114212 + pz : 1.286285 p : 3.902198 + px : 1.179917 + py : 1.435996 + dz2 : 0.075116 d : 0.293325 + dxz : 0.073778 + dyz : 0.006149 + dx2y2 : 0.091492 + dxy : 0.046789 + f0 : 0.017684 f : 0.088836 + f+1 : 0.015861 + f-1 : 0.001402 + f+2 : 0.017839 + f-2 : 0.003081 + f+3 : 0.018314 + f-3 : 0.014655 + 1 N s : 3.002606 s : 3.002606 + pz : 1.233995 p : 2.833698 + px : 0.912628 + py : 0.687075 + dz2 : 0.277889 d : 0.972387 + dxz : 0.308941 + dyz : 0.114163 + dx2y2 : 0.146328 + dxy : 0.125065 + f0 : 0.110269 f : 0.460240 + f+1 : 0.137251 + f-1 : 0.063361 + f+2 : 0.049352 + f-2 : 0.008693 + f+3 : 0.036690 + f-3 : 0.054626 + 2 O s : 3.316596 s : 3.316596 + pz : 1.404241 p : 4.008149 + px : 1.514780 + py : 1.089128 + dz2 : 0.153737 d : 0.324110 + dxz : 0.098236 + dyz : 0.048775 + dx2y2 : 0.015875 + dxy : 0.007486 + f0 : 0.049252 f : 0.117686 + f+1 : 0.031925 + f-1 : 0.020305 + f+2 : 0.010509 + f-2 : 0.004602 + f+3 : 0.000830 + f-3 : 0.000264 + 3 H s : 0.620109 s : 0.620109 + pz : 0.262673 p : 0.551442 + px : 0.130410 + py : 0.158359 + dz2 : 0.131312 d : 0.394407 + dxz : 0.117811 + dyz : 0.122315 + dx2y2 : 0.017919 + dxy : 0.005050 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3454 8.0000 -0.3454 1.9437 1.9437 -0.0000 + 1 N 6.6565 7.0000 0.3435 2.5351 2.5351 0.0000 + 2 O 8.2786 8.0000 -0.2786 1.7250 1.7250 0.0000 + 3 H 0.7195 1.0000 0.2805 0.9362 0.9362 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.9256 B( 0-O , 3-H ) : 0.9616 B( 1-N , 2-O ) : 1.6517 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.265 sec +Sum of individual times .... 2.092 sec ( 92.4%) + +Fock matrix formation .... 1.734 sec ( 76.5%) +Diagonalization .... 0.172 sec ( 7.6%) +Density matrix formation .... 0.013 sec ( 0.6%) +Population analysis .... 0.012 sec ( 0.5%) +Initial guess .... 0.009 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.2%) +DIIS solution .... 0.152 sec ( 6.7%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.204 sec +Reference energy ... -204.722822139 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.401 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.409 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.028 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.028 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.040 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.023 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.025 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.363 sec +AO-integral generation ... 0.257 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.052 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.151 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.251 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090666455 +EMP2(bb)= -0.090666455 +EMP2(ab)= -0.516822866 + +Initial guess performed in 0.133 sec +E(0) ... -204.722822139 +E(MP2) ... -0.698155776 +Initial E(tot) ... -205.420977916 + ... 0.188366748 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.420977916 -0.698155776 -0.000000000 0.027324865 2.65 0.000002039 + *** Turning on DIIS *** + 1 -205.391492463 -0.668670324 0.029485453 0.012005262 2.74 0.058191268 + 2 -205.411055949 -0.688233810 -0.019563486 0.006048391 2.71 0.061079006 + 3 -205.414761488 -0.691939348 -0.003705539 0.002482865 2.97 0.075536372 + 4 -205.416336992 -0.693514853 -0.001575505 0.001600939 2.76 0.082428728 + 5 -205.416898315 -0.694076176 -0.000561323 0.000851961 2.87 0.088186303 + 6 -205.417010017 -0.694187878 -0.000111702 0.000502483 2.78 0.090985568 + 7 -205.417053933 -0.694231794 -0.000043916 0.000194873 2.77 0.092202228 + 8 -205.417065501 -0.694243361 -0.000011568 0.000100836 2.83 0.092639171 + 9 -205.417061386 -0.694239247 0.000004115 0.000026284 2.75 0.092764709 + 10 -205.417065701 -0.694243562 -0.000004315 0.000009047 2.72 0.092799175 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.722822139 +E(CORR) ... -0.694243562 +E(TOT) ... -205.417065701 +Singles norm **1/2 ... 0.092799175 ( 0.046399588, 0.046399588) +T1 diagnostic ... 0.021872975 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.065580 + 10a-> 13a 10b-> 13b 0.054329 + 8b-> 13b -1b-> -1b 0.045521 + 8a-> 13a -1a-> -1a 0.045521 + 8a-> 13a 10b-> 13b 0.036728 + 10a-> 13a 8b-> 13b 0.036728 + 10b-> 13b -1b-> -1b 0.032803 + 10a-> 13a -1a-> -1a 0.032803 + 11a-> 26a 11b-> 26b 0.029647 + 11b-> 26b -1b-> -1b 0.029259 + 11a-> 26a -1a-> -1a 0.029259 + 11a-> 13a 11b-> 13b 0.028065 + 5a-> 13a 5b-> 13b 0.025567 + 11a-> 26a 10b-> 13b 0.024173 + 10a-> 13a 11b-> 26b 0.024173 + 8a-> 13a 8b-> 22b 0.023835 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034828156 + alpha-alpha-alpha ... -0.000902182 ( 2.6%) + alpha-alpha-beta ... -0.016511896 ( 47.4%) + alpha-beta -beta ... -0.016511896 ( 47.4%) + beta -beta -beta ... -0.000902182 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034828156 + +Final correlation energy ... -0.729071718 +E(CCSD) ... -205.417065701 +E(CCSD(T)) ... -205.451893857 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209931685 sqrt= 1.099968947 +W(HF) = 0.826492944 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.255886 0.000000 + 1 N : 0.153090 -0.000000 + 2 O : -0.164488 0.000000 + 3 H : 0.267284 -0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.846816 s : 3.846816 + pz : 1.365141 p : 4.344149 + px : 1.235838 + py : 1.743170 + dz2 : 0.016562 d : 0.056420 + dxz : 0.005481 + dyz : 0.007908 + dx2y2 : 0.011146 + dxy : 0.015324 + f0 : 0.001279 f : 0.008500 + f+1 : 0.001493 + f-1 : 0.000726 + f+2 : 0.001189 + f-2 : 0.000553 + f+3 : 0.001299 + f-3 : 0.001961 + 1 N s : 3.879559 s : 3.879559 + pz : 1.047925 p : 2.763139 + px : 0.867630 + py : 0.847585 + dz2 : 0.036049 d : 0.175009 + dxz : 0.046561 + dyz : 0.032078 + dx2y2 : 0.029011 + dxy : 0.031310 + f0 : 0.004841 f : 0.029203 + f+1 : 0.008854 + f-1 : 0.004779 + f+2 : 0.002607 + f-2 : 0.000921 + f+3 : 0.002092 + f-3 : 0.005109 + 2 O s : 3.867425 s : 3.867425 + pz : 1.190611 p : 4.201788 + px : 1.774558 + py : 1.236620 + dz2 : 0.016617 d : 0.084867 + dxz : 0.023952 + dyz : 0.030115 + dx2y2 : 0.006218 + dxy : 0.007964 + f0 : 0.002266 f : 0.010408 + f+1 : 0.002836 + f-1 : 0.002594 + f+2 : 0.000666 + f-2 : 0.001029 + f+3 : 0.000537 + f-3 : 0.000480 + 3 H s : 0.632403 s : 0.632403 + pz : 0.009779 p : 0.081054 + px : 0.023729 + py : 0.047545 + dz2 : -0.000081 d : 0.019260 + dxz : 0.010339 + dyz : 0.008773 + dx2y2 : 0.000254 + dxy : -0.000024 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.618564 0.000000 + 1 N : -0.319530 0.000000 + 2 O : 0.266897 0.000000 + 3 H : -0.565931 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.121647 s : 3.121647 + pz : 1.274761 p : 3.839420 + px : 1.188826 + py : 1.375833 + dz2 : 0.081967 d : 0.324565 + dxz : 0.078872 + dyz : 0.011824 + dx2y2 : 0.098251 + dxy : 0.053652 + f0 : 0.018682 f : 0.095804 + f+1 : 0.016689 + f-1 : 0.002257 + f+2 : 0.018071 + f-2 : 0.003524 + f+3 : 0.019695 + f-3 : 0.016886 + 1 N s : 3.007816 s : 3.007816 + pz : 1.203239 p : 2.882523 + px : 0.923450 + py : 0.755833 + dz2 : 0.284044 d : 0.981174 + dxz : 0.306214 + dyz : 0.110835 + dx2y2 : 0.153864 + dxy : 0.126217 + f0 : 0.107295 f : 0.448017 + f+1 : 0.134134 + f-1 : 0.062698 + f+2 : 0.047117 + f-2 : 0.009172 + f+3 : 0.037569 + f-3 : 0.050033 + 2 O s : 3.318395 s : 3.318395 + pz : 1.395167 p : 3.932553 + px : 1.462836 + py : 1.074549 + dz2 : 0.157760 d : 0.355773 + dxz : 0.101112 + dyz : 0.060943 + dx2y2 : 0.021411 + dxy : 0.014547 + f0 : 0.049003 f : 0.126382 + f+1 : 0.032943 + f-1 : 0.025307 + f+2 : 0.010708 + f-2 : 0.006193 + f+3 : 0.001365 + f-3 : 0.000863 + 3 H s : 0.622435 s : 0.622435 + pz : 0.265581 p : 0.559517 + px : 0.131447 + py : 0.162489 + dz2 : 0.130956 d : 0.383979 + dxz : 0.113925 + dyz : 0.115037 + dx2y2 : 0.018286 + dxy : 0.005775 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2559 8.0000 -0.2559 2.3108 1.8494 0.4613 + 1 N 6.8469 7.0000 0.1531 2.8264 2.3506 0.4758 + 2 O 8.1645 8.0000 -0.1645 2.1285 1.6313 0.4972 + 3 H 0.7327 1.0000 0.2673 0.9583 0.8881 0.0702 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8609 B( 0-O , 3-H ) : 0.8888 B( 1-N , 2-O ) : 1.5110 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 45.498 sec + +Fock Matrix Formation ... 0.204 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.3%) +DIIS Solver ... 1.282 sec ( 2.8%) +State Vector Update ... 0.067 sec ( 0.1%) +Sigma-vector construction ... 29.199 sec ( 64.2%) + <0|H|D> ... 0.003 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.019 sec ( 0.1% of sigma) + (0-ext) ... 0.054 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (2-ext) ... 0.731 sec ( 2.5% of sigma) + (4-ext) ... 15.748 sec ( 53.9% of sigma) + ... 1.120 sec ( 3.8% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.087 sec ( 0.3% of sigma) + Fock-dressing ... 1.672 sec ( 5.7% of sigma) + (ik|jl)-dressing ... 0.059 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 7.588 sec ( 26.0% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.840 sec ( 15.0% of ALL) + I/O of integral and amplitudes ... 0.794 sec ( 11.6% of (T)) + External N**7 contributions ... 3.925 sec ( 57.4% of (T)) + Internal N**7 contributions ... 0.322 sec ( 4.7% of (T)) + N**6 triples energy contributions ... 1.715 sec ( 25.1% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.451893857070 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.000154788 -0.002595999 -0.002328612 + 2 N : -0.000856521 -0.002624042 0.003137486 + 3 O : 0.000940416 0.002329162 -0.003135578 + 4 H : 0.000070893 0.002890880 0.002326704 + +Norm of the cartesian gradient ... 0.007717878 +RMS gradient ... 0.002227960 +MAX gradient ... 0.003137486 + +------- +TIMINGS +------- + +Total numerical gradient time ... 316.691 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 583.97 cm**-1 + 7: 623.82 cm**-1 + 8: 819.10 cm**-1 + 9: 1312.95 cm**-1 + 10: 1701.07 cm**-1 + 11: 3708.84 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 -0.068025 -0.369780 0.198742 -0.048642 -0.102924 0.005557 + 1 -0.050493 0.062677 -0.040010 0.000861 0.007812 -0.006598 + 2 0.037728 0.233715 0.090704 -0.072211 -0.043573 -0.062210 + 3 0.024080 0.072613 -0.520012 0.042699 -0.026976 -0.000269 + 4 -0.070673 0.052949 0.049702 0.003072 -0.018877 0.000208 + 5 -0.028217 -0.194255 -0.084338 -0.003403 0.619623 -0.001789 + 6 0.040225 0.293310 0.207721 -0.050952 0.089906 -0.000386 + 7 0.050436 -0.064990 -0.010828 0.001785 0.011730 -0.000134 + 8 -0.009477 -0.086414 -0.024129 0.074089 -0.501751 0.001434 + 9 0.106624 0.204711 0.774619 0.987425 0.581481 -0.078328 + 10 0.982975 -0.699062 0.116241 -0.084688 -0.047858 0.103954 + 11 -0.056297 0.361364 0.115257 0.017482 0.045221 0.989499 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 583.97 0.023377 118.14 0.012492 ( 0.052136 0.092240 -0.035582) + 7: 623.82 0.020690 104.56 0.010350 ( 0.082434 -0.036708 -0.046980) + 8: 819.10 0.027278 137.85 0.010393 (-0.086413 0.014243 0.052178) + 9: 1312.95 0.031778 160.59 0.007553 ( 0.081286 -0.009206 -0.029342) + 10: 1701.07 0.021921 110.78 0.004021 (-0.044369 0.002618 0.045233) + 11: 3708.84 0.014354 72.54 0.001208 (-0.015466 0.004331 0.030819) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 583.97 E(vib) ... 0.11 +freq. 623.82 E(vib) ... 0.09 +freq. 819.10 E(vib) ... 0.05 +freq. 1312.95 E(vib) ... 0.01 +freq. 1701.07 E(vib) ... 0.00 +freq. 3708.84 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.45189385 Eh +Zero point energy ... 0.01993339 Eh 12.51 kcal/mol +Thermal vibrational correction ... 0.00040215 Eh 0.25 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42872578 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00323469 Eh 2.03 kcal/mol +Non-thermal (ZPE) correction 0.01993339 Eh 12.51 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02316808 Eh 14.54 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42872578 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.42778157 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 3.068726 0.418370 0.368431 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00052875 Eh 0.33 kcal/mol +Rotational entropy ... 0.00986423 Eh 6.19 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02819530 Eh 17.69 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00986423 Eh 6.19 kcal/mol| +| sn= 2 | S(rot)= 0.00920977 Eh 5.78 kcal/mol| +| sn= 3 | S(rot)= 0.00882694 Eh 5.54 kcal/mol| +| sn= 4 | S(rot)= 0.00855532 Eh 5.37 kcal/mol| +| sn= 5 | S(rot)= 0.00834463 Eh 5.24 kcal/mol| +| sn= 6 | S(rot)= 0.00817249 Eh 5.13 kcal/mol| +| sn= 7 | S(rot)= 0.00802694 Eh 5.04 kcal/mol| +| sn= 8 | S(rot)= 0.00790086 Eh 4.96 kcal/mol| +| sn= 9 | S(rot)= 0.00778965 Eh 4.89 kcal/mol| +| sn=10 | S(rot)= 0.00769017 Eh 4.83 kcal/mol| +| sn=11 | S(rot)= 0.00760018 Eh 4.77 kcal/mol| +| sn=12 | S(rot)= 0.00751803 Eh 4.72 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.42778157 Eh +Total entropy correction ... -0.02819530 Eh -17.69 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.45597687 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00408301 Eh -2.56 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.451893855 Eh +Current gradient norm .... 0.007717886 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.035049264 0.137231394 0.192590164 0.488758821 0.526720890 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999972801 +Lowest eigenvalues of augmented Hessian: + -0.000028505 0.137076734 0.192542552 0.488771315 0.526719649 +Length of the computed step .... 0.007375665 +The final length of the internal step .... 0.007375665 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0030111026 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0014866668 RMS(Int)= 0.0030109754 + Iter 1: RMS(Cart)= 0.0000010963 RMS(Int)= 0.0000018515 + Iter 2: RMS(Cart)= 0.0000000026 RMS(Int)= 0.0000000033 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0017219247 0.0001000000 NO + MAX gradient 0.0033087500 0.0003000000 NO + RMS step 0.0030111026 0.0020000000 NO + MAX step 0.0053183021 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0028 Max(Angles) 0.04 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4321 0.000109 0.0012 1.4333 + 2. B(O 2,N 1) 1.1761 0.003309 -0.0024 1.1738 + 3. B(H 3,O 0) 0.9717 0.002609 -0.0028 0.9689 + 4. A(N 1,O 0,H 3) 101.98 -0.000083 0.03 102.01 + 5. A(O 0,N 1,O 2) 110.54 -0.000132 0.04 110.58 + 6. D(O 2,N 1,O 0,H 3) -171.82 0.004743 0.00 -171.82 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.758038 0.037027 0.136953 + N 0.656979 -0.098433 -0.046571 + O 0.928812 -0.078043 -1.188265 + H -0.827752 0.139448 1.097883 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.432484 0.069971 0.258803 + 1 N 7.0000 0 14.007 1.241510 -0.186011 -0.088007 + 2 O 8.0000 0 15.999 1.755200 -0.147480 -2.245495 + 3 H 1.0000 0 1.008 -1.564224 0.263519 2.074698 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.433283870900 0.00000000 0.00000000 + O 2 1 0 1.173785484053 110.58134918 0.00000000 + H 1 2 3 0.968884561768 102.00633126 188.18181804 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.708513988168 0.00000000 0.00000000 + O 2 1 0 2.218133104833 110.58134918 0.00000000 + H 1 2 3 1.830926477127 102.00633126 188.18181804 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.481079072557 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.972e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7232215216 0.000000000000 0.00018257 0.00000411 0.0008213 0.7000 + 1 -204.7232240703 -0.000002548715 0.00015313 0.00000330 0.0006166 0.7000 + ***Turning on DIIS*** + 2 -204.7232260724 -0.000002002108 0.00038848 0.00000835 0.0004591 0.0000 + 3 -204.7229646297 0.000261442685 0.00006559 0.00000233 0.0001230 0.0000 + 4 -204.7231844537 -0.000219823942 0.00002531 0.00000081 0.0000474 0.0000 + 5 -204.7233950220 -0.000210568376 0.00000646 0.00000027 0.0000253 0.0000 + 6 -204.7231962966 0.000198725394 0.00000740 0.00000017 0.0000112 0.0000 + 7 -204.7232325219 -0.000036225240 0.00000214 0.00000006 0.0000038 0.0000 + 8 -204.7232394101 -0.000006888191 0.00000121 0.00000003 0.0000012 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + +Total Energy : -204.72322881 Eh -5570.80227 eV + Last Energy change ... 1.0601e-05 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.2013e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.204 sec +Reference energy ... -204.723232029 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.415 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.403 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.025 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.029 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.040 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.036 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.349 sec +AO-integral generation ... 0.244 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.153 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.254 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090610925 +EMP2(bb)= -0.090610925 +EMP2(ab)= -0.516514253 + +Initial guess performed in 0.133 sec +E(0) ... -204.723232029 +E(MP2) ... -0.697736103 +Initial E(tot) ... -205.420968132 + ... 0.188004809 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.420968132 -0.697736103 -0.000000000 0.027097949 2.67 0.000001386 + *** Turning on DIIS *** + 1 -205.391655007 -0.668422978 0.029313125 0.011888135 2.64 0.058072773 + 2 -205.411158486 -0.687926457 -0.019503479 0.005982745 2.71 0.060969116 + 3 -205.414852149 -0.691620120 -0.003693663 0.002463078 2.79 0.075396870 + 4 -205.416420636 -0.693188607 -0.001568487 0.001619521 2.75 0.082275890 + 5 -205.416979839 -0.693747810 -0.000559204 0.000858385 2.84 0.088036116 + 6 -205.417091799 -0.693859770 -0.000111960 0.000504311 2.79 0.090849162 + 7 -205.417135894 -0.693903865 -0.000044095 0.000193480 2.85 0.092074603 + 8 -205.417147501 -0.693915472 -0.000011607 0.000099909 2.87 0.092512376 + 9 -205.417143378 -0.693911349 0.000004123 0.000025846 2.82 0.092637647 + 10 -205.417147668 -0.693915639 -0.000004290 0.000008938 2.79 0.092671840 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.723232029 +E(CORR) ... -0.693915639 +E(TOT) ... -205.417147668 +Singles norm **1/2 ... 0.092671840 ( 0.046335920, 0.046335920) +T1 diagnostic ... 0.021842962 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.065660 + 10a-> 13a 10b-> 13b 0.053445 + 8b-> 13b -1b-> -1b 0.044987 + 8a-> 13a -1a-> -1a 0.044987 + 8a-> 13a 10b-> 13b 0.036368 + 10a-> 13a 8b-> 13b 0.036368 + 10b-> 13b -1b-> -1b 0.033316 + 10a-> 13a -1a-> -1a 0.033316 + 11a-> 26a 11b-> 26b 0.029858 + 11a-> 26a -1a-> -1a 0.029138 + 11b-> 26b -1b-> -1b 0.029138 + 11a-> 13a 11b-> 13b 0.027970 + 5a-> 13a 5b-> 13b 0.025490 + 11a-> 26a 10b-> 13b 0.024165 + 10a-> 13a 11b-> 26b 0.024165 + 8a-> 22a 8b-> 13b 0.024096 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034760440 + alpha-alpha-alpha ... -0.000901108 ( 2.6%) + alpha-alpha-beta ... -0.016479112 ( 47.4%) + alpha-beta -beta ... -0.016479112 ( 47.4%) + beta -beta -beta ... -0.000901108 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034760440 + +Final correlation energy ... -0.728676079 +E(CCSD) ... -205.417147668 +E(CCSD(T)) ... -205.451908108 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209554533 sqrt= 1.099797497 +W(HF) = 0.826750653 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 46.044 sec + +Fock Matrix Formation ... 0.204 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.3%) +DIIS Solver ... 1.465 sec ( 3.2%) +State Vector Update ... 0.064 sec ( 0.1%) +Sigma-vector construction ... 28.982 sec ( 62.9%) + <0|H|D> ... 0.003 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (0-ext) ... 0.054 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (2-ext) ... 0.730 sec ( 2.5% of sigma) + (4-ext) ... 15.547 sec ( 53.6% of sigma) + ... 1.156 sec ( 4.0% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.086 sec ( 0.3% of sigma) + Fock-dressing ... 1.667 sec ( 5.8% of sigma) + (ik|jl)-dressing ... 0.059 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 7.572 sec ( 26.1% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.789 sec ( 14.7% of ALL) + I/O of integral and amplitudes ... 0.795 sec ( 11.7% of (T)) + External N**7 contributions ... 3.900 sec ( 57.5% of (T)) + Internal N**7 contributions ... 0.318 sec ( 4.7% of (T)) + N**6 triples energy contributions ... 1.689 sec ( 24.9% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.451908107862 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.000177706 -0.002333504 0.000356202 + 2 N : -0.000262922 -0.002549066 -0.000187021 + 3 O : 0.000225967 0.002264856 0.000121323 + 4 H : 0.000214661 0.002617713 -0.000290505 + +Norm of the cartesian gradient ... 0.004937995 +RMS gradient ... 0.001425476 +MAX gradient ... 0.002617713 + +------- +TIMINGS +------- + +Total numerical gradient time ... 306.803 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.451908108 Eh +Current gradient norm .... 0.004937995 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999998 +Lowest eigenvalues of augmented Hessian: + -0.000000002 0.137022873 0.192641751 0.491872734 0.526738949 +Length of the computed step .... 0.000069791 +The final length of the internal step .... 0.000069791 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0000284919 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0000141114 RMS(Int)= 0.0000284919 + Iter 1: RMS(Cart)= 0.0000000002 RMS(Int)= 0.0000000002 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000142529 0.0000050000 NO + RMS gradient 0.0000152019 0.0001000000 YES + MAX gradient 0.0000261316 0.0003000000 YES + RMS step 0.0000284919 0.0020000000 YES + MAX step 0.0000531797 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0000 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4333 -0.000002 -0.0000 1.4333 + 2. B(O 2,N 1) 1.1738 -0.000026 0.0000 1.1738 + 3. B(H 3,O 0) 0.9689 -0.000026 0.0000 0.9689 + 4. A(N 1,O 0,H 3) 102.01 0.000005 -0.00 102.00 + 5. A(O 0,N 1,O 2) 110.58 0.000003 -0.00 110.58 + 6. D(O 2,N 1,O 0,H 3) -171.82 0.004732 -0.00 -171.82 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.758044 0.037025 0.136938 + N 0.656974 -0.098432 -0.046564 + O 0.928818 -0.078043 -1.188272 + H -0.827747 0.139450 1.097897 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.432496 0.069968 0.258776 + 1 N 7.0000 0 14.007 1.241501 -0.186010 -0.087992 + 2 O 8.0000 0 15.999 1.755212 -0.147480 -2.245509 + 3 H 1.0000 0 1.008 -1.564215 0.263522 2.074725 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.433282086523 0.00000000 0.00000000 + O 2 1 0 1.173802932942 110.58083751 0.00000000 + H 1 2 3 0.968912703270 102.00464685 188.18181804 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.708510616184 0.00000000 0.00000000 + O 2 1 0 2.218166078454 110.58083751 0.00000000 + H 1 2 3 1.830979656858 102.00464685 188.18181804 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.480556644499 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.4805566445 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.972e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7232279081 0.000000000000 0.00000193 0.00000004 0.0000074 0.7000 + 1 -204.7232279082 -0.000000000129 0.00000160 0.00000003 0.0000057 0.7000 + ***Turning on DIIS*** + 2 -204.7232279084 -0.000000000170 0.00000403 0.00000008 0.0000042 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 3 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72322997 Eh -5570.80230 eV + +Components: +Nuclear Repulsion : 69.48055664 Eh 1890.66207 eV +Electronic Energy : -274.20378661 Eh -7461.46437 eV +One Electron Energy: -418.66398965 Eh -11392.42634 eV +Two Electron Energy: 144.46020304 Eh 3930.96197 eV + +Virial components: +Potential Energy : -408.97105356 Eh -11128.66814 eV +Kinetic Energy : 204.24782359 Eh 5557.86584 eV +Virial Ratio : 2.00232760 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -2.0608e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.0110e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.8020e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.7859e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.666843 -562.3734 + 1 1.0000 -20.640146 -561.6469 + 2 1.0000 -15.799083 -429.9149 + 3 1.0000 -1.605084 -43.6765 + 4 1.0000 -1.400678 -38.1144 + 5 1.0000 -0.948512 -25.8103 + 6 1.0000 -0.784022 -21.3343 + 7 1.0000 -0.729892 -19.8614 + 8 1.0000 -0.682526 -18.5725 + 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0.938879 25.5482 + 50 0.0000 0.947449 25.7814 + 51 0.0000 0.997107 27.1327 + 52 0.0000 1.048065 28.5193 + 53 0.0000 1.062158 28.9028 + 54 0.0000 1.077683 29.3252 + 55 0.0000 1.104088 30.0438 + 56 0.0000 1.160813 31.5873 + 57 0.0000 1.194349 32.4999 + 58 0.0000 1.252353 34.0783 + 59 0.0000 1.273814 34.6622 + 60 0.0000 1.364344 37.1257 + 61 0.0000 1.431543 38.9543 + 62 0.0000 1.491950 40.5980 + 63 0.0000 1.521196 41.3938 + 64 0.0000 1.525225 41.5035 + 65 0.0000 1.546205 42.0744 + 66 0.0000 1.553873 42.2830 + 67 0.0000 1.606899 43.7260 + 68 0.0000 1.660388 45.1815 + 69 0.0000 1.729229 47.0547 + 70 0.0000 1.755420 47.7674 + 71 0.0000 1.819751 49.5179 + 72 0.0000 1.857079 50.5337 + 73 0.0000 1.960513 53.3483 + 74 0.0000 1.970085 53.6087 + 75 0.0000 2.000443 54.4348 + 76 0.0000 2.075172 56.4683 + 77 0.0000 2.116871 57.6030 + 78 0.0000 2.148386 58.4606 + 79 0.0000 2.182533 59.3897 + 80 0.0000 2.275642 61.9234 + 81 0.0000 2.307739 62.7968 + 82 0.0000 2.326996 63.3208 + 83 0.0000 2.380522 64.7773 + 84 0.0000 2.449496 66.6542 + 85 0.0000 2.468989 67.1846 + 86 0.0000 2.498450 67.9863 + 87 0.0000 2.502570 68.0984 + 88 0.0000 2.520900 68.5972 + 89 0.0000 2.543742 69.2187 + 90 0.0000 2.570124 69.9366 + 91 0.0000 2.603304 70.8395 + 92 0.0000 2.620570 71.3093 + 93 0.0000 2.665928 72.5436 + 94 0.0000 2.767117 75.2971 + 95 0.0000 2.774309 75.4928 + 96 0.0000 2.845009 77.4166 + 97 0.0000 2.929464 79.7148 + 98 0.0000 2.946274 80.1722 + 99 0.0000 3.111094 84.6572 + 100 0.0000 3.150121 85.7191 + 101 0.0000 3.183814 86.6360 + 102 0.0000 3.249329 88.4187 + 103 0.0000 3.458385 94.1074 + 104 0.0000 3.819779 103.9415 + 105 0.0000 3.863906 105.1422 + 106 0.0000 4.029943 109.6603 + 107 0.0000 4.174081 113.5825 + 108 0.0000 4.180253 113.7505 + 109 0.0000 4.222399 114.8973 + 110 0.0000 4.366330 118.8139 + 111 0.0000 4.378667 119.1496 + 112 0.0000 4.579136 124.6046 + 113 0.0000 4.629826 125.9840 + 114 0.0000 4.750664 129.2721 + 115 0.0000 4.814284 131.0033 + 116 0.0000 4.863232 132.3353 + 117 0.0000 4.891439 133.1028 + 118 0.0000 4.980256 135.5197 + 119 0.0000 5.002658 136.1292 + 120 0.0000 5.073231 138.0496 + 121 0.0000 5.092191 138.5656 + 122 0.0000 5.170196 140.6882 + 123 0.0000 5.249222 142.8386 + 124 0.0000 5.256538 143.0377 + 125 0.0000 5.334913 145.1704 + 126 0.0000 5.352499 145.6489 + 127 0.0000 5.390659 146.6873 + 128 0.0000 5.573289 151.6569 + 129 0.0000 5.673816 154.3924 + 130 0.0000 5.796917 157.7421 + 131 0.0000 5.993796 163.0995 + 132 0.0000 6.111697 166.3077 + 133 0.0000 6.431339 175.0056 + 134 0.0000 6.507025 177.0652 + 135 0.0000 6.508821 177.1140 + 136 0.0000 6.676132 181.6668 + 137 0.0000 6.715212 182.7302 + 138 0.0000 6.744247 183.5203 + 139 0.0000 6.848671 186.3618 + 140 0.0000 6.915409 188.1778 + 141 0.0000 7.070247 192.3912 + 142 0.0000 7.121155 193.7765 + 143 0.0000 7.182541 195.4469 + 144 0.0000 7.229524 196.7253 + 145 0.0000 7.252621 197.3539 + 146 0.0000 7.260255 197.5616 + 147 0.0000 7.338783 199.6984 + 148 0.0000 7.384080 200.9310 + 149 0.0000 7.433855 202.2855 + 150 0.0000 7.478211 203.4925 + 151 0.0000 7.611535 207.1204 + 152 0.0000 7.646754 208.0788 + 153 0.0000 7.700679 209.5461 + 154 0.0000 7.791843 212.0268 + 155 0.0000 7.971919 216.9269 + 156 0.0000 8.068114 219.5445 + 157 0.0000 8.422929 229.1996 + 158 0.0000 14.201788 386.4503 + 159 0.0000 15.116503 411.3410 + 160 0.0000 16.049316 436.7241 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.344272 0.000000 + 1 N : 0.343915 0.000000 + 2 O : -0.277462 0.000000 + 3 H : 0.277818 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.866648 s : 3.866648 + pz : 1.381516 p : 4.449144 + px : 1.239971 + py : 1.827657 + dz2 : 0.011917 d : 0.023824 + dxz : -0.002799 + dyz : 0.000835 + dx2y2 : 0.005987 + dxy : 0.007884 + f0 : 0.000544 f : 0.004656 + f+1 : 0.001063 + f-1 : 0.000096 + f+2 : 0.000640 + f-2 : -0.000127 + f+3 : 0.001028 + f-3 : 0.001413 + 1 N s : 3.829979 s : 3.829979 + pz : 1.083600 p : 2.651559 + px : 0.831292 + py : 0.736667 + dz2 : 0.031630 d : 0.144818 + dxz : 0.035119 + dyz : 0.032070 + dx2y2 : 0.023581 + dxy : 0.022418 + f0 : 0.005272 f : 0.029728 + f+1 : 0.009164 + f-1 : 0.005939 + f+2 : 0.002130 + f-2 : 0.000302 + f+3 : 0.001956 + f-3 : 0.004966 + 2 O s : 3.877022 s : 3.877022 + pz : 1.202322 p : 4.329139 + px : 1.854794 + py : 1.272023 + dz2 : 0.013993 d : 0.063461 + dxz : 0.017201 + dyz : 0.030690 + dx2y2 : -0.000219 + dxy : 0.001796 + f0 : 0.002178 f : 0.007841 + f+1 : 0.002433 + f-1 : 0.002857 + f+2 : 0.000030 + f-2 : 0.000479 + f+3 : -0.000041 + f-3 : -0.000095 + 3 H s : 0.621745 s : 0.621745 + pz : 0.015700 p : 0.077776 + px : 0.020222 + py : 0.041854 + dz2 : 0.001057 d : 0.022661 + dxz : 0.011585 + dyz : 0.010558 + dx2y2 : -0.000278 + dxy : -0.000261 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.604505 0.000000 + 1 N : -0.268225 0.000000 + 2 O : 0.235092 0.000000 + 3 H : -0.571372 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.113178 s : 3.113178 + pz : 1.286572 p : 3.901332 + px : 1.179411 + py : 1.435349 + dz2 : 0.075006 d : 0.292449 + dxz : 0.073396 + dyz : 0.006155 + dx2y2 : 0.091337 + dxy : 0.046555 + f0 : 0.017582 f : 0.088536 + f+1 : 0.015860 + f-1 : 0.001395 + f+2 : 0.017738 + f-2 : 0.003093 + f+3 : 0.018278 + f-3 : 0.014589 + 1 N s : 3.002108 s : 3.002108 + pz : 1.234827 p : 2.833366 + px : 0.911240 + py : 0.687299 + dz2 : 0.278121 d : 0.972685 + dxz : 0.309297 + dyz : 0.114430 + dx2y2 : 0.146199 + dxy : 0.124638 + f0 : 0.110189 f : 0.460067 + f+1 : 0.137555 + f-1 : 0.063400 + f+2 : 0.049163 + f-2 : 0.008697 + f+3 : 0.036611 + f-3 : 0.054451 + 2 O s : 3.315209 s : 3.315209 + pz : 1.405555 p : 4.006615 + px : 1.512963 + py : 1.088098 + dz2 : 0.154024 d : 0.325006 + dxz : 0.098584 + dyz : 0.048988 + dx2y2 : 0.015912 + dxy : 0.007498 + f0 : 0.049395 f : 0.118078 + f+1 : 0.032037 + f-1 : 0.020421 + f+2 : 0.010527 + f-2 : 0.004605 + f+3 : 0.000830 + f-3 : 0.000263 + 3 H s : 0.621410 s : 0.621410 + pz : 0.263554 p : 0.554551 + px : 0.131373 + py : 0.159625 + dz2 : 0.131421 d : 0.395411 + dxz : 0.118258 + dyz : 0.122755 + dx2y2 : 0.017937 + dxy : 0.005040 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3443 8.0000 -0.3443 1.9445 1.9445 0.0000 + 1 N 6.6561 7.0000 0.3439 2.5341 2.5341 0.0000 + 2 O 8.2775 8.0000 -0.2775 1.7255 1.7255 -0.0000 + 3 H 0.7222 1.0000 0.2778 0.9383 0.9383 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.9241 B( 0-O , 3-H ) : 0.9638 B( 1-N , 2-O ) : 1.6522 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.643 sec +Sum of individual times .... 0.492 sec ( 76.4%) + +Fock matrix formation .... 0.394 sec ( 61.2%) +Diagonalization .... 0.045 sec ( 7.0%) +Density matrix formation .... 0.003 sec ( 0.5%) +Population analysis .... 0.014 sec ( 2.1%) +Initial guess .... 0.009 sec ( 1.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.8%) +DIIS solution .... 0.027 sec ( 4.2%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.205 sec +Reference energy ... -204.723227909 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.450 sec +AO-integral generation ... 0.140 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.454 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.025 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.029 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.040 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.034 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.025 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.041 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.025 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.364 sec +AO-integral generation ... 0.257 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.156 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.253 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090611522 +EMP2(bb)= -0.090611522 +EMP2(ab)= -0.516517574 + +Initial guess performed in 0.134 sec +E(0) ... -204.723227909 +E(MP2) ... -0.697740618 +Initial E(tot) ... -205.420968527 + ... 0.188008611 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.420968527 -0.697740618 -0.000000000 0.027099382 2.75 0.000000901 + *** Turning on DIIS *** + 1 -205.391653471 -0.668425563 0.029315055 0.011889034 2.67 0.058073744 + 2 -205.411157576 -0.687929667 -0.019504105 0.005983156 2.75 0.060969833 + 3 -205.414851341 -0.691623433 -0.003693765 0.002463236 2.76 0.075397822 + 4 -205.416419887 -0.693191978 -0.001568546 0.001619440 2.76 0.082276918 + 5 -205.416979112 -0.693751204 -0.000559225 0.000858363 2.82 0.088037176 + 6 -205.417091072 -0.693863163 -0.000111959 0.000504316 2.76 0.090850183 + 7 -205.417135167 -0.693907258 -0.000044096 0.000193494 2.79 0.092075619 + 8 -205.417146774 -0.693918866 -0.000011607 0.000099918 2.81 0.092513408 + 9 -205.417142651 -0.693914742 0.000004123 0.000025850 2.71 0.092638687 + 10 -205.417146941 -0.693919032 -0.000004290 0.000008940 2.68 0.092672883 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.723227909 +E(CORR) ... -0.693919032 +E(TOT) ... -205.417146941 +Singles norm **1/2 ... 0.092672883 ( 0.046336441, 0.046336441) +T1 diagnostic ... 0.021843208 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.065661 + 10a-> 13a 10b-> 13b 0.053451 + 8b-> 13b -1b-> -1b 0.044991 + 8a-> 13a -1a-> -1a 0.044991 + 8a-> 13a 10b-> 13b 0.036371 + 10a-> 13a 8b-> 13b 0.036371 + 10a-> 13a -1a-> -1a 0.033313 + 10b-> 13b -1b-> -1b 0.033313 + 11a-> 26a 11b-> 26b 0.029857 + 11b-> 26b -1b-> -1b 0.029138 + 11a-> 26a -1a-> -1a 0.029138 + 11a-> 13a 11b-> 13b 0.027971 + 5a-> 13a 5b-> 13b 0.025491 + 11a-> 26a 10b-> 13b 0.024165 + 10a-> 13a 11b-> 26b 0.024165 + 8a-> 22a 8b-> 13b 0.024095 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034761170 + alpha-alpha-alpha ... -0.000901120 ( 2.6%) + alpha-alpha-beta ... -0.016479465 ( 47.4%) + alpha-beta -beta ... -0.016479465 ( 47.4%) + beta -beta -beta ... -0.000901120 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034761170 + +Final correlation energy ... -0.728680202 +E(CCSD) ... -205.417146941 +E(CCSD(T)) ... -205.451908111 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209558326 sqrt= 1.099799221 +W(HF) = 0.826748060 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.255366 0.000000 + 1 N : 0.153743 -0.000000 + 2 O : -0.163482 0.000000 + 3 H : 0.265106 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.846823 s : 3.846823 + pz : 1.363850 p : 4.343882 + px : 1.236604 + py : 1.743429 + dz2 : 0.016397 d : 0.056189 + dxz : 0.005491 + dyz : 0.007891 + dx2y2 : 0.011130 + dxy : 0.015280 + f0 : 0.001259 f : 0.008472 + f+1 : 0.001499 + f-1 : 0.000726 + f+2 : 0.001185 + f-2 : 0.000553 + f+3 : 0.001295 + f-3 : 0.001955 + 1 N s : 3.879833 s : 3.879833 + pz : 1.048005 p : 2.762268 + px : 0.867615 + py : 0.846649 + dz2 : 0.035967 d : 0.174990 + dxz : 0.046609 + dyz : 0.032107 + dx2y2 : 0.029044 + dxy : 0.031263 + f0 : 0.004841 f : 0.029166 + f+1 : 0.008863 + f-1 : 0.004758 + f+2 : 0.002591 + f-2 : 0.000917 + f+3 : 0.002096 + f-3 : 0.005100 + 2 O s : 3.866736 s : 3.866736 + pz : 1.190827 p : 4.201101 + px : 1.773528 + py : 1.236746 + dz2 : 0.016666 d : 0.085221 + dxz : 0.024117 + dyz : 0.030250 + dx2y2 : 0.006222 + dxy : 0.007966 + f0 : 0.002266 f : 0.010424 + f+1 : 0.002846 + f-1 : 0.002602 + f+2 : 0.000667 + f-2 : 0.001029 + f+3 : 0.000536 + f-3 : 0.000479 + 3 H s : 0.633785 s : 0.633785 + pz : 0.009669 p : 0.081673 + px : 0.024010 + py : 0.047994 + dz2 : -0.000042 d : 0.019437 + dxz : 0.010410 + dyz : 0.008844 + dx2y2 : 0.000252 + dxy : -0.000027 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.621565 0.000000 + 1 N : -0.318676 -0.000000 + 2 O : 0.268261 0.000000 + 3 H : -0.571149 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.120591 s : 3.120591 + pz : 1.275101 p : 3.838671 + px : 1.188277 + py : 1.375293 + dz2 : 0.081849 d : 0.323681 + dxz : 0.078507 + dyz : 0.011829 + dx2y2 : 0.098110 + dxy : 0.053385 + f0 : 0.018585 f : 0.095492 + f+1 : 0.016685 + f-1 : 0.002247 + f+2 : 0.017984 + f-2 : 0.003536 + f+3 : 0.019660 + f-3 : 0.016794 + 1 N s : 3.007305 s : 3.007305 + pz : 1.204227 p : 2.882034 + px : 0.922434 + py : 0.755373 + dz2 : 0.284226 d : 0.981456 + dxz : 0.306483 + dyz : 0.111213 + dx2y2 : 0.153691 + dxy : 0.125844 + f0 : 0.107226 f : 0.447881 + f+1 : 0.134384 + f-1 : 0.062781 + f+2 : 0.046947 + f-2 : 0.009178 + f+3 : 0.037492 + f-3 : 0.049873 + 2 O s : 3.317007 s : 3.317007 + pz : 1.396345 p : 3.931334 + px : 1.460958 + py : 1.074031 + dz2 : 0.158029 d : 0.356627 + dxz : 0.101470 + dyz : 0.061129 + dx2y2 : 0.021444 + dxy : 0.014555 + f0 : 0.049139 f : 0.126771 + f+1 : 0.033074 + f-1 : 0.025412 + f+2 : 0.010726 + f-2 : 0.006194 + f+3 : 0.001364 + f-3 : 0.000862 + 3 H s : 0.623641 s : 0.623641 + pz : 0.266475 p : 0.562570 + px : 0.132375 + py : 0.163720 + dz2 : 0.131065 d : 0.384938 + dxz : 0.114350 + dyz : 0.115447 + dx2y2 : 0.018309 + dxy : 0.005766 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2554 8.0000 -0.2554 2.3109 1.8499 0.4610 + 1 N 6.8463 7.0000 0.1537 2.8249 2.3500 0.4749 + 2 O 8.1635 8.0000 -0.1635 2.1282 1.6321 0.4961 + 3 H 0.7349 1.0000 0.2651 0.9598 0.8897 0.0700 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8595 B( 0-O , 3-H ) : 0.8906 B( 1-N , 2-O ) : 1.5118 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 45.241 sec + +Fock Matrix Formation ... 0.205 sec ( 0.5%) +Initial Guess ... 0.134 sec ( 0.3%) +DIIS Solver ... 1.369 sec ( 3.0%) +State Vector Update ... 0.064 sec ( 0.1%) +Sigma-vector construction ... 28.831 sec ( 63.7%) + <0|H|D> ... 0.003 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.019 sec ( 0.1% of sigma) + (0-ext) ... 0.053 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (2-ext) ... 0.732 sec ( 2.5% of sigma) + (4-ext) ... 15.542 sec ( 53.9% of sigma) + ... 1.099 sec ( 3.8% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.085 sec ( 0.3% of sigma) + Fock-dressing ... 1.655 sec ( 5.7% of sigma) + (ik|jl)-dressing ... 0.058 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 7.451 sec ( 25.8% of sigma) + Pair energies ... 0.004 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.799 sec ( 15.0% of ALL) + I/O of integral and amplitudes ... 0.790 sec ( 11.6% of (T)) + External N**7 contributions ... 3.930 sec ( 57.8% of (T)) + Internal N**7 contributions ... 0.314 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.682 sec ( 24.7% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.451908110773 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.002.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.002.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.446177, -0.076147 -0.657838) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.87058 -0.09948 -0.48311 +Nuclear contribution : -1.00022 0.16890 1.35302 + ----------------------------------------- +Total Dipole Moment : -0.12964 0.06942 0.86991 + ----------------------------------------- +Magnitude (a.u.) : 0.88225 +Magnitude (Debye) : 2.24250 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.077289 0.418448 0.368613 +Rotational constants in MHz : 92254.815556 12544.756521 11050.735742 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.637772 0.604167 -0.081220 +x,y,z [Debye]: 1.621088 1.535670 -0.206444 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.446177, -0.076147 -0.657838) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.84724 -0.09796 -0.66043 +Nuclear contribution : -1.00022 0.16890 1.35302 + ----------------------------------------- +Total Dipole Moment : -0.15298 0.07094 0.69259 + ----------------------------------------- +Magnitude (a.u.) : 0.71283 +Magnitude (Debye) : 1.81186 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.077289 0.418448 0.368613 +Rotational constants in MHz : 92254.815556 12544.756521 11050.735742 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.548011 0.449579 -0.075383 +x,y,z [Debye]: 1.392934 1.142739 -0.191608 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 3 * + * * + * Dihedral ( 2, 1, 0, 3) : -163.63636364 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0395887660 RMS(Int)= 0.0002472262 + Iter 1: RMS(Cart)= 0.0000685392 RMS(Int)= 0.0000012836 + Iter 2: RMS(Cart)= 0.0000003558 RMS(Int)= 0.0000000067 + Iter 3: RMS(Cart)= 0.0000000019 RMS(Int)= 0.0000000000 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4333 0.000000 + 2. B(O 2,N 1) 1.1760 0.000000 + 3. B(H 3,O 0) 0.9717 0.000000 + 4. A(N 1,O 0,H 3) 101.9783 0.000000 + 5. A(O 0,N 1,O 2) 110.5328 0.000000 + 6. D(O 2,N 1,O 0,H 3) -163.6364 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.761009 0.002556 0.139521 + N 0.653351 -0.135969 -0.046791 + O 0.930226 -0.044458 -1.186032 + H -0.822567 0.177871 1.093302 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.438099 0.004831 0.263657 + 1 N 7.0000 0 14.007 1.234654 -0.256945 -0.088423 + 2 O 8.0000 0 15.999 1.757873 -0.084014 -2.241275 + 3 H 1.0000 0 1.008 -1.554426 0.336128 2.066041 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.433282086523 0.00000000 0.00000000 + O 2 1 0 1.173802932942 110.58083751 0.00000000 + H 1 2 3 0.968912703270 102.00464685 188.18181804 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.708510616184 0.00000000 0.00000000 + O 2 1 0 2.218166078454 110.58083751 0.00000000 + H 1 2 3 1.830979656858 102.00464685 188.18181804 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.415556648774 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.4155566488 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.976e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7175200694 0.000000000000 0.00181965 0.00005311 0.0197679 0.7000 + 1 -204.7184209733 -0.000900903888 0.00172739 0.00004790 0.0163633 0.7000 + ***Turning on DIIS*** + 2 -204.7191882553 -0.000767282075 0.00470432 0.00012935 0.0132962 0.0000 + 3 -204.7231183714 -0.003930116048 0.00193340 0.00005192 0.0053453 0.0000 + 4 -204.7209404929 0.002177878518 0.00088090 0.00002289 0.0021148 0.0000 + 5 -204.7225051200 -0.001564627162 0.00057860 0.00001745 0.0010295 0.0000 + 6 -204.7218650937 0.000640026348 0.00060499 0.00002050 0.0006215 0.0000 + 7 -204.7214527457 0.000412347997 0.00032510 0.00001072 0.0002655 0.0000 + 8 -204.7221781994 -0.000725453748 0.00017814 0.00000674 0.0001927 0.0000 + 9 -204.7217899111 0.000388288289 0.00014564 0.00000475 0.0001300 0.0000 + 10 -204.7219167576 -0.000126846422 0.00006931 0.00000200 0.0000585 0.0000 + 11 -204.7220403818 -0.000123624240 0.00002928 0.00000079 0.0000245 0.0000 + 12 -204.7219398268 0.000100554985 0.00000771 0.00000020 0.0000071 0.0000 + 13 -204.7219658773 -0.000026050518 0.00000194 0.00000006 0.0000023 0.0000 + 14 -204.7219571742 0.000008703130 0.00000078 0.00000002 0.0000014 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 15 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72195886 Eh -5570.76771 eV + +Components: +Nuclear Repulsion : 69.41555665 Eh 1888.89333 eV +Electronic Energy : -274.13751551 Eh -7459.66104 eV +One Electron Energy: -418.54159817 Eh -11389.09590 eV +Two Electron Energy: 144.40408265 Eh 3929.43486 eV + +Virial components: +Potential Energy : -408.95762189 Eh -11128.30264 eV +Kinetic Energy : 204.23566302 Eh 5557.53493 eV +Virial Ratio : 2.00238105 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.6903e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.2002e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.4496e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.5369e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.667342 -562.3870 + 1 1.0000 -20.640050 -561.6443 + 2 1.0000 -15.799100 -429.9154 + 3 1.0000 -1.603464 -43.6325 + 4 1.0000 -1.399691 -38.0875 + 5 1.0000 -0.948729 -25.8162 + 6 1.0000 -0.782735 -21.2993 + 7 1.0000 -0.729276 -19.8446 + 8 1.0000 -0.683461 -18.5979 + 9 1.0000 -0.622494 -16.9389 + 10 1.0000 -0.528686 -14.3863 + 11 1.0000 -0.461689 -12.5632 + 12 0.0000 0.028166 0.7664 + 13 0.0000 0.079460 2.1622 + 14 0.0000 0.093806 2.5526 + 15 0.0000 0.097962 2.6657 + 16 0.0000 0.126953 3.4546 + 17 0.0000 0.145042 3.9468 + 18 0.0000 0.157006 4.2724 + 19 0.0000 0.172271 4.6877 + 20 0.0000 0.187009 5.0888 + 21 0.0000 0.196190 5.3386 + 22 0.0000 0.205012 5.5787 + 23 0.0000 0.234178 6.3723 + 24 0.0000 0.259673 7.0661 + 25 0.0000 0.294092 8.0027 + 26 0.0000 0.309279 8.4159 + 27 0.0000 0.329731 8.9724 + 28 0.0000 0.363213 9.8835 + 29 0.0000 0.378719 10.3055 + 30 0.0000 0.423350 11.5199 + 31 0.0000 0.516310 14.0495 + 32 0.0000 0.530016 14.4225 + 33 0.0000 0.548600 14.9282 + 34 0.0000 0.570669 15.5287 + 35 0.0000 0.614088 16.7102 + 36 0.0000 0.631924 17.1955 + 37 0.0000 0.647194 17.6111 + 38 0.0000 0.686751 18.6874 + 39 0.0000 0.717880 19.5345 + 40 0.0000 0.719436 19.5768 + 41 0.0000 0.746465 20.3123 + 42 0.0000 0.772310 21.0156 + 43 0.0000 0.785985 21.3877 + 44 0.0000 0.807053 21.9610 + 45 0.0000 0.816327 22.2134 + 46 0.0000 0.859042 23.3757 + 47 0.0000 0.872590 23.7444 + 48 0.0000 0.926581 25.2136 + 49 0.0000 0.938548 25.5392 + 50 0.0000 0.949671 25.8419 + 51 0.0000 0.999484 27.1973 + 52 0.0000 1.045165 28.4404 + 53 0.0000 1.059175 28.8216 + 54 0.0000 1.068454 29.0741 + 55 0.0000 1.098577 29.8938 + 56 0.0000 1.160729 31.5850 + 57 0.0000 1.194726 32.5101 + 58 0.0000 1.251025 34.0421 + 59 0.0000 1.285713 34.9860 + 60 0.0000 1.366624 37.1877 + 61 0.0000 1.423111 38.7248 + 62 0.0000 1.493499 40.6402 + 63 0.0000 1.517655 41.2975 + 64 0.0000 1.522759 41.4364 + 65 0.0000 1.541880 41.9567 + 66 0.0000 1.562815 42.5263 + 67 0.0000 1.604430 43.6588 + 68 0.0000 1.664757 45.3004 + 69 0.0000 1.730675 47.0941 + 70 0.0000 1.762129 47.9500 + 71 0.0000 1.814899 49.3859 + 72 0.0000 1.863327 50.7037 + 73 0.0000 1.952607 53.1331 + 74 0.0000 1.962723 53.4084 + 75 0.0000 2.010342 54.7042 + 76 0.0000 2.079169 56.5771 + 77 0.0000 2.102813 57.2204 + 78 0.0000 2.161712 58.8232 + 79 0.0000 2.174400 59.1684 + 80 0.0000 2.283274 62.1310 + 81 0.0000 2.304220 62.7010 + 82 0.0000 2.322176 63.1896 + 83 0.0000 2.376542 64.6690 + 84 0.0000 2.447346 66.5957 + 85 0.0000 2.469573 67.2005 + 86 0.0000 2.495236 67.8988 + 87 0.0000 2.502746 68.1032 + 88 0.0000 2.519356 68.5552 + 89 0.0000 2.541048 69.1454 + 90 0.0000 2.570962 69.9594 + 91 0.0000 2.601048 70.7781 + 92 0.0000 2.636414 71.7405 + 93 0.0000 2.677503 72.8586 + 94 0.0000 2.751833 74.8812 + 95 0.0000 2.765007 75.2397 + 96 0.0000 2.864106 77.9363 + 97 0.0000 2.908030 79.1315 + 98 0.0000 2.949610 80.2630 + 99 0.0000 3.105625 84.5084 + 100 0.0000 3.153233 85.8038 + 101 0.0000 3.182992 86.6136 + 102 0.0000 3.253846 88.5417 + 103 0.0000 3.461426 94.1902 + 104 0.0000 3.794514 103.2540 + 105 0.0000 3.879327 105.5618 + 106 0.0000 4.027917 109.6052 + 107 0.0000 4.165978 113.3620 + 108 0.0000 4.175309 113.6159 + 109 0.0000 4.239779 115.3703 + 110 0.0000 4.360367 118.6516 + 111 0.0000 4.388326 119.4124 + 112 0.0000 4.571032 124.3841 + 113 0.0000 4.621995 125.7709 + 114 0.0000 4.746684 129.1638 + 115 0.0000 4.814710 131.0149 + 116 0.0000 4.843825 131.8072 + 117 0.0000 4.893885 133.1694 + 118 0.0000 4.970935 135.2660 + 119 0.0000 5.003560 136.1538 + 120 0.0000 5.070488 137.9750 + 121 0.0000 5.094028 138.6155 + 122 0.0000 5.169474 140.6685 + 123 0.0000 5.246445 142.7630 + 124 0.0000 5.256249 143.0298 + 125 0.0000 5.326377 144.9381 + 126 0.0000 5.336782 145.2212 + 127 0.0000 5.402008 146.9961 + 128 0.0000 5.572419 151.6332 + 129 0.0000 5.674915 154.4223 + 130 0.0000 5.793495 157.6490 + 131 0.0000 5.994590 163.1211 + 132 0.0000 6.115859 166.4210 + 133 0.0000 6.426173 174.8651 + 134 0.0000 6.507220 177.0705 + 135 0.0000 6.509274 177.1263 + 136 0.0000 6.680336 181.7812 + 137 0.0000 6.711331 182.6246 + 138 0.0000 6.742251 183.4660 + 139 0.0000 6.848572 186.3591 + 140 0.0000 6.916004 188.1940 + 141 0.0000 7.067875 192.3266 + 142 0.0000 7.124066 193.8557 + 143 0.0000 7.174748 195.2348 + 144 0.0000 7.217711 196.4039 + 145 0.0000 7.241255 197.0446 + 146 0.0000 7.259016 197.5279 + 147 0.0000 7.335990 199.6224 + 148 0.0000 7.382481 200.8875 + 149 0.0000 7.437018 202.3715 + 150 0.0000 7.478436 203.4986 + 151 0.0000 7.606755 206.9903 + 152 0.0000 7.642068 207.9512 + 153 0.0000 7.695523 209.4058 + 154 0.0000 7.801657 212.2939 + 155 0.0000 7.963191 216.6895 + 156 0.0000 8.064843 219.4555 + 157 0.0000 8.407286 228.7739 + 158 0.0000 14.154822 385.1723 + 159 0.0000 15.052360 409.5956 + 160 0.0000 15.992596 435.1806 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.667342 -562.3870 + 1 1.0000 -20.640050 -561.6443 + 2 1.0000 -15.799100 -429.9154 + 3 1.0000 -1.603464 -43.6325 + 4 1.0000 -1.399691 -38.0875 + 5 1.0000 -0.948729 -25.8162 + 6 1.0000 -0.782735 -21.2993 + 7 1.0000 -0.729276 -19.8446 + 8 1.0000 -0.683461 -18.5979 + 9 1.0000 -0.622494 -16.9389 + 10 1.0000 -0.528686 -14.3863 + 11 1.0000 -0.461689 -12.5632 + 12 0.0000 0.028166 0.7664 + 13 0.0000 0.079460 2.1622 + 14 0.0000 0.093806 2.5526 + 15 0.0000 0.097962 2.6657 + 16 0.0000 0.126953 3.4546 + 17 0.0000 0.145042 3.9468 + 18 0.0000 0.157006 4.2724 + 19 0.0000 0.172271 4.6877 + 20 0.0000 0.187009 5.0888 + 21 0.0000 0.196190 5.3386 + 22 0.0000 0.205012 5.5787 + 23 0.0000 0.234178 6.3723 + 24 0.0000 0.259673 7.0661 + 25 0.0000 0.294092 8.0027 + 26 0.0000 0.309279 8.4159 + 27 0.0000 0.329731 8.9724 + 28 0.0000 0.363213 9.8835 + 29 0.0000 0.378719 10.3055 + 30 0.0000 0.423350 11.5199 + 31 0.0000 0.516310 14.0495 + 32 0.0000 0.530016 14.4225 + 33 0.0000 0.548600 14.9282 + 34 0.0000 0.570669 15.5287 + 35 0.0000 0.614088 16.7102 + 36 0.0000 0.631924 17.1955 + 37 0.0000 0.647194 17.6111 + 38 0.0000 0.686751 18.6874 + 39 0.0000 0.717880 19.5345 + 40 0.0000 0.719436 19.5768 + 41 0.0000 0.746465 20.3123 + 42 0.0000 0.772310 21.0156 + 43 0.0000 0.785985 21.3877 + 44 0.0000 0.807053 21.9610 + 45 0.0000 0.816327 22.2134 + 46 0.0000 0.859042 23.3757 + 47 0.0000 0.872590 23.7444 + 48 0.0000 0.926581 25.2136 + 49 0.0000 0.938548 25.5392 + 50 0.0000 0.949671 25.8419 + 51 0.0000 0.999484 27.1973 + 52 0.0000 1.045165 28.4404 + 53 0.0000 1.059175 28.8216 + 54 0.0000 1.068454 29.0741 + 55 0.0000 1.098577 29.8938 + 56 0.0000 1.160729 31.5850 + 57 0.0000 1.194726 32.5101 + 58 0.0000 1.251025 34.0421 + 59 0.0000 1.285713 34.9860 + 60 0.0000 1.366624 37.1877 + 61 0.0000 1.423111 38.7248 + 62 0.0000 1.493499 40.6402 + 63 0.0000 1.517655 41.2975 + 64 0.0000 1.522759 41.4364 + 65 0.0000 1.541880 41.9567 + 66 0.0000 1.562815 42.5263 + 67 0.0000 1.604430 43.6588 + 68 0.0000 1.664757 45.3004 + 69 0.0000 1.730675 47.0941 + 70 0.0000 1.762129 47.9500 + 71 0.0000 1.814899 49.3859 + 72 0.0000 1.863327 50.7037 + 73 0.0000 1.952607 53.1331 + 74 0.0000 1.962723 53.4084 + 75 0.0000 2.010342 54.7042 + 76 0.0000 2.079169 56.5771 + 77 0.0000 2.102813 57.2204 + 78 0.0000 2.161712 58.8232 + 79 0.0000 2.174400 59.1684 + 80 0.0000 2.283274 62.1310 + 81 0.0000 2.304220 62.7010 + 82 0.0000 2.322176 63.1896 + 83 0.0000 2.376542 64.6690 + 84 0.0000 2.447346 66.5957 + 85 0.0000 2.469573 67.2005 + 86 0.0000 2.495236 67.8988 + 87 0.0000 2.502746 68.1032 + 88 0.0000 2.519356 68.5552 + 89 0.0000 2.541048 69.1454 + 90 0.0000 2.570962 69.9594 + 91 0.0000 2.601048 70.7781 + 92 0.0000 2.636414 71.7405 + 93 0.0000 2.677503 72.8586 + 94 0.0000 2.751833 74.8812 + 95 0.0000 2.765007 75.2397 + 96 0.0000 2.864106 77.9363 + 97 0.0000 2.908030 79.1315 + 98 0.0000 2.949610 80.2630 + 99 0.0000 3.105625 84.5084 + 100 0.0000 3.153233 85.8038 + 101 0.0000 3.182992 86.6136 + 102 0.0000 3.253846 88.5417 + 103 0.0000 3.461426 94.1902 + 104 0.0000 3.794514 103.2540 + 105 0.0000 3.879327 105.5618 + 106 0.0000 4.027917 109.6052 + 107 0.0000 4.165978 113.3620 + 108 0.0000 4.175309 113.6159 + 109 0.0000 4.239779 115.3703 + 110 0.0000 4.360367 118.6516 + 111 0.0000 4.388326 119.4124 + 112 0.0000 4.571032 124.3841 + 113 0.0000 4.621995 125.7709 + 114 0.0000 4.746684 129.1638 + 115 0.0000 4.814710 131.0149 + 116 0.0000 4.843825 131.8072 + 117 0.0000 4.893885 133.1694 + 118 0.0000 4.970935 135.2660 + 119 0.0000 5.003560 136.1538 + 120 0.0000 5.070488 137.9750 + 121 0.0000 5.094028 138.6155 + 122 0.0000 5.169474 140.6685 + 123 0.0000 5.246445 142.7630 + 124 0.0000 5.256249 143.0298 + 125 0.0000 5.326377 144.9381 + 126 0.0000 5.336782 145.2212 + 127 0.0000 5.402008 146.9961 + 128 0.0000 5.572419 151.6332 + 129 0.0000 5.674915 154.4223 + 130 0.0000 5.793495 157.6490 + 131 0.0000 5.994590 163.1211 + 132 0.0000 6.115859 166.4210 + 133 0.0000 6.426173 174.8651 + 134 0.0000 6.507220 177.0705 + 135 0.0000 6.509274 177.1263 + 136 0.0000 6.680336 181.7812 + 137 0.0000 6.711331 182.6246 + 138 0.0000 6.742251 183.4660 + 139 0.0000 6.848572 186.3591 + 140 0.0000 6.916004 188.1940 + 141 0.0000 7.067875 192.3266 + 142 0.0000 7.124066 193.8557 + 143 0.0000 7.174748 195.2348 + 144 0.0000 7.217711 196.4039 + 145 0.0000 7.241255 197.0446 + 146 0.0000 7.259016 197.5279 + 147 0.0000 7.335990 199.6224 + 148 0.0000 7.382481 200.8875 + 149 0.0000 7.437018 202.3715 + 150 0.0000 7.478436 203.4986 + 151 0.0000 7.606755 206.9903 + 152 0.0000 7.642068 207.9512 + 153 0.0000 7.695523 209.4058 + 154 0.0000 7.801657 212.2939 + 155 0.0000 7.963191 216.6895 + 156 0.0000 8.064843 219.4555 + 157 0.0000 8.407286 228.7739 + 158 0.0000 14.154822 385.1723 + 159 0.0000 15.052360 409.5956 + 160 0.0000 15.992596 435.1806 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.345561 0.000000 + 1 N : 0.343152 0.000000 + 2 O : -0.276973 0.000000 + 3 H : 0.279382 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.866794 s : 3.866794 + pz : 1.392401 p : 4.450072 + px : 1.238373 + py : 1.819298 + dz2 : 0.011778 d : 0.024010 + dxz : -0.002467 + dyz : 0.000923 + dx2y2 : 0.006088 + dxy : 0.007688 + f0 : 0.000506 f : 0.004685 + f+1 : 0.001050 + f-1 : 0.000177 + f+2 : 0.000607 + f-2 : -0.000102 + f+3 : 0.001027 + f-3 : 0.001420 + 1 N s : 3.829671 s : 3.829671 + pz : 1.078704 p : 2.653683 + px : 0.831459 + py : 0.743521 + dz2 : 0.031778 d : 0.143607 + dxz : 0.034581 + dyz : 0.031107 + dx2y2 : 0.023467 + dxy : 0.022674 + f0 : 0.005303 f : 0.029888 + f+1 : 0.009060 + f-1 : 0.005749 + f+2 : 0.002359 + f-2 : 0.000401 + f+3 : 0.002044 + f-3 : 0.004971 + 2 O s : 3.878338 s : 3.878338 + pz : 1.202316 p : 4.327795 + px : 1.851969 + py : 1.273510 + dz2 : 0.014458 d : 0.063049 + dxz : 0.016828 + dyz : 0.029965 + dx2y2 : -0.000091 + dxy : 0.001888 + f0 : 0.002201 f : 0.007790 + f+1 : 0.002370 + f-1 : 0.002772 + f+2 : 0.000058 + f-2 : 0.000495 + f+3 : -0.000023 + f-3 : -0.000083 + 3 H s : 0.620591 s : 0.620591 + pz : 0.016558 p : 0.077665 + px : 0.019993 + py : 0.041115 + dz2 : 0.001635 d : 0.022362 + dxz : 0.011275 + dyz : 0.009561 + dx2y2 : -0.000140 + dxy : 0.000030 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.600228 0.000000 + 1 N : -0.268582 0.000000 + 2 O : 0.234317 0.000000 + 3 H : -0.565963 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.114537 s : 3.114537 + pz : 1.290238 p : 3.904208 + px : 1.179837 + py : 1.434133 + dz2 : 0.073040 d : 0.292428 + dxz : 0.072877 + dyz : 0.008201 + dx2y2 : 0.090936 + dxy : 0.047373 + f0 : 0.016538 f : 0.088599 + f+1 : 0.016026 + f-1 : 0.002098 + f+2 : 0.017888 + f-2 : 0.003019 + f+3 : 0.018034 + f-3 : 0.014997 + 1 N s : 3.003412 s : 3.003412 + pz : 1.228688 p : 2.834473 + px : 0.911477 + py : 0.694308 + dz2 : 0.274624 d : 0.971002 + dxz : 0.307625 + dyz : 0.116249 + dx2y2 : 0.147144 + dxy : 0.125360 + f0 : 0.108255 f : 0.459695 + f+1 : 0.135400 + f-1 : 0.063573 + f+2 : 0.050467 + f-2 : 0.010190 + f+3 : 0.037098 + f-3 : 0.054712 + 2 O s : 3.316782 s : 3.316782 + pz : 1.402125 p : 4.006895 + px : 1.513085 + py : 1.091684 + dz2 : 0.150841 d : 0.324284 + dxz : 0.097786 + dyz : 0.051181 + dx2y2 : 0.016812 + dxy : 0.007662 + f0 : 0.047892 f : 0.117723 + f+1 : 0.031477 + f-1 : 0.021057 + f+2 : 0.011264 + f-2 : 0.004811 + f+3 : 0.000910 + f-3 : 0.000313 + 3 H s : 0.620045 s : 0.620045 + pz : 0.260356 p : 0.551844 + px : 0.130519 + py : 0.160969 + dz2 : 0.130342 d : 0.394074 + dxz : 0.115761 + dyz : 0.120358 + dx2y2 : 0.019826 + dxy : 0.007787 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3456 8.0000 -0.3456 1.9359 1.9359 -0.0000 + 1 N 6.6568 7.0000 0.3432 2.5359 2.5359 -0.0000 + 2 O 8.2770 8.0000 -0.2770 1.7279 1.7279 -0.0000 + 3 H 0.7206 1.0000 0.2794 0.9384 0.9384 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.9182 B( 0-O , 3-H ) : 0.9616 B( 1-N , 2-O ) : 1.6563 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.243 sec +Sum of individual times .... 2.074 sec ( 92.5%) + +Fock matrix formation .... 1.713 sec ( 76.4%) +Diagonalization .... 0.176 sec ( 7.8%) +Density matrix formation .... 0.013 sec ( 0.6%) +Population analysis .... 0.014 sec ( 0.6%) +Initial guess .... 0.009 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.2%) +DIIS solution .... 0.150 sec ( 6.7%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.204 sec +Reference energy ... -204.721959565 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.414 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.420 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.027 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.029 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.040 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.040 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.025 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.360 sec +AO-integral generation ... 0.250 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.055 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.150 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.251 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090612332 +EMP2(bb)= -0.090612332 +EMP2(ab)= -0.516721541 + +Initial guess performed in 0.133 sec +E(0) ... -204.721959565 +E(MP2) ... -0.697946204 +Initial E(tot) ... -205.419905769 + ... 0.188264735 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.419905769 -0.697946204 -0.000000000 0.026570448 2.85 0.000002117 + *** Turning on DIIS *** + 1 -205.390578931 -0.668619366 0.029326838 0.011586451 2.70 0.057991338 + 2 -205.410110549 -0.688150985 -0.019531619 0.005849654 2.76 0.060912114 + 3 -205.413820925 -0.691861360 -0.003710375 0.002407647 2.70 0.075315270 + 4 -205.415392906 -0.693433341 -0.001571981 0.001611394 2.79 0.082176646 + 5 -205.415952170 -0.693992605 -0.000559264 0.000867690 2.82 0.087911338 + 6 -205.416063986 -0.694104421 -0.000111816 0.000513838 2.76 0.090721550 + 7 -205.416108262 -0.694148697 -0.000044276 0.000202818 2.76 0.091957452 + 8 -205.416119983 -0.694160418 -0.000011721 0.000104722 2.77 0.092407373 + 9 -205.416115814 -0.694156250 0.000004168 0.000027657 2.74 0.092537333 + 10 -205.416120241 -0.694160676 -0.000004427 0.000010039 2.72 0.092574139 + 11 -205.416117896 -0.694158331 0.000002345 0.000008176 2.77 0.092567804 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.721959565 +E(CORR) ... -0.694158331 +E(TOT) ... -205.416117896 +Singles norm **1/2 ... 0.092567804 ( 0.046283902, 0.046283902) +T1 diagnostic ... 0.021818441 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.062668 + 10a-> 13a 10b-> 13b 0.052181 + 8a-> 13a -1a-> -1a 0.043934 + 8b-> 13b -1b-> -1b 0.043934 + 10a-> 13a 8b-> 13b 0.035013 + 8a-> 13a 10b-> 13b 0.035013 + 10b-> 13b -1b-> -1b 0.032930 + 10a-> 13a -1a-> -1a 0.032930 + 11a-> 13a 11b-> 13b 0.028138 + 11a-> 26a -1a-> -1a 0.027776 + 11b-> 26b -1b-> -1b 0.027776 + 11a-> 26a 11b-> 26b 0.027295 + 5a-> 13a 5b-> 13b 0.025719 + 11a-> 26a 10b-> 13b 0.022503 + 10a-> 13a 11b-> 26b 0.022503 + 8a-> 22a 8b-> 13b 0.022396 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034774483 + alpha-alpha-alpha ... -0.000899964 ( 2.6%) + alpha-alpha-beta ... -0.016487278 ( 47.4%) + alpha-beta -beta ... -0.016487278 ( 47.4%) + beta -beta -beta ... -0.000899964 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034774483 + +Final correlation energy ... -0.728932814 +E(CCSD) ... -205.416117896 +E(CCSD(T)) ... -205.450892379 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209900113 sqrt= 1.099954596 +W(HF) = 0.826514511 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.257162 0.000000 + 1 N : 0.153221 -0.000000 + 2 O : -0.162209 -0.000000 + 3 H : 0.266150 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.846232 s : 3.846232 + pz : 1.374093 p : 4.346161 + px : 1.234906 + py : 1.737162 + dz2 : 0.016355 d : 0.056275 + dxz : 0.005763 + dyz : 0.007912 + dx2y2 : 0.011137 + dxy : 0.015109 + f0 : 0.001216 f : 0.008494 + f+1 : 0.001485 + f-1 : 0.000808 + f+2 : 0.001158 + f-2 : 0.000578 + f+3 : 0.001294 + f-3 : 0.001955 + 1 N s : 3.880188 s : 3.880188 + pz : 1.044599 p : 2.763369 + px : 0.868048 + py : 0.850722 + dz2 : 0.035955 d : 0.173918 + dxz : 0.046090 + dyz : 0.031399 + dx2y2 : 0.029085 + dxy : 0.031389 + f0 : 0.004797 f : 0.029304 + f+1 : 0.008779 + f-1 : 0.004674 + f+2 : 0.002787 + f-2 : 0.000983 + f+3 : 0.002181 + f-3 : 0.005103 + 2 O s : 3.867327 s : 3.867327 + pz : 1.190598 p : 4.199746 + px : 1.771043 + py : 1.238105 + dz2 : 0.016999 d : 0.084768 + dxz : 0.023683 + dyz : 0.029705 + dx2y2 : 0.006350 + dxy : 0.008032 + f0 : 0.002267 f : 0.010368 + f+1 : 0.002786 + f-1 : 0.002552 + f+2 : 0.000687 + f-2 : 0.001032 + f+3 : 0.000554 + f-3 : 0.000491 + 3 H s : 0.632837 s : 0.632837 + pz : 0.010876 p : 0.081787 + px : 0.023772 + py : 0.047139 + dz2 : 0.000500 d : 0.019225 + dxz : 0.010156 + dyz : 0.007970 + dx2y2 : 0.000375 + dxy : 0.000224 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.616938 0.000000 + 1 N : -0.318766 0.000000 + 2 O : 0.268006 -0.000000 + 3 H : -0.566178 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.121833 s : 3.121833 + pz : 1.278292 p : 3.842060 + px : 1.188502 + py : 1.375267 + dz2 : 0.079818 d : 0.323607 + dxz : 0.078040 + dyz : 0.013976 + dx2y2 : 0.097685 + dxy : 0.054088 + f0 : 0.017497 f : 0.095562 + f+1 : 0.016827 + f-1 : 0.003025 + f+2 : 0.018153 + f-2 : 0.003475 + f+3 : 0.019466 + f-3 : 0.017120 + 1 N s : 3.008621 s : 3.008621 + pz : 1.199014 p : 2.882598 + px : 0.922873 + py : 0.760710 + dz2 : 0.280379 d : 0.979929 + dxz : 0.305226 + dyz : 0.113112 + dx2y2 : 0.154662 + dxy : 0.126550 + f0 : 0.105255 f : 0.447617 + f+1 : 0.132359 + f-1 : 0.062963 + f+2 : 0.048172 + f-2 : 0.010650 + f+3 : 0.037985 + f-3 : 0.050232 + 2 O s : 3.318605 s : 3.318605 + pz : 1.392964 p : 3.931252 + px : 1.461042 + py : 1.077246 + dz2 : 0.155116 d : 0.355754 + dxz : 0.100644 + dyz : 0.062893 + dx2y2 : 0.022328 + dxy : 0.014772 + f0 : 0.047937 f : 0.126383 + f+1 : 0.032487 + f-1 : 0.025671 + f+2 : 0.011459 + f-2 : 0.006464 + f+3 : 0.001450 + f-3 : 0.000914 + 3 H s : 0.622270 s : 0.622270 + pz : 0.263439 p : 0.560209 + px : 0.131579 + py : 0.165192 + dz2 : 0.129605 d : 0.383699 + dxz : 0.111944 + dyz : 0.113645 + dx2y2 : 0.020219 + dxy : 0.008286 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2572 8.0000 -0.2572 2.3023 1.8417 0.4607 + 1 N 6.8468 7.0000 0.1532 2.8261 2.3496 0.4765 + 2 O 8.1622 8.0000 -0.1622 2.1303 1.6329 0.4974 + 3 H 0.7338 1.0000 0.2662 0.9605 0.8901 0.0704 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8534 B( 0-O , 3-H ) : 0.8893 B( 1-N , 2-O ) : 1.5147 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 48.124 sec + +Fock Matrix Formation ... 0.204 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.3%) +DIIS Solver ... 1.393 sec ( 2.9%) +State Vector Update ... 0.070 sec ( 0.1%) +Sigma-vector construction ... 31.673 sec ( 65.8%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.022 sec ( 0.1% of sigma) + (0-ext) ... 0.059 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.022 sec ( 0.1% of sigma) + (2-ext) ... 0.800 sec ( 2.5% of sigma) + (4-ext) ... 17.055 sec ( 53.8% of sigma) + ... 1.178 sec ( 3.7% of sigma) + ... 0.003 sec ( 0.0% of sigma) + (1-ext) ... 0.007 sec ( 0.0% of sigma) + (1-ext) ... 0.093 sec ( 0.3% of sigma) + Fock-dressing ... 1.822 sec ( 5.8% of sigma) + (ik|jl)-dressing ... 0.063 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 8.299 sec ( 26.2% of sigma) + Pair energies ... 0.004 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.799 sec ( 14.1% of ALL) + I/O of integral and amplitudes ... 0.782 sec ( 11.5% of (T)) + External N**7 contributions ... 3.902 sec ( 57.4% of (T)) + Internal N**7 contributions ... 0.311 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.728 sec ( 25.4% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.450892378765 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.000644675 -0.005306731 -0.001968645 + 2 N : -0.001489842 -0.005437780 0.003037599 + 3 O : 0.000819924 0.004949522 -0.003027389 + 4 H : 0.000025243 0.005794988 0.001958434 + +Norm of the cartesian gradient ... 0.012050799 +RMS gradient ... 0.003478766 +MAX gradient ... 0.005794988 + +------- +TIMINGS +------- + +Total numerical gradient time ... 317.740 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 167.02 cm**-1 + 7: 617.77 cm**-1 + 8: 860.98 cm**-1 + 9: 1334.13 cm**-1 + 10: 1677.78 cm**-1 + 11: 3490.36 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 0.002419 -0.573496 -0.147628 -0.032936 -0.104066 0.009267 + 1 0.030493 0.003288 0.077499 -0.031771 -0.001651 -0.008211 + 2 0.005768 0.328732 -0.121709 -0.059546 -0.034524 -0.059836 + 3 -0.109123 0.209207 0.376784 0.018547 -0.041138 0.001806 + 4 0.078263 -0.013062 0.011246 -0.026386 -0.066178 0.002600 + 5 -0.025227 -0.272234 0.083907 -0.004868 0.632405 -0.003007 + 6 0.057938 0.381412 -0.183435 -0.038774 0.107244 -0.001963 + 7 -0.049251 -0.014299 -0.032043 0.025872 0.052098 -0.002589 + 8 0.003877 -0.113910 0.046726 0.063462 -0.524401 0.000800 + 9 0.558368 0.141665 0.018907 0.880464 0.521203 -0.141015 + 10 -0.789807 0.356273 -0.877754 0.460271 0.118891 0.135297 + 11 0.197470 0.373259 0.024177 0.005487 0.083477 0.978798 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 167.02 0.011433 57.78 0.021361 (-0.012142 -0.137720 0.047401) + 7: 617.77 0.030644 154.86 0.015480 ( 0.106052 0.005218 -0.064851) + 8: 860.98 0.031968 161.55 0.011587 ( 0.088192 -0.047263 -0.039689) + 9: 1334.13 0.028425 143.65 0.006649 ( 0.071631 0.026185 -0.028845) + 10: 1677.78 0.023785 120.20 0.004424 (-0.047309 0.003629 0.046612) + 11: 3490.36 0.016351 82.63 0.001462 (-0.018994 0.005106 0.032788) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 167.02 E(vib) ... 0.39 +freq. 617.77 E(vib) ... 0.09 +freq. 860.98 E(vib) ... 0.04 +freq. 1334.13 E(vib) ... 0.01 +freq. 1677.78 E(vib) ... 0.00 +freq. 3490.36 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.45089238 Eh +Zero point energy ... 0.01856259 Eh 11.65 kcal/mol +Thermal vibrational correction ... 0.00083934 Eh 0.53 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42865791 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00367188 Eh 2.30 kcal/mol +Non-thermal (ZPE) correction 0.01856259 Eh 11.65 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02223447 Eh 13.95 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42865791 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.42771370 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 3.052838 0.418016 0.368677 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00145755 Eh 0.91 kcal/mol +Rotational entropy ... 0.00986677 Eh 6.19 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02912664 Eh 18.28 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00986677 Eh 6.19 kcal/mol| +| sn= 2 | S(rot)= 0.00921231 Eh 5.78 kcal/mol| +| sn= 3 | S(rot)= 0.00882948 Eh 5.54 kcal/mol| +| sn= 4 | S(rot)= 0.00855785 Eh 5.37 kcal/mol| +| sn= 5 | S(rot)= 0.00834716 Eh 5.24 kcal/mol| +| sn= 6 | S(rot)= 0.00817502 Eh 5.13 kcal/mol| +| sn= 7 | S(rot)= 0.00802947 Eh 5.04 kcal/mol| +| sn= 8 | S(rot)= 0.00790340 Eh 4.96 kcal/mol| +| sn= 9 | S(rot)= 0.00779219 Eh 4.89 kcal/mol| +| sn=10 | S(rot)= 0.00769271 Eh 4.83 kcal/mol| +| sn=11 | S(rot)= 0.00760272 Eh 4.77 kcal/mol| +| sn=12 | S(rot)= 0.00752056 Eh 4.72 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.42771370 Eh +Total entropy correction ... -0.02912664 Eh -18.28 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.45684034 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00594796 Eh -3.73 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.450892377 Eh +Current gradient norm .... 0.012050796 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.035864031 0.093745355 0.149079458 0.475954658 0.503730623 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999933854 +Lowest eigenvalues of augmented Hessian: + -0.000044694 0.093602841 0.131772487 0.474607393 0.503199470 +Length of the computed step .... 0.011502356 +The final length of the internal step .... 0.011502356 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0046958173 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0023806664 RMS(Int)= 0.0046950233 + Iter 1: RMS(Cart)= 0.0000057376 RMS(Int)= 0.0000096247 + Iter 2: RMS(Cart)= 0.0000000219 RMS(Int)= 0.0000000376 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0019373712 0.0001000000 NO + MAX gradient 0.0034854291 0.0003000000 NO + RMS step 0.0046958173 0.0020000000 NO + MAX step 0.0074647370 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0040 Max(Angles) 0.13 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4333 -0.000584 0.0040 1.4372 + 2. B(O 2,N 1) 1.1760 0.003485 -0.0030 1.1730 + 3. B(H 3,O 0) 0.9717 0.002951 -0.0031 0.9686 + 4. A(N 1,O 0,H 3) 101.98 0.000375 -0.13 101.85 + 5. A(O 0,N 1,O 2) 110.53 -0.001087 0.13 110.66 + 6. D(O 2,N 1,O 0,H 3) -163.64 0.009651 0.00 -163.64 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.763752 0.002833 0.141006 + N 0.654211 -0.135637 -0.048364 + O 0.930839 -0.044705 -1.184624 + H -0.821298 0.177509 1.091982 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.443282 0.005354 0.266463 + 1 N 7.0000 0 14.007 1.236280 -0.256317 -0.091394 + 2 O 8.0000 0 15.999 1.759031 -0.084480 -2.238616 + 3 H 1.0000 0 1.008 -1.552028 0.335443 2.063547 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.437238445873 0.00000000 0.00000000 + O 2 1 0 1.172979080697 110.66091993 0.00000000 + H 1 2 3 0.968596040996 101.85011139 196.36363645 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.715987051843 0.00000000 0.00000000 + O 2 1 0 2.216609223336 110.66091993 0.00000000 + H 1 2 3 1.830381251883 101.85011139 196.36363645 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.418800611762 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.972e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7221837623 0.000000000000 0.00020671 0.00000548 0.0011137 0.7000 + 1 -204.7221899696 -0.000006207284 0.00016082 0.00000455 0.0008366 0.7000 + ***Turning on DIIS*** + 2 -204.7221950009 -0.000005031326 0.00041344 0.00001195 0.0006257 0.0000 + 3 -204.7217923596 0.000402641308 0.00012809 0.00000428 0.0001899 0.0000 + 4 -204.7221856950 -0.000393335385 0.00003582 0.00000149 0.0000725 0.0000 + 5 -204.7224773855 -0.000291690503 0.00001786 0.00000051 0.0000424 0.0000 + 6 -204.7221584600 0.000318925484 0.00001576 0.00000033 0.0000168 0.0000 + 7 -204.7222121011 -0.000053641022 0.00000363 0.00000010 0.0000054 0.0000 + 8 -204.7222253410 -0.000013239902 0.00000175 0.00000005 0.0000026 0.0000 + 9 -204.7222048437 0.000020497238 0.00000082 0.00000003 0.0000014 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 10 CYCLES * + ***************************************************** + +Total Energy : -204.72221354 Eh -5570.77464 eV + Last Energy change ... -8.7012e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.8604e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.204 sec +Reference energy ... -204.722210928 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.429 sec +AO-integral generation ... 0.143 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.432 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.026 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.025 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.029 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.040 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.023 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.350 sec +AO-integral generation ... 0.243 sec +Half transformation ... 0.043 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.149 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.253 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090574584 +EMP2(bb)= -0.090574584 +EMP2(ab)= -0.516535503 + +Initial guess performed in 0.134 sec +E(0) ... -204.722210928 +E(MP2) ... -0.697684671 +Initial E(tot) ... -205.419895598 + ... 0.188056494 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.419895598 -0.697684671 -0.000000000 0.026294135 2.67 0.000002008 + *** Turning on DIIS *** + 1 -205.390659504 -0.668448577 0.029236094 0.011441807 2.67 0.057970960 + 2 -205.410160691 -0.687949763 -0.019501187 0.005767728 2.74 0.060882497 + 3 -205.413864025 -0.691653097 -0.003703334 0.002386854 2.72 0.075292933 + 4 -205.415432793 -0.693221865 -0.001568768 0.001652156 2.74 0.082163277 + 5 -205.415993324 -0.693782397 -0.000560531 0.000884689 2.77 0.087941775 + 6 -205.416106482 -0.693895554 -0.000113157 0.000521759 2.75 0.090797981 + 7 -205.416151613 -0.693940686 -0.000045132 0.000202489 2.80 0.092064189 + 8 -205.416163610 -0.693952682 -0.000011997 0.000104362 2.80 0.092522083 + 9 -205.416159393 -0.693948466 0.000004217 0.000027272 2.72 0.092653565 + 10 -205.416163853 -0.693952926 -0.000004460 0.000009575 2.69 0.092690637 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.722210928 +E(CORR) ... -0.693952926 +E(TOT) ... -205.416163853 +Singles norm **1/2 ... 0.092690637 ( 0.046345318, 0.046345318) +T1 diagnostic ... 0.021847393 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.063152 + 10a-> 13a 10b-> 13b 0.050796 + 8b-> 13b -1b-> -1b 0.043289 + 8a-> 13a -1a-> -1a 0.043289 + 10a-> 13a 8b-> 13b 0.034572 + 8a-> 13a 10b-> 13b 0.034572 + 10a-> 13a -1a-> -1a 0.033935 + 10b-> 13b -1b-> -1b 0.033935 + 11a-> 13a 11b-> 13b 0.028001 + 11a-> 26a -1a-> -1a 0.027373 + 11b-> 26b -1b-> -1b 0.027373 + 11a-> 26a 11b-> 26b 0.027188 + 5a-> 13a 5b-> 13b 0.025749 + 8a-> 22a 8b-> 13b 0.022802 + 8a-> 13a 8b-> 22b 0.022802 + 10a-> 13a 11b-> 26b 0.022291 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034747773 + alpha-alpha-alpha ... -0.000899558 ( 2.6%) + alpha-alpha-beta ... -0.016474328 ( 47.4%) + alpha-beta -beta ... -0.016474328 ( 47.4%) + beta -beta -beta ... -0.000899558 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034747773 + +Final correlation energy ... -0.728700699 +E(CCSD) ... -205.416163853 +E(CCSD(T)) ... -205.450911626 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209763096 sqrt= 1.099892311 +W(HF) = 0.826608121 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 45.337 sec + +Fock Matrix Formation ... 0.204 sec ( 0.5%) +Initial Guess ... 0.134 sec ( 0.3%) +DIIS Solver ... 1.338 sec ( 3.0%) +State Vector Update ... 0.064 sec ( 0.1%) +Sigma-vector construction ... 28.650 sec ( 63.2%) + <0|H|D> ... 0.003 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.018 sec ( 0.1% of sigma) + (0-ext) ... 0.055 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (2-ext) ... 0.734 sec ( 2.6% of sigma) + (4-ext) ... 15.445 sec ( 53.9% of sigma) + ... 1.057 sec ( 3.7% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.087 sec ( 0.3% of sigma) + Fock-dressing ... 1.682 sec ( 5.9% of sigma) + (ik|jl)-dressing ... 0.058 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 7.420 sec ( 25.9% of sigma) + Pair energies ... 0.004 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.758 sec ( 14.9% of ALL) + I/O of integral and amplitudes ... 0.783 sec ( 11.6% of (T)) + External N**7 contributions ... 3.900 sec ( 57.7% of (T)) + Internal N**7 contributions ... 0.318 sec ( 4.7% of (T)) + N**6 triples energy contributions ... 1.685 sec ( 24.9% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.450911626326 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.000523287 -0.004414997 0.001556233 + 2 N : -0.000769599 -0.004790388 -0.001210427 + 3 O : 0.000682133 0.004281883 0.000869996 + 4 H : 0.000610754 0.004923501 -0.001215802 + +Norm of the cartesian gradient ... 0.009635450 +RMS gradient ... 0.002781515 +MAX gradient ... 0.004923501 + +------- +TIMINGS +------- + +Total numerical gradient time ... 307.127 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.450911626 Eh +Current gradient norm .... 0.009635450 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999989248 +Lowest eigenvalues of augmented Hessian: + -0.000002942 0.090344072 0.136066266 0.484644253 0.563924562 +Length of the computed step .... 0.004637269 +The final length of the internal step .... 0.004637269 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0018931572 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0018389973 RMS(Int)= 0.0018931438 + Iter 1: RMS(Cart)= 0.0000036573 RMS(Int)= 0.0000058131 + Iter 2: RMS(Cart)= 0.0000000106 RMS(Int)= 0.0000000120 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000192493 0.0000050000 NO + RMS gradient 0.0003672170 0.0001000000 NO + MAX gradient 0.0006344348 0.0003000000 NO + RMS step 0.0018931572 0.0020000000 YES + MAX step 0.0041186744 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0004 Max(Angles) 0.24 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4372 0.000006 0.0004 1.4377 + 2. B(O 2,N 1) 1.1730 -0.000349 0.0001 1.1731 + 3. B(H 3,O 0) 0.9686 -0.000341 -0.0000 0.9686 + 4. A(N 1,O 0,H 3) 101.85 -0.000410 0.24 102.09 + 5. A(O 0,N 1,O 2) 110.66 0.000634 -0.11 110.55 + 6. D(O 2,N 1,O 0,H 3) -163.64 0.009122 -0.00 -163.64 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.762385 0.003114 0.141508 + N 0.655875 -0.136165 -0.048432 + O 0.930004 -0.044597 -1.185322 + H -0.823493 0.177648 1.092247 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.440699 0.005885 0.267411 + 1 N 7.0000 0 14.007 1.239425 -0.257315 -0.091524 + 2 O 8.0000 0 15.999 1.757452 -0.084276 -2.239934 + 3 H 1.0000 0 1.008 -1.556176 0.335706 2.064047 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.437685227725 0.00000000 0.00000000 + O 2 1 0 1.173051216546 110.54917560 0.00000000 + H 1 2 3 0.968556185441 102.08609405 196.36363645 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.716831347184 0.00000000 0.00000000 + O 2 1 0 2.216745540336 110.54917560 0.00000000 + H 1 2 3 1.830305935800 102.08609405 196.36363645 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.414015775547 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.973e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7221862363 0.000000000000 0.00006964 0.00000229 0.0005734 0.7000 + 1 -204.7221875294 -0.000001293186 0.00006107 0.00000198 0.0004656 0.7000 + ***Turning on DIIS*** + 2 -204.7221885999 -0.000001070493 0.00017142 0.00000532 0.0003723 0.0000 + 3 -204.7223019463 -0.000113346384 0.00006986 0.00000210 0.0001233 0.0000 + 4 -204.7221910715 0.000110874794 0.00001395 0.00000059 0.0000225 0.0000 + 5 -204.7220903047 0.000100766783 0.00000664 0.00000028 0.0000207 0.0000 + 6 -204.7222178365 -0.000127531794 0.00000762 0.00000029 0.0000100 0.0000 + 7 -204.7221776290 0.000040207553 0.00000708 0.00000025 0.0000067 0.0000 + 8 -204.7221865686 -0.000008939637 0.00000428 0.00000015 0.0000034 0.0000 + 9 -204.7221993887 -0.000012820095 0.00000191 0.00000007 0.0000014 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 10 CYCLES * + ***************************************************** + +Total Energy : -204.72218952 Eh -5570.77399 eV + Last Energy change ... 9.8733e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.9812e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.204 sec +Reference energy ... -204.722192117 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.416 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.427 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.025 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.025 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.029 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.040 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.023 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.041 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.024 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.358 sec +AO-integral generation ... 0.248 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.055 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.155 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.257 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090573912 +EMP2(bb)= -0.090573912 +EMP2(ab)= -0.516550020 + +Initial guess performed in 0.134 sec +E(0) ... -204.722192117 +E(MP2) ... -0.697697844 +Initial E(tot) ... -205.419889961 + ... 0.188083489 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.419889961 -0.697697844 -0.000000000 0.026276978 2.75 0.000001039 + *** Turning on DIIS *** + 1 -205.390649155 -0.668457038 0.029240806 0.011431175 2.66 0.057978472 + 2 -205.410153784 -0.687961667 -0.019504629 0.005763646 2.71 0.060888800 + 3 -205.413858375 -0.691666258 -0.003704591 0.002385423 2.74 0.075302281 + 4 -205.415427575 -0.693235458 -0.001569200 0.001653508 2.71 0.082173416 + 5 -205.415988357 -0.693796240 -0.000560782 0.000885788 2.81 0.087954605 + 6 -205.416101588 -0.693909471 -0.000113231 0.000522762 2.78 0.090813010 + 7 -205.416146779 -0.693954662 -0.000045191 0.000203026 2.81 0.092081864 + 8 -205.416158816 -0.693966699 -0.000012037 0.000104665 2.79 0.092541244 + 9 -205.416154599 -0.693962482 0.000004217 0.000027351 2.72 0.092673474 + 10 -205.416159071 -0.693966954 -0.000004472 0.000009799 2.72 0.092710705 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.722192117 +E(CORR) ... -0.693966954 +E(TOT) ... -205.416159071 +Singles norm **1/2 ... 0.092710705 ( 0.046355353, 0.046355353) +T1 diagnostic ... 0.021852123 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.063288 + 10a-> 13a 10b-> 13b 0.050727 + 8a-> 13a -1a-> -1a 0.043264 + 8b-> 13b -1b-> -1b 0.043264 + 10a-> 13a 8b-> 13b 0.034625 + 8a-> 13a 10b-> 13b 0.034625 + 10b-> 13b -1b-> -1b 0.033966 + 10a-> 13a -1a-> -1a 0.033966 + 11a-> 13a 11b-> 13b 0.027976 + 11a-> 26a -1a-> -1a 0.027295 + 11b-> 26b -1b-> -1b 0.027295 + 11a-> 26a 11b-> 26b 0.027155 + 5a-> 13a 5b-> 13b 0.025762 + 8a-> 13a 8b-> 22b 0.022829 + 8a-> 22a 8b-> 13b 0.022829 + 11a-> 26a 10b-> 13b 0.022252 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034753329 + alpha-alpha-alpha ... -0.000899519 ( 2.6%) + alpha-alpha-beta ... -0.016477145 ( 47.4%) + alpha-beta -beta ... -0.016477145 ( 47.4%) + beta -beta -beta ... -0.000899519 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034753329 + +Final correlation energy ... -0.728720283 +E(CCSD) ... -205.416159071 +E(CCSD(T)) ... -205.450912400 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209806096 sqrt= 1.099911858 +W(HF) = 0.826578741 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 45.053 sec + +Fock Matrix Formation ... 0.204 sec ( 0.5%) +Initial Guess ... 0.134 sec ( 0.3%) +DIIS Solver ... 1.280 sec ( 2.8%) +State Vector Update ... 0.066 sec ( 0.1%) +Sigma-vector construction ... 28.822 sec ( 64.0%) + <0|H|D> ... 0.003 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.019 sec ( 0.1% of sigma) + (0-ext) ... 0.055 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (2-ext) ... 0.727 sec ( 2.5% of sigma) + (4-ext) ... 15.522 sec ( 53.9% of sigma) + ... 1.164 sec ( 4.0% of sigma) + ... 0.004 sec ( 0.0% of sigma) + (1-ext) ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.084 sec ( 0.3% of sigma) + Fock-dressing ... 1.649 sec ( 5.7% of sigma) + (ik|jl)-dressing ... 0.058 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 7.410 sec ( 25.7% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.757 sec ( 15.0% of ALL) + I/O of integral and amplitudes ... 0.658 sec ( 9.7% of (T)) + External N**7 contributions ... 3.898 sec ( 57.7% of (T)) + Internal N**7 contributions ... 0.317 sec ( 4.7% of (T)) + N**6 triples energy contributions ... 1.570 sec ( 23.2% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.450912399720 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.000361883 -0.004362616 0.001303564 + 2 N : -0.000312102 -0.004900531 -0.000690996 + 3 O : 0.000424088 0.004324178 0.000649015 + 4 H : 0.000249898 0.004938969 -0.001261583 + +Norm of the cartesian gradient ... 0.009528892 +RMS gradient ... 0.002750754 +MAX gradient ... 0.004938969 + +------- +TIMINGS +------- + +Total numerical gradient time ... 315.432 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.450912400 Eh +Current gradient norm .... 0.009528892 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999998567 +Lowest eigenvalues of augmented Hessian: + -0.000000614 0.124556784 0.132968604 0.474355480 0.583497403 +Length of the computed step .... 0.001692902 +The final length of the internal step .... 0.001692902 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0006911243 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0005116521 RMS(Int)= 0.0006911703 + Iter 1: RMS(Cart)= 0.0000002540 RMS(Int)= 0.0000003735 + Iter 2: RMS(Cart)= 0.0000000002 RMS(Int)= 0.0000000002 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000007734 0.0000050000 YES + RMS gradient 0.0001913503 0.0001000000 NO + MAX gradient 0.0003144986 0.0003000000 NO + RMS step 0.0006911243 0.0020000000 YES + MAX step 0.0010553371 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0006 Max(Angles) 0.05 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4377 0.000082 -0.0006 1.4371 + 2. B(O 2,N 1) 1.1731 -0.000136 0.0002 1.1732 + 3. B(H 3,O 0) 0.9686 -0.000299 0.0004 0.9689 + 4. A(N 1,O 0,H 3) 102.09 0.000079 -0.05 102.04 + 5. A(O 0,N 1,O 2) 110.55 -0.000314 0.04 110.59 + 6. D(O 2,N 1,O 0,H 3) -163.64 0.009084 -0.00 -163.64 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 4 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.762526 0.002995 0.141250 + N 0.655236 -0.136017 -0.048384 + O 0.930303 -0.044627 -1.185249 + H -0.823011 0.177650 1.092383 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.440965 0.005659 0.266925 + 1 N 7.0000 0 14.007 1.238216 -0.257035 -0.091433 + 2 O 8.0000 0 15.999 1.758017 -0.084333 -2.239797 + 3 H 1.0000 0 1.008 -1.555266 0.335709 2.064306 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.437126767359 0.00000000 0.00000000 + O 2 1 0 1.173233224116 110.58655321 0.00000000 + H 1 2 3 0.968925632602 102.03744705 196.36363645 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.715776010037 0.00000000 0.00000000 + O 2 1 0 2.217089484797 110.58655321 0.00000000 + H 1 2 3 1.831004089754 102.03744705 196.36363645 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.416314614487 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.973e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7221902631 0.000000000000 0.00002806 0.00000088 0.0001995 0.7000 + 1 -204.7221904392 -0.000000176120 0.00002243 0.00000073 0.0001616 0.7000 + ***Turning on DIIS*** + 2 -204.7221905838 -0.000000144543 0.00005378 0.00000190 0.0001282 0.0000 + 3 -204.7222062053 -0.000015621468 0.00001843 0.00000067 0.0000405 0.0000 + 4 -204.7221939262 0.000012279096 0.00000387 0.00000019 0.0000074 0.0000 + 5 -204.7221899877 0.000003938501 0.00000272 0.00000009 0.0000044 0.0000 + 6 -204.7221862370 0.000003750683 0.00000142 0.00000006 0.0000025 0.0000 + 7 -204.7221933258 -0.000007088795 0.00000180 0.00000007 0.0000019 0.0000 + 8 -204.7221897301 0.000003595661 0.00000135 0.00000005 0.0000010 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + +Total Energy : -204.72219059 Eh -5570.77402 eV + Last Energy change ... -8.6037e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.5312e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.204 sec +Reference energy ... -204.722191045 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.455 sec +AO-integral generation ... 0.142 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.461 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.026 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.025 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.029 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.040 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.025 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.041 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.025 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.356 sec +AO-integral generation ... 0.248 sec +Half transformation ... 0.044 sec +J-integral sorting ... 0.051 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.157 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.253 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090575951 +EMP2(bb)= -0.090575951 +EMP2(ab)= -0.516551541 + +Initial guess performed in 0.134 sec +E(0) ... -204.722191045 +E(MP2) ... -0.697703443 +Initial E(tot) ... -205.419894489 + ... 0.188081509 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.419894489 -0.697703443 -0.000000000 0.026305613 2.80 0.000000755 + *** Turning on DIIS *** + 1 -205.390652512 -0.668461466 0.029241977 0.011445301 2.68 0.057974035 + 2 -205.410156813 -0.687965768 -0.019504301 0.005771576 2.74 0.060886003 + 3 -205.413861280 -0.691670235 -0.003704467 0.002387140 2.72 0.075296523 + 4 -205.415430438 -0.693239393 -0.001569157 0.001649275 2.74 0.082165929 + 5 -205.415990906 -0.693799861 -0.000560468 0.000883761 2.81 0.087941362 + 6 -205.416103969 -0.693912923 -0.000113062 0.000521545 2.74 0.090794403 + 7 -205.416149052 -0.693958007 -0.000045084 0.000202783 2.81 0.092059175 + 8 -205.416161042 -0.693969997 -0.000011990 0.000104540 2.76 0.092517060 + 9 -205.416156831 -0.693965786 0.000004211 0.000027343 2.72 0.092648804 + 10 -205.416161293 -0.693970248 -0.000004462 0.000009728 2.70 0.092685924 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.722191045 +E(CORR) ... -0.693970248 +E(TOT) ... -205.416161293 +Singles norm **1/2 ... 0.092685924 ( 0.046342962, 0.046342962) +T1 diagnostic ... 0.021846282 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.063194 + 10a-> 13a 10b-> 13b 0.050859 + 8b-> 13b -1b-> -1b 0.043324 + 8a-> 13a -1a-> -1a 0.043324 + 8a-> 13a 10b-> 13b 0.034636 + 10a-> 13a 8b-> 13b 0.034636 + 10a-> 13a -1a-> -1a 0.033863 + 10b-> 13b -1b-> -1b 0.033863 + 11a-> 13a 11b-> 13b 0.028000 + 11b-> 26b -1b-> -1b 0.027380 + 11a-> 26a -1a-> -1a 0.027380 + 11a-> 26a 11b-> 26b 0.027215 + 5a-> 13a 5b-> 13b 0.025747 + 8a-> 22a 8b-> 13b 0.022788 + 8a-> 13a 8b-> 22b 0.022788 + 10a-> 13a 11b-> 26b 0.022300 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034751543 + alpha-alpha-alpha ... -0.000899549 ( 2.6%) + alpha-alpha-beta ... -0.016476223 ( 47.4%) + alpha-beta -beta ... -0.016476223 ( 47.4%) + beta -beta -beta ... -0.000899549 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034751543 + +Final correlation energy ... -0.728721791 +E(CCSD) ... -205.416161293 +E(CCSD(T)) ... -205.450912837 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209790798 sqrt= 1.099904904 +W(HF) = 0.826589193 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 45.199 sec + +Fock Matrix Formation ... 0.204 sec ( 0.5%) +Initial Guess ... 0.134 sec ( 0.3%) +DIIS Solver ... 1.326 sec ( 2.9%) +State Vector Update ... 0.064 sec ( 0.1%) +Sigma-vector construction ... 28.831 sec ( 63.8%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (0-ext) ... 0.053 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (2-ext) ... 0.734 sec ( 2.5% of sigma) + (4-ext) ... 15.656 sec ( 54.3% of sigma) + ... 1.093 sec ( 3.8% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.085 sec ( 0.3% of sigma) + Fock-dressing ... 1.644 sec ( 5.7% of sigma) + (ik|jl)-dressing ... 0.058 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 7.385 sec ( 25.6% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.761 sec ( 15.0% of ALL) + I/O of integral and amplitudes ... 0.741 sec ( 11.0% of (T)) + External N**7 contributions ... 3.878 sec ( 57.4% of (T)) + Internal N**7 contributions ... 0.307 sec ( 4.5% of (T)) + N**6 triples energy contributions ... 1.574 sec ( 23.3% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.450912836619 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.000278921 -0.004451025 0.000980266 + 2 N : -0.000603639 -0.004878461 -0.000567677 + 3 O : 0.000579687 0.004328544 0.000498099 + 4 H : 0.000302873 0.005000942 -0.000910687 + +Norm of the cartesian gradient ... 0.009517736 +RMS gradient ... 0.002747534 +MAX gradient ... 0.005000942 + +------- +TIMINGS +------- + +Total numerical gradient time ... 316.658 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: -35.02 cm**-1 ***imaginary mode*** + 7: 668.66 cm**-1 + 8: 1024.36 cm**-1 + 9: 1292.30 cm**-1 + 10: 1750.25 cm**-1 + 11: 3746.09 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 0.095485 -0.419722 0.118114 0.047891 -0.109709 0.004117 + 1 -0.065690 -0.022114 0.015180 0.004707 -0.003160 -0.010956 + 2 0.006831 0.293844 0.033643 0.073808 -0.050863 -0.062037 + 3 -0.142512 0.017223 -0.303754 -0.046484 0.009733 0.001203 + 4 -0.050362 -0.002658 0.096502 -0.003478 -0.082506 0.000235 + 5 -0.013063 -0.234253 -0.008047 -0.002153 0.646528 -0.000683 + 6 0.018263 0.374516 0.118037 0.055231 0.070408 -0.000889 + 7 0.049934 -0.005642 -0.050911 -0.002087 0.061488 -0.000281 + 8 0.015063 -0.105858 -0.039604 -0.072206 -0.512967 0.000881 + 9 0.174909 0.478196 0.472714 -0.990820 0.488535 -0.067951 + 10 0.949900 0.477469 -0.773869 0.006740 0.220696 0.175097 + 11 -0.165975 0.271430 0.206444 0.004494 -0.034914 0.980171 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 7: 668.66 0.019497 98.53 0.009099 ( 0.080444 0.013810 -0.049367) + 8: 1024.36 0.033922 171.43 0.010334 (-0.078932 -0.031892 0.055558) + 9: 1292.30 0.031340 158.38 0.007568 (-0.081441 0.005563 0.030072) + 10: 1750.25 0.020951 105.88 0.003736 (-0.043063 0.005301 0.043047) + 11: 3746.09 0.014283 72.18 0.001190 (-0.015121 0.006360 0.030343) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 7 +The total number of vibrations considered is 5 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 668.66 E(vib) ... 0.08 +freq. 1024.36 E(vib) ... 0.02 +freq. 1292.30 E(vib) ... 0.01 +freq. 1750.25 E(vib) ... 0.00 +freq. 3746.09 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.45091283 Eh +Zero point energy ... 0.01932264 Eh 12.13 kcal/mol +Thermal vibrational correction ... 0.00017271 Eh 0.11 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42858495 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00300525 Eh 1.89 kcal/mol +Non-thermal (ZPE) correction 0.01932264 Eh 12.13 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02232789 Eh 14.01 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42858495 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.42764074 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 3.058944 0.417246 0.368160 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00021992 Eh 0.14 kcal/mol +Rotational entropy ... 0.00986736 Eh 6.19 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02788960 Eh 17.50 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00986736 Eh 6.19 kcal/mol| +| sn= 2 | S(rot)= 0.00921290 Eh 5.78 kcal/mol| +| sn= 3 | S(rot)= 0.00883007 Eh 5.54 kcal/mol| +| sn= 4 | S(rot)= 0.00855844 Eh 5.37 kcal/mol| +| sn= 5 | S(rot)= 0.00834775 Eh 5.24 kcal/mol| +| sn= 6 | S(rot)= 0.00817561 Eh 5.13 kcal/mol| +| sn= 7 | S(rot)= 0.00803006 Eh 5.04 kcal/mol| +| sn= 8 | S(rot)= 0.00790399 Eh 4.96 kcal/mol| +| sn= 9 | S(rot)= 0.00779278 Eh 4.89 kcal/mol| +| sn=10 | S(rot)= 0.00769330 Eh 4.83 kcal/mol| +| sn=11 | S(rot)= 0.00760331 Eh 4.77 kcal/mol| +| sn=12 | S(rot)= 0.00752115 Eh 4.72 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.42764074 Eh +Total entropy correction ... -0.02788960 Eh -17.50 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.45553034 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00461750 Eh -2.90 kcal/mol + + +Actual Hessian File stored as input.002.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.450912835 Eh +Current gradient norm .... 0.009517735 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating recalculated hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.026738368 0.133812548 0.226071008 0.511505428 0.670518977 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999922 +Lowest eigenvalues of augmented Hessian: + -0.000000042 0.130242101 0.220186986 0.511364673 0.661148337 +Length of the computed step .... 0.000393825 +The final length of the internal step .... 0.000393825 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0001607785 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001211464 RMS(Int)= 0.0001607796 + Iter 1: RMS(Cart)= 0.0000000061 RMS(Int)= 0.0000000113 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000004351 0.0000050000 YES + RMS gradient 0.0000486433 0.0001000000 YES + MAX gradient 0.0000599609 0.0003000000 YES + RMS step 0.0001607785 0.0020000000 YES + MAX step 0.0002626672 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4371 -0.000051 0.0001 1.4373 + 2. B(O 2,N 1) 1.1732 0.000047 -0.0001 1.1732 + 3. B(H 3,O 0) 0.9689 0.000053 -0.0001 0.9689 + 4. A(N 1,O 0,H 3) 102.04 -0.000060 0.01 102.05 + 5. A(O 0,N 1,O 2) 110.59 -0.000054 0.00 110.59 + 6. D(O 2,N 1,O 0,H 3) -163.64 0.009095 0.00 -163.64 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 4 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.762534 0.003016 0.141344 + N 0.655340 -0.136034 -0.048470 + O 0.930338 -0.044637 -1.185291 + H -0.823143 0.177654 1.092417 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.440981 0.005700 0.267101 + 1 N 7.0000 0 14.007 1.238414 -0.257066 -0.091594 + 2 O 8.0000 0 15.999 1.758084 -0.084351 -2.239875 + 3 H 1.0000 0 1.008 -1.555515 0.335718 2.064368 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.437265764879 0.00000000 0.00000000 + O 2 1 0 1.173174859605 110.59000718 0.00000000 + H 1 2 3 0.968871170006 102.05144802 196.36363645 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.716038677282 0.00000000 0.00000000 + O 2 1 0 2.216979191856 110.59000718 0.00000000 + H 1 2 3 1.830901170363 102.05144802 196.36363645 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.414607072565 Eh + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.4146070726 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.973e-04 +Time for diagonalization ... 0.005 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.004 sec +Total time needed ... 0.010 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7221912609 0.000000000000 0.00000394 0.00000015 0.0000294 0.7000 + 1 -204.7221912664 -0.000000005500 0.00000312 0.00000013 0.0000246 0.7000 + ***Turning on DIIS*** + 2 -204.7221912708 -0.000000004406 0.00000800 0.00000034 0.0000200 0.0000 + 3 -204.7221881071 0.000003163745 0.00000384 0.00000012 0.0000065 0.0000 + 4 -204.7221913702 -0.000003263120 0.00000094 0.00000004 0.0000021 0.0000 + 5 -204.7221921423 -0.000000772115 0.00000050 0.00000002 0.0000013 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 6 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72219114 Eh -5570.77403 eV + +Components: +Nuclear Repulsion : 69.41460707 Eh 1888.86749 eV +Electronic Energy : -274.13679821 Eh -7459.64152 eV +One Electron Energy: -418.53395197 Eh -11388.88783 eV +Two Electron Energy: 144.39715375 Eh 3929.24631 eV + +Virial components: +Potential Energy : -408.96894278 Eh -11128.61070 eV +Kinetic Energy : 204.24675163 Eh 5557.83667 eV +Virial Ratio : 2.00232777 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 9.9991e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.9446e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.4047e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.2095e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.668407 -562.4160 + 1 1.0000 -20.638538 -561.6032 + 2 1.0000 -15.799311 -429.9211 + 3 1.0000 -1.605632 -43.6915 + 4 1.0000 -1.399049 -38.0701 + 5 1.0000 -0.948677 -25.8148 + 6 1.0000 -0.783084 -21.3088 + 7 1.0000 -0.729735 -19.8571 + 8 1.0000 -0.684012 -18.6129 + 9 1.0000 -0.623456 -16.9651 + 10 1.0000 -0.528895 -14.3920 + 11 1.0000 -0.461027 -12.5452 + 12 0.0000 0.028383 0.7723 + 13 0.0000 0.079780 2.1709 + 14 0.0000 0.093611 2.5473 + 15 0.0000 0.097968 2.6659 + 16 0.0000 0.127011 3.4561 + 17 0.0000 0.145443 3.9577 + 18 0.0000 0.156928 4.2702 + 19 0.0000 0.172379 4.6907 + 20 0.0000 0.187053 5.0900 + 21 0.0000 0.196105 5.3363 + 22 0.0000 0.204964 5.5774 + 23 0.0000 0.233946 6.3660 + 24 0.0000 0.259919 7.0728 + 25 0.0000 0.294052 8.0016 + 26 0.0000 0.308174 8.3858 + 27 0.0000 0.329623 8.9695 + 28 0.0000 0.362856 9.8738 + 29 0.0000 0.378584 10.3018 + 30 0.0000 0.424402 11.5486 + 31 0.0000 0.516329 14.0500 + 32 0.0000 0.529863 14.4183 + 33 0.0000 0.548292 14.9198 + 34 0.0000 0.570642 15.5280 + 35 0.0000 0.613990 16.7075 + 36 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1.761735 47.9393 + 71 0.0000 1.814158 49.3657 + 72 0.0000 1.862663 50.6856 + 73 0.0000 1.952437 53.1285 + 74 0.0000 1.964540 53.4579 + 75 0.0000 2.008944 54.6662 + 76 0.0000 2.077580 56.5338 + 77 0.0000 2.103172 57.2302 + 78 0.0000 2.162379 58.8413 + 79 0.0000 2.174563 59.1729 + 80 0.0000 2.283678 62.1420 + 81 0.0000 2.304084 62.6973 + 82 0.0000 2.321271 63.1650 + 83 0.0000 2.377653 64.6992 + 84 0.0000 2.447041 66.5874 + 85 0.0000 2.469112 67.1879 + 86 0.0000 2.495394 67.9031 + 87 0.0000 2.502525 68.0972 + 88 0.0000 2.519783 68.5668 + 89 0.0000 2.541270 69.1515 + 90 0.0000 2.571721 69.9801 + 91 0.0000 2.601744 70.7971 + 92 0.0000 2.635950 71.7279 + 93 0.0000 2.678532 72.8866 + 94 0.0000 2.753554 74.9280 + 95 0.0000 2.764247 75.2190 + 96 0.0000 2.863477 77.9192 + 97 0.0000 2.907816 79.1257 + 98 0.0000 2.944384 80.1208 + 99 0.0000 3.104316 84.4727 + 100 0.0000 3.152519 85.7844 + 101 0.0000 3.183384 86.6243 + 102 0.0000 3.254623 88.5628 + 103 0.0000 3.460511 94.1653 + 104 0.0000 3.796822 103.3168 + 105 0.0000 3.879283 105.5607 + 106 0.0000 4.028992 109.6345 + 107 0.0000 4.170038 113.4725 + 108 0.0000 4.178577 113.7049 + 109 0.0000 4.240504 115.3900 + 110 0.0000 4.363860 118.7467 + 111 0.0000 4.389605 119.4472 + 112 0.0000 4.572263 124.4176 + 113 0.0000 4.624327 125.8343 + 114 0.0000 4.751552 129.2963 + 115 0.0000 4.811579 130.9297 + 116 0.0000 4.845136 131.8429 + 117 0.0000 4.894487 133.1858 + 118 0.0000 4.972721 135.3146 + 119 0.0000 5.003406 136.1496 + 120 0.0000 5.071899 138.0134 + 121 0.0000 5.097377 138.7067 + 122 0.0000 5.171238 140.7165 + 123 0.0000 5.249631 142.8497 + 124 0.0000 5.255154 143.0000 + 125 0.0000 5.330665 145.0548 + 126 0.0000 5.339099 145.2843 + 127 0.0000 5.403750 147.0435 + 128 0.0000 5.568451 151.5253 + 129 0.0000 5.678673 154.5245 + 130 0.0000 5.797060 157.7460 + 131 0.0000 5.997747 163.2070 + 132 0.0000 6.111146 166.2927 + 133 0.0000 6.424622 174.8228 + 134 0.0000 6.506304 177.0455 + 135 0.0000 6.508158 177.0960 + 136 0.0000 6.680436 181.7839 + 137 0.0000 6.712067 182.6446 + 138 0.0000 6.742603 183.4756 + 139 0.0000 6.848845 186.3665 + 140 0.0000 6.915376 188.1769 + 141 0.0000 7.069330 192.3663 + 142 0.0000 7.124261 193.8610 + 143 0.0000 7.181339 195.4142 + 144 0.0000 7.218130 196.4153 + 145 0.0000 7.243247 197.0988 + 146 0.0000 7.261384 197.5923 + 147 0.0000 7.342013 199.7863 + 148 0.0000 7.386974 201.0098 + 149 0.0000 7.436081 202.3461 + 150 0.0000 7.478473 203.4996 + 151 0.0000 7.610863 207.1021 + 152 0.0000 7.642809 207.9714 + 153 0.0000 7.695867 209.4152 + 154 0.0000 7.803567 212.3459 + 155 0.0000 7.959677 216.5938 + 156 0.0000 8.062368 219.3882 + 157 0.0000 8.411574 228.8906 + 158 0.0000 14.171900 385.6370 + 159 0.0000 15.076821 410.2612 + 160 0.0000 16.064802 437.1455 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.668407 -562.4160 + 1 1.0000 -20.638538 -561.6032 + 2 1.0000 -15.799311 -429.9211 + 3 1.0000 -1.605632 -43.6915 + 4 1.0000 -1.399049 -38.0701 + 5 1.0000 -0.948677 -25.8148 + 6 1.0000 -0.783084 -21.3088 + 7 1.0000 -0.729735 -19.8571 + 8 1.0000 -0.684012 -18.6129 + 9 1.0000 -0.623456 -16.9651 + 10 1.0000 -0.528895 -14.3920 + 11 1.0000 -0.461027 -12.5452 + 12 0.0000 0.028383 0.7723 + 13 0.0000 0.079780 2.1709 + 14 0.0000 0.093611 2.5473 + 15 0.0000 0.097968 2.6659 + 16 0.0000 0.127011 3.4561 + 17 0.0000 0.145443 3.9577 + 18 0.0000 0.156928 4.2702 + 19 0.0000 0.172379 4.6907 + 20 0.0000 0.187053 5.0900 + 21 0.0000 0.196105 5.3363 + 22 0.0000 0.204964 5.5774 + 23 0.0000 0.233946 6.3660 + 24 0.0000 0.259919 7.0728 + 25 0.0000 0.294052 8.0016 + 26 0.0000 0.308174 8.3858 + 27 0.0000 0.329623 8.9695 + 28 0.0000 0.362856 9.8738 + 29 0.0000 0.378584 10.3018 + 30 0.0000 0.424402 11.5486 + 31 0.0000 0.516329 14.0500 + 32 0.0000 0.529863 14.4183 + 33 0.0000 0.548292 14.9198 + 34 0.0000 0.570642 15.5280 + 35 0.0000 0.613990 16.7075 + 36 0.0000 0.633068 17.2266 + 37 0.0000 0.647509 17.6196 + 38 0.0000 0.686134 18.6707 + 39 0.0000 0.717618 19.5274 + 40 0.0000 0.719584 19.5809 + 41 0.0000 0.746871 20.3234 + 42 0.0000 0.772160 21.0115 + 43 0.0000 0.786574 21.4038 + 44 0.0000 0.807082 21.9618 + 45 0.0000 0.816396 22.2153 + 46 0.0000 0.858992 23.3743 + 47 0.0000 0.872819 23.7506 + 48 0.0000 0.926975 25.2243 + 49 0.0000 0.939140 25.5553 + 50 0.0000 0.950537 25.8654 + 51 0.0000 1.000398 27.2222 + 52 0.0000 1.045074 28.4379 + 53 0.0000 1.059616 28.8336 + 54 0.0000 1.068741 29.0819 + 55 0.0000 1.098619 29.8950 + 56 0.0000 1.160875 31.5890 + 57 0.0000 1.194363 32.5003 + 58 0.0000 1.251266 34.0487 + 59 0.0000 1.285974 34.9931 + 60 0.0000 1.367749 37.2183 + 61 0.0000 1.423545 38.7366 + 62 0.0000 1.494156 40.6581 + 63 0.0000 1.517559 41.2949 + 64 0.0000 1.523371 41.4530 + 65 0.0000 1.541125 41.9361 + 66 0.0000 1.563362 42.5413 + 67 0.0000 1.604361 43.6569 + 68 0.0000 1.664527 45.2941 + 69 0.0000 1.730351 47.0852 + 70 0.0000 1.761735 47.9393 + 71 0.0000 1.814158 49.3657 + 72 0.0000 1.862663 50.6856 + 73 0.0000 1.952437 53.1285 + 74 0.0000 1.964540 53.4579 + 75 0.0000 2.008944 54.6662 + 76 0.0000 2.077580 56.5338 + 77 0.0000 2.103172 57.2302 + 78 0.0000 2.162379 58.8413 + 79 0.0000 2.174563 59.1729 + 80 0.0000 2.283678 62.1420 + 81 0.0000 2.304084 62.6973 + 82 0.0000 2.321271 63.1650 + 83 0.0000 2.377653 64.6992 + 84 0.0000 2.447041 66.5874 + 85 0.0000 2.469112 67.1879 + 86 0.0000 2.495394 67.9031 + 87 0.0000 2.502525 68.0972 + 88 0.0000 2.519783 68.5668 + 89 0.0000 2.541270 69.1515 + 90 0.0000 2.571721 69.9801 + 91 0.0000 2.601744 70.7971 + 92 0.0000 2.635950 71.7279 + 93 0.0000 2.678532 72.8866 + 94 0.0000 2.753554 74.9280 + 95 0.0000 2.764247 75.2190 + 96 0.0000 2.863477 77.9192 + 97 0.0000 2.907816 79.1257 + 98 0.0000 2.944384 80.1208 + 99 0.0000 3.104316 84.4727 + 100 0.0000 3.152519 85.7844 + 101 0.0000 3.183384 86.6243 + 102 0.0000 3.254623 88.5628 + 103 0.0000 3.460511 94.1653 + 104 0.0000 3.796822 103.3168 + 105 0.0000 3.879283 105.5607 + 106 0.0000 4.028992 109.6345 + 107 0.0000 4.170038 113.4725 + 108 0.0000 4.178577 113.7049 + 109 0.0000 4.240504 115.3900 + 110 0.0000 4.363860 118.7467 + 111 0.0000 4.389605 119.4472 + 112 0.0000 4.572263 124.4176 + 113 0.0000 4.624327 125.8343 + 114 0.0000 4.751552 129.2963 + 115 0.0000 4.811579 130.9297 + 116 0.0000 4.845136 131.8429 + 117 0.0000 4.894487 133.1858 + 118 0.0000 4.972721 135.3146 + 119 0.0000 5.003406 136.1496 + 120 0.0000 5.071899 138.0134 + 121 0.0000 5.097377 138.7067 + 122 0.0000 5.171238 140.7165 + 123 0.0000 5.249631 142.8497 + 124 0.0000 5.255154 143.0000 + 125 0.0000 5.330665 145.0548 + 126 0.0000 5.339099 145.2843 + 127 0.0000 5.403750 147.0435 + 128 0.0000 5.568451 151.5253 + 129 0.0000 5.678673 154.5245 + 130 0.0000 5.797060 157.7460 + 131 0.0000 5.997747 163.2070 + 132 0.0000 6.111146 166.2927 + 133 0.0000 6.424622 174.8228 + 134 0.0000 6.506304 177.0455 + 135 0.0000 6.508158 177.0960 + 136 0.0000 6.680436 181.7839 + 137 0.0000 6.712067 182.6446 + 138 0.0000 6.742603 183.4756 + 139 0.0000 6.848845 186.3665 + 140 0.0000 6.915376 188.1769 + 141 0.0000 7.069330 192.3663 + 142 0.0000 7.124261 193.8610 + 143 0.0000 7.181339 195.4142 + 144 0.0000 7.218130 196.4153 + 145 0.0000 7.243247 197.0988 + 146 0.0000 7.261384 197.5923 + 147 0.0000 7.342013 199.7863 + 148 0.0000 7.386974 201.0098 + 149 0.0000 7.436081 202.3461 + 150 0.0000 7.478473 203.4996 + 151 0.0000 7.610863 207.1021 + 152 0.0000 7.642809 207.9714 + 153 0.0000 7.695867 209.4152 + 154 0.0000 7.803567 212.3459 + 155 0.0000 7.959677 216.5938 + 156 0.0000 8.062368 219.3882 + 157 0.0000 8.411574 228.8906 + 158 0.0000 14.171900 385.6370 + 159 0.0000 15.076821 410.2612 + 160 0.0000 16.064802 437.1455 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.346094 0.000000 + 1 N : 0.344509 0.000000 + 2 O : -0.274716 0.000000 + 3 H : 0.276302 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.866770 s : 3.866770 + pz : 1.390715 p : 4.451036 + px : 1.240060 + py : 1.820261 + dz2 : 0.011568 d : 0.023651 + dxz : -0.002434 + dyz : 0.000894 + dx2y2 : 0.006048 + dxy : 0.007574 + f0 : 0.000483 f : 0.004637 + f+1 : 0.001054 + f-1 : 0.000174 + f+2 : 0.000600 + f-2 : -0.000100 + f+3 : 0.001022 + f-3 : 0.001405 + 1 N s : 3.829937 s : 3.829937 + pz : 1.078225 p : 2.652305 + px : 0.830903 + py : 0.743177 + dz2 : 0.031667 d : 0.143444 + dxz : 0.034713 + dyz : 0.031093 + dx2y2 : 0.023521 + dxy : 0.022451 + f0 : 0.005292 f : 0.029805 + f+1 : 0.009087 + f-1 : 0.005711 + f+2 : 0.002334 + f-2 : 0.000397 + f+3 : 0.002049 + f-3 : 0.004936 + 2 O s : 3.877487 s : 3.877487 + pz : 1.202842 p : 4.325832 + px : 1.850382 + py : 1.272607 + dz2 : 0.014535 d : 0.063580 + dxz : 0.017065 + dyz : 0.030171 + dx2y2 : -0.000082 + dxy : 0.001890 + f0 : 0.002198 f : 0.007818 + f+1 : 0.002387 + f-1 : 0.002787 + f+2 : 0.000060 + f-2 : 0.000492 + f+3 : -0.000024 + f-3 : -0.000083 + 3 H s : 0.622664 s : 0.622664 + pz : 0.016473 p : 0.078465 + px : 0.020346 + py : 0.041645 + dz2 : 0.001680 d : 0.022570 + dxz : 0.011357 + dyz : 0.009650 + dx2y2 : -0.000144 + dxy : 0.000026 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.602673 0.000000 + 1 N : -0.266367 0.000000 + 2 O : 0.236145 0.000000 + 3 H : -0.572451 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.114430 s : 3.114430 + pz : 1.291176 p : 3.904910 + px : 1.179028 + py : 1.434705 + dz2 : 0.072755 d : 0.290270 + dxz : 0.071968 + dyz : 0.008167 + dx2y2 : 0.090574 + dxy : 0.046806 + f0 : 0.016310 f : 0.087718 + f+1 : 0.015971 + f-1 : 0.002081 + f+2 : 0.017604 + f-2 : 0.003014 + f+3 : 0.017934 + f-3 : 0.014804 + 1 N s : 3.004126 s : 3.004126 + pz : 1.230231 p : 2.833992 + px : 0.908921 + py : 0.694840 + dz2 : 0.274674 d : 0.969702 + dxz : 0.307612 + dyz : 0.116473 + dx2y2 : 0.146699 + dxy : 0.124245 + f0 : 0.107941 f : 0.458547 + f+1 : 0.135765 + f-1 : 0.063562 + f+2 : 0.049946 + f-2 : 0.010173 + f+3 : 0.036902 + f-3 : 0.054257 + 2 O s : 3.315394 s : 3.315394 + pz : 1.403968 p : 4.004951 + px : 1.510552 + py : 1.090432 + dz2 : 0.151310 d : 0.325403 + dxz : 0.098184 + dyz : 0.051466 + dx2y2 : 0.016810 + dxy : 0.007633 + f0 : 0.048062 f : 0.118106 + f+1 : 0.031592 + f-1 : 0.021216 + f+2 : 0.011236 + f-2 : 0.004789 + f+3 : 0.000901 + f-3 : 0.000309 + 3 H s : 0.621783 s : 0.621783 + pz : 0.261485 p : 0.555547 + px : 0.131536 + py : 0.162527 + dz2 : 0.130536 d : 0.395121 + dxz : 0.116197 + dyz : 0.120890 + dx2y2 : 0.019754 + dxy : 0.007744 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3461 8.0000 -0.3461 1.9365 1.9365 -0.0000 + 1 N 6.6555 7.0000 0.3445 2.5361 2.5361 -0.0000 + 2 O 8.2747 8.0000 -0.2747 1.7302 1.7302 0.0000 + 3 H 0.7237 1.0000 0.2763 0.9410 0.9410 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.9159 B( 0-O , 3-H ) : 0.9638 B( 1-N , 2-O ) : 1.6583 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.900 sec +Sum of individual times .... 2.573 sec ( 88.7%) + +Fock matrix formation .... 2.252 sec ( 77.7%) +Diagonalization .... 0.153 sec ( 5.3%) +Density matrix formation .... 0.011 sec ( 0.4%) +Population analysis .... 0.030 sec ( 1.0%) +Initial guess .... 0.021 sec ( 0.7%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.012 sec ( 0.4%) +DIIS solution .... 0.106 sec ( 3.7%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.515 sec +Reference energy ... -204.722191284 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 10.973 sec +AO-integral generation ... 0.372 sec +Half transformation ... 0.183 sec +K-integral sorting ... 8.415 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.080 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.078 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.077 s ( 0.000 ms/b) + 151164 b 0 skpd 0.126 s ( 0.001 ms/b) +: 159120 b 0 skpd 0.072 s ( 0.000 ms/b) +: : 218790 b 0 skpd 0.134 s ( 0.001 ms/b) +: 119340 b 0 skpd 0.105 s ( 0.001 ms/b) + 87516 b 0 skpd 0.077 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.120 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.062 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 1.058 sec +AO-integral generation ... 0.837 sec +Half transformation ... 0.107 sec +J-integral sorting ... 0.085 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.245 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.387 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090575571 +EMP2(bb)= -0.090575571 +EMP2(ab)= -0.516551057 + +Initial guess performed in 0.278 sec +E(0) ... -204.722191284 +E(MP2) ... -0.697702198 +Initial E(tot) ... -205.419893482 + ... 0.188082392 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.419893482 -0.697702198 -0.000000000 0.026299710 6.37 0.000001374 + *** Turning on DIIS *** + 1 -205.390651000 -0.668459716 0.029242482 0.011442191 6.91 0.057977011 + 2 -205.410155653 -0.687964368 -0.019504653 0.005769750 6.52 0.060888304 + 3 -205.413860167 -0.691668883 -0.003704514 0.002386735 6.61 0.075300104 + 4 -205.415429408 -0.693238124 -0.001569241 0.001650445 6.45 0.082170360 + 5 -205.415990000 -0.693798716 -0.000560592 0.000884303 7.28 0.087947652 + 6 -205.416103113 -0.693911829 -0.000113113 0.000521832 6.78 0.090802265 + 7 -205.416148229 -0.693956944 -0.000045116 0.000202824 7.15 0.092068079 + 8 -205.416160230 -0.693968945 -0.000012001 0.000104558 7.12 0.092526300 + 9 -205.416156017 -0.693964733 0.000004212 0.000027341 7.13 0.092658141 + 10 -205.416160482 -0.693969198 -0.000004465 0.000009761 7.83 0.092695288 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.722191284 +E(CORR) ... -0.693969198 +E(TOT) ... -205.416160482 +Singles norm **1/2 ... 0.092695288 ( 0.046347644, 0.046347644) +T1 diagnostic ... 0.021848489 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.063217 + 10a-> 13a 10b-> 13b 0.050823 + 8b-> 13b -1b-> -1b 0.043310 + 8a-> 13a -1a-> -1a 0.043310 + 8a-> 13a 10b-> 13b 0.034629 + 10a-> 13a 8b-> 13b 0.034629 + 10b-> 13b -1b-> -1b 0.033892 + 10a-> 13a -1a-> -1a 0.033892 + 11a-> 13a 11b-> 13b 0.027998 + 11b-> 26b -1b-> -1b 0.027366 + 11a-> 26a -1a-> -1a 0.027366 + 11a-> 26a 11b-> 26b 0.027206 + 5a-> 13a 5b-> 13b 0.025750 + 8a-> 13a 8b-> 22b 0.022798 + 8a-> 22a 8b-> 13b 0.022798 + 10a-> 13a 11b-> 26b 0.022291 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034752266 + alpha-alpha-alpha ... -0.000899556 ( 2.6%) + alpha-alpha-beta ... -0.016476577 ( 47.4%) + alpha-beta -beta ... -0.016476577 ( 47.4%) + beta -beta -beta ... -0.000899556 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034752266 + +Final correlation energy ... -0.728721464 +E(CCSD) ... -205.416160482 +E(CCSD(T)) ... -205.450912748 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209795702 sqrt= 1.099907134 +W(HF) = 0.826585843 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.258327 -0.000000 + 1 N : 0.154642 0.000000 + 2 O : -0.159936 -0.000000 + 3 H : 0.263620 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.846534 s : 3.846534 + pz : 1.372712 p : 4.347384 + px : 1.236495 + py : 1.738178 + dz2 : 0.016172 d : 0.055958 + dxz : 0.005765 + dyz : 0.007882 + dx2y2 : 0.011134 + dxy : 0.015004 + f0 : 0.001195 f : 0.008450 + f+1 : 0.001487 + f-1 : 0.000806 + f+2 : 0.001151 + f-2 : 0.000579 + f+3 : 0.001289 + f-3 : 0.001943 + 1 N s : 3.880347 s : 3.880347 + pz : 1.044186 p : 2.762100 + px : 0.868505 + py : 0.849409 + dz2 : 0.035793 d : 0.173694 + dxz : 0.046171 + dyz : 0.031408 + dx2y2 : 0.029114 + dxy : 0.031208 + f0 : 0.004786 f : 0.029217 + f+1 : 0.008789 + f-1 : 0.004641 + f+2 : 0.002762 + f-2 : 0.000980 + f+3 : 0.002188 + f-3 : 0.005072 + 2 O s : 3.866543 s : 3.866543 + pz : 1.190946 p : 4.197774 + px : 1.768742 + py : 1.238086 + dz2 : 0.017063 d : 0.085234 + dxz : 0.023925 + dyz : 0.029864 + dx2y2 : 0.006354 + dxy : 0.008028 + f0 : 0.002265 f : 0.010385 + f+1 : 0.002801 + f-1 : 0.002560 + f+2 : 0.000688 + f-2 : 0.001030 + f+3 : 0.000552 + f-3 : 0.000490 + 3 H s : 0.634512 s : 0.634512 + pz : 0.010749 p : 0.082503 + px : 0.024089 + py : 0.047665 + dz2 : 0.000529 d : 0.019365 + dxz : 0.010214 + dyz : 0.008032 + dx2y2 : 0.000370 + dxy : 0.000220 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.619324 0.000000 + 1 N : -0.316545 0.000000 + 2 O : 0.269630 0.000000 + 3 H : -0.572409 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.121685 s : 3.121685 + pz : 1.279286 p : 3.842845 + px : 1.187775 + py : 1.375783 + dz2 : 0.079529 d : 0.321473 + dxz : 0.077162 + dyz : 0.013944 + dx2y2 : 0.097366 + dxy : 0.053472 + f0 : 0.017280 f : 0.094673 + f+1 : 0.016771 + f-1 : 0.003002 + f+2 : 0.017894 + f-2 : 0.003473 + f+3 : 0.019370 + f-3 : 0.016883 + 1 N s : 3.009314 s : 3.009314 + pz : 1.200649 p : 2.882089 + px : 0.921054 + py : 0.760385 + dz2 : 0.280357 d : 0.978606 + dxz : 0.305055 + dyz : 0.113493 + dx2y2 : 0.154137 + dxy : 0.125565 + f0 : 0.104970 f : 0.446536 + f+1 : 0.132630 + f-1 : 0.063014 + f+2 : 0.047682 + f-2 : 0.010634 + f+3 : 0.037797 + f-3 : 0.049810 + 2 O s : 3.317220 s : 3.317220 + pz : 1.394700 p : 3.929573 + px : 1.458181 + py : 1.076692 + dz2 : 0.155557 d : 0.356804 + dxz : 0.101048 + dyz : 0.063145 + dx2y2 : 0.022314 + dxy : 0.014740 + f0 : 0.048098 f : 0.126773 + f+1 : 0.032637 + f-1 : 0.025818 + f+2 : 0.011430 + f-2 : 0.006440 + f+3 : 0.001441 + f-3 : 0.000909 + 3 H s : 0.623876 s : 0.623876 + pz : 0.264590 p : 0.563876 + px : 0.132533 + py : 0.166753 + dz2 : 0.129791 d : 0.384657 + dxz : 0.112338 + dyz : 0.114131 + dx2y2 : 0.020157 + dxy : 0.008241 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2583 8.0000 -0.2583 2.3029 1.8418 0.4611 + 1 N 6.8454 7.0000 0.1546 2.8259 2.3499 0.4760 + 2 O 8.1599 8.0000 -0.1599 2.1321 1.6357 0.4964 + 3 H 0.7364 1.0000 0.2636 0.9625 0.8922 0.0703 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8508 B( 0-O , 3-H ) : 0.8913 B( 1-N , 2-O ) : 1.5172 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 108.316 sec + +Fock Matrix Formation ... 0.515 sec ( 0.5%) +Initial Guess ... 0.278 sec ( 0.3%) +DIIS Solver ... 4.356 sec ( 4.0%) +State Vector Update ... 0.229 sec ( 0.2%) +Sigma-vector construction ... 71.569 sec ( 66.1%) + <0|H|D> ... 0.011 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.058 sec ( 0.1% of sigma) + (0-ext) ... 0.150 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.049 sec ( 0.1% of sigma) + (2-ext) ... 1.765 sec ( 2.5% of sigma) + (4-ext) ... 41.655 sec ( 58.2% of sigma) + ... 3.788 sec ( 5.3% of sigma) + ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.023 sec ( 0.0% of sigma) + (1-ext) ... 0.242 sec ( 0.3% of sigma) + Fock-dressing ... 4.372 sec ( 6.1% of sigma) + (ik|jl)-dressing ... 0.155 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 15.816 sec ( 22.1% of sigma) + Pair energies ... 0.026 sec ( 0.0% of sigma) +Total Time for computing (T) ... 16.503 sec ( 15.2% of ALL) + I/O of integral and amplitudes ... 1.497 sec ( 9.1% of (T)) + External N**7 contributions ... 9.421 sec ( 57.1% of (T)) + Internal N**7 contributions ... 0.838 sec ( 5.1% of (T)) + N**6 triples energy contributions ... 2.987 sec ( 18.1% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.450912747957 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.003.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.003.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.443533, -0.096158 -0.654383) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.88306 -0.10940 -0.49319 +Nuclear contribution : -0.99460 0.21483 1.34620 + ----------------------------------------- +Total Dipole Moment : -0.11153 0.10544 0.85301 + ----------------------------------------- +Magnitude (a.u.) : 0.86670 +Magnitude (Debye) : 2.20299 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.059212 0.417193 0.368123 +Rotational constants in MHz : 91712.860973 12507.144612 11036.044331 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.612270 0.591707 -0.161817 +x,y,z [Debye]: 1.556267 1.504000 -0.411305 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.443533, -0.096158 -0.654383) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.86251 -0.10453 -0.66953 +Nuclear contribution : -0.99460 0.21483 1.34620 + ----------------------------------------- +Total Dipole Moment : -0.13209 0.11030 0.67667 + ----------------------------------------- +Magnitude (a.u.) : 0.69820 +Magnitude (Debye) : 1.77469 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.059212 0.417193 0.368123 +Rotational constants in MHz : 91712.860973 12507.144612 11036.044331 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.521155 0.439706 -0.150150 +x,y,z [Debye]: 1.324672 1.117643 -0.381651 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 4 * + * * + * Dihedral ( 2, 1, 0, 3) : -155.45454545 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0396303874 RMS(Int)= 0.0002498913 + Iter 1: RMS(Cart)= 0.0000693509 RMS(Int)= 0.0000013083 + Iter 2: RMS(Cart)= 0.0000003631 RMS(Int)= 0.0000000069 + Iter 3: RMS(Cart)= 0.0000000019 RMS(Int)= 0.0000000000 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4373 0.000000 + 2. B(O 2,N 1) 1.1753 0.000000 + 3. B(H 3,O 0) 0.9717 0.000000 + 4. A(N 1,O 0,H 3) 102.0229 0.000000 + 5. A(O 0,N 1,O 2) 110.5407 0.000000 + 6. D(O 2,N 1,O 0,H 3) -155.4545 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.765297 -0.031129 0.145712 + N 0.651507 -0.173288 -0.049823 + O 0.930152 -0.011060 -1.180067 + H -0.816361 0.215478 1.084178 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.446202 -0.058826 0.275355 + 1 N 7.0000 0 14.007 1.231169 -0.327467 -0.094151 + 2 O 8.0000 0 15.999 1.757733 -0.020900 -2.230003 + 3 H 1.0000 0 1.008 -1.542699 0.407194 2.048799 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.437265764879 0.00000000 0.00000000 + O 2 1 0 1.173174859605 110.59000718 0.00000000 + H 1 2 3 0.968871170006 102.05144802 196.36363645 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.716038677282 0.00000000 0.00000000 + O 2 1 0 2.216979191856 110.59000718 0.00000000 + H 1 2 3 1.830901170363 102.05144802 196.36363645 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.1 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.353435862268 Eh + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.3534358623 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.972e-04 +Time for diagonalization ... 0.005 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.005 sec +Total time needed ... 0.011 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7160193786 0.000000000000 0.00178202 0.00005367 0.0197978 0.7000 + 1 -204.7169220041 -0.000902625486 0.00169724 0.00004841 0.0163902 0.7000 + ***Turning on DIIS*** + 2 -204.7176912078 -0.000769203670 0.00463345 0.00013073 0.0133206 0.0000 + 3 -204.7218048030 -0.004113595203 0.00188881 0.00005256 0.0053525 0.0000 + 4 -204.7194158419 0.002388961058 0.00087890 0.00002345 0.0021229 0.0000 + 5 -204.7210245462 -0.001608704317 0.00056760 0.00001808 0.0010332 0.0000 + 6 -204.7204212061 0.000603340162 0.00061589 0.00002114 0.0006499 0.0000 + 7 -204.7199537689 0.000467437138 0.00032922 0.00001089 0.0002798 0.0000 + 8 -204.7206903391 -0.000736570121 0.00018016 0.00000687 0.0001952 0.0000 + 9 -204.7203077319 0.000382607121 0.00014819 0.00000493 0.0001332 0.0000 + 10 -204.7204435422 -0.000135810243 0.00007089 0.00000209 0.0000600 0.0000 + 11 -204.7205676292 -0.000124087047 0.00002878 0.00000080 0.0000266 0.0000 + 12 -204.7204595034 0.000108125806 0.00000805 0.00000022 0.0000073 0.0000 + 13 -204.7204889723 -0.000029468908 0.00000204 0.00000006 0.0000025 0.0000 + 14 -204.7204789024 0.000010069975 0.00000083 0.00000002 0.0000015 0.0000 + 15 -204.7204812310 -0.000002328628 0.00000048 0.00000002 0.0000010 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 16 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72048283 Eh -5570.72755 eV + +Components: +Nuclear Repulsion : 69.35343586 Eh 1887.20293 eV +Electronic Energy : -274.07391870 Eh -7457.93048 eV +One Electron Energy: -418.41919710 Eh -11385.76519 eV +Two Electron Energy: 144.34527840 Eh 3927.83471 eV + +Virial components: +Potential Energy : -408.95693547 Eh -11128.28397 eV +Kinetic Energy : 204.23645264 Eh 5557.55642 eV +Virial Ratio : 2.00236995 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.6034e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.8681e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.0843e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.0459e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.669270 -562.4394 + 1 1.0000 -20.637978 -561.5879 + 2 1.0000 -15.799178 -429.9175 + 3 1.0000 -1.604148 -43.6511 + 4 1.0000 -1.397861 -38.0377 + 5 1.0000 -0.948984 -25.8232 + 6 1.0000 -0.781562 -21.2674 + 7 1.0000 -0.729087 -19.8395 + 8 1.0000 -0.685809 -18.6618 + 9 1.0000 -0.619816 -16.8661 + 10 1.0000 -0.529068 -14.3967 + 11 1.0000 -0.461556 -12.5596 + 12 0.0000 0.028345 0.7713 + 13 0.0000 0.078498 2.1360 + 14 0.0000 0.093642 2.5481 + 15 0.0000 0.098391 2.6774 + 16 0.0000 0.124918 3.3992 + 17 0.0000 0.146403 3.9838 + 18 0.0000 0.157147 4.2762 + 19 0.0000 0.172420 4.6918 + 20 0.0000 0.186765 5.0821 + 21 0.0000 0.195451 5.3185 + 22 0.0000 0.204576 5.5668 + 23 0.0000 0.235021 6.3952 + 24 0.0000 0.261581 7.1180 + 25 0.0000 0.292160 7.9501 + 26 0.0000 0.311018 8.4632 + 27 0.0000 0.329661 8.9705 + 28 0.0000 0.360445 9.8082 + 29 0.0000 0.374822 10.1994 + 30 0.0000 0.423031 11.5113 + 31 0.0000 0.513403 13.9704 + 32 0.0000 0.528394 14.3783 + 33 0.0000 0.548790 14.9333 + 34 0.0000 0.569851 15.5064 + 35 0.0000 0.613943 16.7062 + 36 0.0000 0.632423 17.2091 + 37 0.0000 0.646489 17.5919 + 38 0.0000 0.693093 18.8600 + 39 0.0000 0.717843 19.5335 + 40 0.0000 0.724694 19.7199 + 41 0.0000 0.745081 20.2747 + 42 0.0000 0.771724 20.9997 + 43 0.0000 0.788626 21.4596 + 44 0.0000 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4.556566 123.9905 + 113 0.0000 4.625155 125.8569 + 114 0.0000 4.746500 129.1588 + 115 0.0000 4.809961 130.8857 + 116 0.0000 4.819431 131.1434 + 117 0.0000 4.891954 133.1168 + 118 0.0000 4.965576 135.1202 + 119 0.0000 5.002551 136.1263 + 120 0.0000 5.069814 137.9566 + 121 0.0000 5.098208 138.7293 + 122 0.0000 5.172111 140.7403 + 123 0.0000 5.238767 142.5541 + 124 0.0000 5.257487 143.0635 + 125 0.0000 5.323046 144.8475 + 126 0.0000 5.334101 145.1483 + 127 0.0000 5.409457 147.1988 + 128 0.0000 5.567166 151.4903 + 129 0.0000 5.681536 154.6025 + 130 0.0000 5.793326 157.6444 + 131 0.0000 5.998964 163.2401 + 132 0.0000 6.117543 166.4668 + 133 0.0000 6.419261 174.6770 + 134 0.0000 6.504148 176.9869 + 135 0.0000 6.510820 177.1684 + 136 0.0000 6.686587 181.9513 + 137 0.0000 6.707491 182.5201 + 138 0.0000 6.740953 183.4307 + 139 0.0000 6.848323 186.3524 + 140 0.0000 6.915008 188.1669 + 141 0.0000 7.068149 192.3341 + 142 0.0000 7.125978 193.9077 + 143 0.0000 7.175173 195.2464 + 144 0.0000 7.202180 195.9813 + 145 0.0000 7.231740 196.7856 + 146 0.0000 7.261129 197.5854 + 147 0.0000 7.340301 199.7397 + 148 0.0000 7.386918 201.0082 + 149 0.0000 7.440262 202.4598 + 150 0.0000 7.479916 203.5389 + 151 0.0000 7.601011 206.8340 + 152 0.0000 7.635595 207.7751 + 153 0.0000 7.687374 209.1841 + 154 0.0000 7.823981 212.9013 + 155 0.0000 7.949442 216.3153 + 156 0.0000 8.056304 219.2232 + 157 0.0000 8.394174 228.4171 + 158 0.0000 14.121993 384.2790 + 159 0.0000 15.006496 408.3475 + 160 0.0000 16.014077 435.7652 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.669270 -562.4394 + 1 1.0000 -20.637978 -561.5879 + 2 1.0000 -15.799178 -429.9175 + 3 1.0000 -1.604148 -43.6511 + 4 1.0000 -1.397861 -38.0377 + 5 1.0000 -0.948984 -25.8232 + 6 1.0000 -0.781562 -21.2674 + 7 1.0000 -0.729087 -19.8395 + 8 1.0000 -0.685809 -18.6618 + 9 1.0000 -0.619816 -16.8661 + 10 1.0000 -0.529068 -14.3967 + 11 1.0000 -0.461556 -12.5596 + 12 0.0000 0.028345 0.7713 + 13 0.0000 0.078498 2.1360 + 14 0.0000 0.093642 2.5481 + 15 0.0000 0.098391 2.6774 + 16 0.0000 0.124918 3.3992 + 17 0.0000 0.146403 3.9838 + 18 0.0000 0.157147 4.2762 + 19 0.0000 0.172420 4.6918 + 20 0.0000 0.186765 5.0821 + 21 0.0000 0.195451 5.3185 + 22 0.0000 0.204576 5.5668 + 23 0.0000 0.235021 6.3952 + 24 0.0000 0.261581 7.1180 + 25 0.0000 0.292160 7.9501 + 26 0.0000 0.311018 8.4632 + 27 0.0000 0.329661 8.9705 + 28 0.0000 0.360445 9.8082 + 29 0.0000 0.374822 10.1994 + 30 0.0000 0.423031 11.5113 + 31 0.0000 0.513403 13.9704 + 32 0.0000 0.528394 14.3783 + 33 0.0000 0.548790 14.9333 + 34 0.0000 0.569851 15.5064 + 35 0.0000 0.613943 16.7062 + 36 0.0000 0.632423 17.2091 + 37 0.0000 0.646489 17.5919 + 38 0.0000 0.693093 18.8600 + 39 0.0000 0.717843 19.5335 + 40 0.0000 0.724694 19.7199 + 41 0.0000 0.745081 20.2747 + 42 0.0000 0.771724 20.9997 + 43 0.0000 0.788626 21.4596 + 44 0.0000 0.805831 21.9278 + 45 0.0000 0.817775 22.2528 + 46 0.0000 0.856870 23.3166 + 47 0.0000 0.867149 23.5963 + 48 0.0000 0.926243 25.2044 + 49 0.0000 0.940666 25.5968 + 50 0.0000 0.953298 25.9406 + 51 0.0000 1.003615 27.3097 + 52 0.0000 1.040064 28.3016 + 53 0.0000 1.053678 28.6720 + 54 0.0000 1.058355 28.7993 + 55 0.0000 1.091538 29.7023 + 56 0.0000 1.159942 31.5636 + 57 0.0000 1.197763 32.5928 + 58 0.0000 1.251384 34.0519 + 59 0.0000 1.298610 35.3370 + 60 0.0000 1.371297 37.3149 + 61 0.0000 1.413090 38.4521 + 62 0.0000 1.491551 40.5872 + 63 0.0000 1.513410 41.1820 + 64 0.0000 1.516566 41.2679 + 65 0.0000 1.540667 41.9237 + 66 0.0000 1.572933 42.8017 + 67 0.0000 1.607354 43.7383 + 68 0.0000 1.668371 45.3987 + 69 0.0000 1.729307 47.0568 + 70 0.0000 1.771754 48.2119 + 71 0.0000 1.808416 49.2095 + 72 0.0000 1.870457 50.8977 + 73 0.0000 1.941480 52.8304 + 74 0.0000 1.960269 53.3416 + 75 0.0000 2.020310 54.9754 + 76 0.0000 2.072612 56.3986 + 77 0.0000 2.100796 57.1656 + 78 0.0000 2.162668 58.8492 + 79 0.0000 2.179109 59.2966 + 80 0.0000 2.283480 62.1366 + 81 0.0000 2.304985 62.7218 + 82 0.0000 2.314477 62.9801 + 83 0.0000 2.374146 64.6038 + 84 0.0000 2.446039 66.5601 + 85 0.0000 2.468792 67.1792 + 86 0.0000 2.491428 67.7952 + 87 0.0000 2.502479 68.0959 + 88 0.0000 2.520584 68.5886 + 89 0.0000 2.533208 68.9321 + 90 0.0000 2.573010 70.0152 + 91 0.0000 2.601064 70.7785 + 92 0.0000 2.647147 72.0325 + 93 0.0000 2.705401 73.6177 + 94 0.0000 2.734902 74.4205 + 95 0.0000 2.757554 75.0369 + 96 0.0000 2.862421 77.8904 + 97 0.0000 2.899879 78.9097 + 98 0.0000 2.950365 80.2835 + 99 0.0000 3.097853 84.2969 + 100 0.0000 3.153939 85.8230 + 101 0.0000 3.180775 86.5533 + 102 0.0000 3.259310 88.6903 + 103 0.0000 3.465513 94.3014 + 104 0.0000 3.771853 102.6373 + 105 0.0000 3.891596 105.8957 + 106 0.0000 4.028150 109.6115 + 107 0.0000 4.159211 113.1779 + 108 0.0000 4.179715 113.7358 + 109 0.0000 4.260586 115.9364 + 110 0.0000 4.359005 118.6146 + 111 0.0000 4.398982 119.7024 + 112 0.0000 4.556566 123.9905 + 113 0.0000 4.625155 125.8569 + 114 0.0000 4.746500 129.1588 + 115 0.0000 4.809961 130.8857 + 116 0.0000 4.819431 131.1434 + 117 0.0000 4.891954 133.1168 + 118 0.0000 4.965576 135.1202 + 119 0.0000 5.002551 136.1263 + 120 0.0000 5.069814 137.9566 + 121 0.0000 5.098208 138.7293 + 122 0.0000 5.172111 140.7403 + 123 0.0000 5.238767 142.5541 + 124 0.0000 5.257487 143.0635 + 125 0.0000 5.323046 144.8475 + 126 0.0000 5.334101 145.1483 + 127 0.0000 5.409457 147.1988 + 128 0.0000 5.567166 151.4903 + 129 0.0000 5.681536 154.6025 + 130 0.0000 5.793326 157.6444 + 131 0.0000 5.998964 163.2401 + 132 0.0000 6.117543 166.4668 + 133 0.0000 6.419261 174.6770 + 134 0.0000 6.504148 176.9869 + 135 0.0000 6.510820 177.1684 + 136 0.0000 6.686587 181.9513 + 137 0.0000 6.707491 182.5201 + 138 0.0000 6.740953 183.4307 + 139 0.0000 6.848323 186.3524 + 140 0.0000 6.915008 188.1669 + 141 0.0000 7.068149 192.3341 + 142 0.0000 7.125978 193.9077 + 143 0.0000 7.175173 195.2464 + 144 0.0000 7.202180 195.9813 + 145 0.0000 7.231740 196.7856 + 146 0.0000 7.261129 197.5854 + 147 0.0000 7.340301 199.7397 + 148 0.0000 7.386918 201.0082 + 149 0.0000 7.440262 202.4598 + 150 0.0000 7.479916 203.5389 + 151 0.0000 7.601011 206.8340 + 152 0.0000 7.635595 207.7751 + 153 0.0000 7.687374 209.1841 + 154 0.0000 7.823981 212.9013 + 155 0.0000 7.949442 216.3153 + 156 0.0000 8.056304 219.2232 + 157 0.0000 8.394174 228.4171 + 158 0.0000 14.121993 384.2790 + 159 0.0000 15.006496 408.3475 + 160 0.0000 16.014077 435.7652 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.347063 0.000000 + 1 N : 0.343479 0.000000 + 2 O : -0.273576 0.000000 + 3 H : 0.277160 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.866814 s : 3.866814 + pz : 1.406442 p : 4.451766 + px : 1.237808 + py : 1.807516 + dz2 : 0.011233 d : 0.023808 + dxz : -0.001925 + dyz : 0.001020 + dx2y2 : 0.006295 + dxy : 0.007185 + f0 : 0.000431 f : 0.004675 + f+1 : 0.001031 + f-1 : 0.000291 + f+2 : 0.000563 + f-2 : -0.000072 + f+3 : 0.001037 + f-3 : 0.001394 + 1 N s : 3.829439 s : 3.829439 + pz : 1.069666 p : 2.655265 + px : 0.832315 + py : 0.753285 + dz2 : 0.031996 d : 0.141775 + dxz : 0.033840 + dyz : 0.029537 + dx2y2 : 0.023640 + dxy : 0.022762 + f0 : 0.005352 f : 0.030041 + f+1 : 0.008907 + f-1 : 0.005362 + f+2 : 0.002657 + f-2 : 0.000601 + f+3 : 0.002171 + f-3 : 0.004991 + 2 O s : 3.879031 s : 3.879031 + pz : 1.203159 p : 4.323717 + px : 1.848258 + py : 1.272300 + dz2 : 0.015421 d : 0.063082 + dxz : 0.016516 + dyz : 0.028838 + dx2y2 : 0.000268 + dxy : 0.002039 + f0 : 0.002249 f : 0.007747 + f+1 : 0.002288 + f-1 : 0.002615 + f+2 : 0.000135 + f-2 : 0.000515 + f+3 : 0.000007 + f-3 : -0.000062 + 3 H s : 0.621919 s : 0.621919 + pz : 0.017790 p : 0.078687 + px : 0.020124 + py : 0.040773 + dz2 : 0.002525 d : 0.022235 + dxz : 0.010893 + dyz : 0.008295 + dx2y2 : 0.000074 + dxy : 0.000449 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.597902 0.000000 + 1 N : -0.266950 0.000000 + 2 O : 0.235838 0.000000 + 3 H : -0.566790 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.115723 s : 3.115723 + pz : 1.296713 p : 3.908547 + px : 1.179155 + py : 1.432678 + dz2 : 0.069850 d : 0.290050 + dxz : 0.071212 + dyz : 0.010995 + dx2y2 : 0.090192 + dxy : 0.047801 + f0 : 0.014811 f : 0.087778 + f+1 : 0.016232 + f-1 : 0.003024 + f+2 : 0.017741 + f-2 : 0.002971 + f+3 : 0.017687 + f-3 : 0.015313 + 1 N s : 3.005574 s : 3.005574 + pz : 1.219238 p : 2.835596 + px : 0.909704 + py : 0.706654 + dz2 : 0.268555 d : 0.967630 + dxz : 0.304822 + dyz : 0.119981 + dx2y2 : 0.148397 + dxy : 0.125876 + f0 : 0.104483 f : 0.458149 + f+1 : 0.132175 + f-1 : 0.063704 + f+2 : 0.052116 + f-2 : 0.013168 + f+3 : 0.037595 + f-3 : 0.054908 + 2 O s : 3.317026 s : 3.317026 + pz : 1.398141 p : 4.004623 + px : 1.511030 + py : 1.095453 + dz2 : 0.145675 d : 0.324735 + dxz : 0.096939 + dyz : 0.055555 + dx2y2 : 0.018265 + dxy : 0.008300 + f0 : 0.045490 f : 0.117778 + f+1 : 0.030630 + f-1 : 0.022346 + f+2 : 0.012406 + f-2 : 0.005439 + f+3 : 0.001010 + f-3 : 0.000459 + 3 H s : 0.620285 s : 0.620285 + pz : 0.257039 p : 0.552945 + px : 0.130703 + py : 0.165204 + dz2 : 0.128856 d : 0.393560 + dxz : 0.112566 + dyz : 0.117632 + dx2y2 : 0.022823 + dxy : 0.011683 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3471 8.0000 -0.3471 1.9235 1.9235 0.0000 + 1 N 6.6565 7.0000 0.3435 2.5385 2.5385 0.0000 + 2 O 8.2736 8.0000 -0.2736 1.7338 1.7338 -0.0000 + 3 H 0.7228 1.0000 0.2772 0.9423 0.9423 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.9062 B( 0-O , 3-H ) : 0.9614 B( 1-N , 2-O ) : 1.6646 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 7 sec + +Total time .... 7.373 sec +Sum of individual times .... 6.930 sec ( 94.0%) + +Fock matrix formation .... 5.997 sec ( 81.3%) +Diagonalization .... 0.419 sec ( 5.7%) +Density matrix formation .... 0.033 sec ( 0.5%) +Population analysis .... 0.047 sec ( 0.6%) +Initial guess .... 0.033 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.023 sec ( 0.3%) +DIIS solution .... 0.401 sec ( 5.4%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.605 sec +Reference energy ... -204.720481431 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 11.523 sec +AO-integral generation ... 0.357 sec +Half transformation ... 0.179 sec +K-integral sorting ... 8.737 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.068 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.063 s ( 0.000 ms/b) + 277134 b 0 skpd 0.075 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.103 s ( 0.001 ms/b) +: 159120 b 0 skpd 0.046 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.094 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.077 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.060 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.103 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.063 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.866 sec +AO-integral generation ... 0.650 sec +Half transformation ... 0.106 sec +J-integral sorting ... 0.082 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.340 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.398 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090536894 +EMP2(bb)= -0.090536894 +EMP2(ab)= -0.516650521 + +Initial guess performed in 0.192 sec +E(0) ... -204.720481431 +E(MP2) ... -0.697724309 +Initial E(tot) ... -205.418205741 + ... 0.188221039 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.418205741 -0.697724309 -0.000000000 0.025464462 6.01 0.000001672 + *** Turning on DIIS *** + 1 -205.389074053 -0.668592621 0.029131688 0.010866603 7.14 0.057732534 + 2 -205.408576822 -0.688095391 -0.019502770 0.005555044 6.95 0.060688908 + 3 -205.412298507 -0.691817076 -0.003721685 0.002277339 7.31 0.075019534 + 4 -205.413867234 -0.693385802 -0.001568726 0.001636404 6.80 0.081837095 + 5 -205.414424631 -0.693943199 -0.000557397 0.000897393 7.35 0.087546673 + 6 -205.414536898 -0.694055467 -0.000112267 0.000535258 6.57 0.090383777 + 7 -205.414582032 -0.694100600 -0.000045134 0.000216884 6.34 0.091659722 + 8 -205.414594106 -0.694112674 -0.000012074 0.000111651 5.42 0.092134675 + 9 -205.414589854 -0.694108422 0.000004252 0.000030113 5.81 0.092273226 + 10 -205.414594493 -0.694113062 -0.000004640 0.000015087 7.27 0.092314451 + 11 -205.414591958 -0.694110527 0.000002535 0.000012135 7.94 0.092307569 + 12 -205.414592974 -0.694111542 -0.000001016 0.000009448 6.30 0.092316444 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.720481431 +E(CORR) ... -0.694111542 +E(TOT) ... -205.414592974 +Singles norm **1/2 ... 0.092316444 ( 0.046158222, 0.046158222) +T1 diagnostic ... 0.021759195 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.059226 + 10a-> 13a 10b-> 13b 0.048302 + 8b-> 13b -1b-> -1b 0.041602 + 8a-> 13a -1a-> -1a 0.041602 + 10a-> 13a -1a-> -1a 0.033338 + 10b-> 13b -1b-> -1b 0.033338 + 8a-> 13a 10b-> 13b 0.032554 + 10a-> 13a 8b-> 13b 0.032554 + 11a-> 13a 11b-> 13b 0.028238 + 11b-> 26b -1b-> -1b 0.026622 + 11a-> 26a -1a-> -1a 0.026622 + 11a-> 26a 11b-> 26b 0.026147 + 5a-> 13a 5b-> 13b 0.026058 + 8a-> 13a 9b-> 13b 0.024952 + 9a-> 13a 8b-> 13b 0.024952 + 9a-> 13a 10b-> 13b 0.021023 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034718626 + alpha-alpha-alpha ... -0.000896775 ( 2.6%) + alpha-alpha-beta ... -0.016462538 ( 47.4%) + alpha-beta -beta ... -0.016462538 ( 47.4%) + beta -beta -beta ... -0.000896775 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034718626 + +Final correlation energy ... -0.728830169 +E(CCSD) ... -205.414592974 +E(CCSD(T)) ... -205.449311600 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210013743 sqrt= 1.100006247 +W(HF) = 0.826436895 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.260617 -0.000000 + 1 N : 0.154372 0.000000 + 2 O : -0.157750 -0.000000 + 3 H : 0.263995 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.845573 s : 3.845573 + pz : 1.387696 p : 4.350592 + px : 1.234014 + py : 1.728881 + dz2 : 0.015995 d : 0.055976 + dxz : 0.006176 + dyz : 0.007911 + dx2y2 : 0.011247 + dxy : 0.014647 + f0 : 0.001134 f : 0.008476 + f+1 : 0.001463 + f-1 : 0.000924 + f+2 : 0.001120 + f-2 : 0.000610 + f+3 : 0.001302 + f-3 : 0.001924 + 1 N s : 3.880841 s : 3.880841 + pz : 1.038305 p : 2.763150 + px : 0.870080 + py : 0.854764 + dz2 : 0.035801 d : 0.172215 + dxz : 0.045342 + dyz : 0.030281 + dx2y2 : 0.029391 + dxy : 0.031399 + f0 : 0.004719 f : 0.029423 + f+1 : 0.008646 + f-1 : 0.004471 + f+2 : 0.003027 + f-2 : 0.001133 + f+3 : 0.002306 + f-3 : 0.005121 + 2 O s : 3.867155 s : 3.867155 + pz : 1.190767 p : 4.195611 + px : 1.766998 + py : 1.237847 + dz2 : 0.017721 d : 0.084678 + dxz : 0.023331 + dyz : 0.028803 + dx2y2 : 0.006673 + dxy : 0.008150 + f0 : 0.002281 f : 0.010307 + f+1 : 0.002709 + f-1 : 0.002446 + f+2 : 0.000740 + f-2 : 0.001039 + f+3 : 0.000582 + f-3 : 0.000510 + 3 H s : 0.633830 s : 0.633830 + pz : 0.012583 p : 0.083035 + px : 0.023822 + py : 0.046631 + dz2 : 0.001329 d : 0.019139 + dxz : 0.009828 + dyz : 0.006838 + dx2y2 : 0.000560 + dxy : 0.000584 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.613874 -0.000000 + 1 N : -0.316543 -0.000000 + 2 O : 0.270029 0.000000 + 3 H : -0.567361 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.122780 s : 3.122780 + pz : 1.284179 p : 3.847458 + px : 1.187559 + py : 1.375720 + dz2 : 0.076518 d : 0.321154 + dxz : 0.076486 + dyz : 0.016931 + dx2y2 : 0.096925 + dxy : 0.054293 + f0 : 0.015728 f : 0.094734 + f+1 : 0.016996 + f-1 : 0.004035 + f+2 : 0.018074 + f-2 : 0.003452 + f+3 : 0.019169 + f-3 : 0.017280 + 1 N s : 3.010781 s : 3.010781 + pz : 1.191460 p : 2.882679 + px : 0.922013 + py : 0.769206 + dz2 : 0.273580 d : 0.976761 + dxz : 0.302797 + dyz : 0.117371 + dx2y2 : 0.155824 + dxy : 0.127189 + f0 : 0.101462 f : 0.446322 + f+1 : 0.129229 + f-1 : 0.063213 + f+2 : 0.049798 + f-2 : 0.013490 + f+3 : 0.038517 + f-3 : 0.050613 + 2 O s : 3.318902 s : 3.318902 + pz : 1.388885 p : 3.928813 + px : 1.458637 + py : 1.081291 + dz2 : 0.150367 d : 0.355871 + dxz : 0.099790 + dyz : 0.066484 + dx2y2 : 0.023822 + dxy : 0.015407 + f0 : 0.046032 f : 0.126386 + f+1 : 0.031640 + f-1 : 0.026303 + f+2 : 0.012667 + f-2 : 0.007120 + f+3 : 0.001573 + f-3 : 0.001051 + 3 H s : 0.622319 s : 0.622319 + pz : 0.260403 p : 0.561799 + px : 0.131746 + py : 0.169650 + dz2 : 0.127575 d : 0.383243 + dxz : 0.108837 + dyz : 0.111722 + dx2y2 : 0.023212 + dxy : 0.011898 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2606 8.0000 -0.2606 2.2890 1.8289 0.4601 + 1 N 6.8456 7.0000 0.1544 2.8268 2.3490 0.4778 + 2 O 8.1578 8.0000 -0.1578 2.1345 1.6368 0.4978 + 3 H 0.7360 1.0000 0.2640 0.9644 0.8937 0.0708 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8407 B( 0-O , 3-H ) : 0.8902 B( 1-N , 2-O ) : 1.5218 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 119.179 sec + +Fock Matrix Formation ... 0.605 sec ( 0.5%) +Initial Guess ... 0.192 sec ( 0.2%) +DIIS Solver ... 5.800 sec ( 4.9%) +State Vector Update ... 0.329 sec ( 0.3%) +Sigma-vector construction ... 81.077 sec ( 68.0%) + <0|H|D> ... 0.011 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.057 sec ( 0.1% of sigma) + (0-ext) ... 0.175 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.057 sec ( 0.1% of sigma) + (2-ext) ... 2.104 sec ( 2.6% of sigma) + (4-ext) ... 47.379 sec ( 58.4% of sigma) + ... 4.084 sec ( 5.0% of sigma) + ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.020 sec ( 0.0% of sigma) + (1-ext) ... 0.229 sec ( 0.3% of sigma) + Fock-dressing ... 5.170 sec ( 6.4% of sigma) + (ik|jl)-dressing ... 0.176 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 17.650 sec ( 21.8% of sigma) + Pair energies ... 0.022 sec ( 0.0% of sigma) +Total Time for computing (T) ... 16.028 sec ( 13.4% of ALL) + I/O of integral and amplitudes ... 1.945 sec ( 12.1% of (T)) + External N**7 contributions ... 9.600 sec ( 59.9% of (T)) + Internal N**7 contributions ... 0.916 sec ( 5.7% of (T)) + N**6 triples energy contributions ... 3.427 sec ( 21.4% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.449311600306 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.000834845 -0.006972011 -0.000346839 + 2 N : -0.002707120 -0.007205608 0.001716938 + 3 O : 0.001432781 0.006558314 -0.001979361 + 4 H : 0.000439494 0.007619306 0.000609262 + +Norm of the cartesian gradient ... 0.014806207 +RMS gradient ... 0.004274184 +MAX gradient ... 0.007619306 + +------- +TIMINGS +------- + +Total numerical gradient time ... 827.695 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 501.09 cm**-1 + 7: 627.29 cm**-1 + 8: 822.87 cm**-1 + 9: 1293.52 cm**-1 + 10: 1700.61 cm**-1 + 11: 3711.50 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 0.072881 -0.372910 0.187685 -0.050113 -0.102981 0.004358 + 1 0.049917 0.028304 -0.075429 -0.002833 0.007436 -0.015590 + 2 -0.041601 0.236355 0.088264 -0.070417 -0.039228 -0.060693 + 3 -0.046315 0.061115 -0.493639 0.043352 -0.032854 -0.000182 + 4 0.071509 0.082948 0.064017 0.015284 -0.095038 0.000651 + 5 0.031237 -0.190845 -0.074746 0.002953 0.636487 -0.001599 + 6 -0.027599 0.305812 0.197548 -0.050151 0.098216 -0.000442 + 7 -0.051762 -0.060783 -0.000824 -0.006031 0.077917 -0.000545 + 8 0.001178 -0.097312 -0.023930 0.067188 -0.520507 0.001287 + 9 -0.075132 0.215747 0.745097 0.988984 0.532162 -0.059621 + 10 -0.964404 -0.637125 0.320706 -0.071702 -0.034095 0.247068 + 11 0.207533 0.445058 0.017554 0.010229 0.039623 0.965118 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 501.09 0.031617 159.78 0.019690 (-0.075430 -0.098142 0.066093) + 7: 627.29 0.016823 85.02 0.008369 ( 0.076654 -0.029820 -0.040048) + 8: 822.87 0.024320 122.90 0.009223 (-0.082252 0.019090 0.045752) + 9: 1293.52 0.030002 151.62 0.007238 ( 0.079450 -0.011306 -0.028246) + 10: 1700.61 0.023216 117.32 0.004260 (-0.046467 -0.001870 0.045799) + 11: 3711.50 0.014519 73.37 0.001221 (-0.015251 0.008501 0.030263) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 501.09 E(vib) ... 0.14 +freq. 627.29 E(vib) ... 0.09 +freq. 822.87 E(vib) ... 0.05 +freq. 1293.52 E(vib) ... 0.01 +freq. 1700.61 E(vib) ... 0.00 +freq. 3711.50 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.44931160 Eh +Zero point energy ... 0.01972182 Eh 12.38 kcal/mol +Thermal vibrational correction ... 0.00045454 Eh 0.29 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42630270 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00328708 Eh 2.06 kcal/mol +Non-thermal (ZPE) correction 0.01972182 Eh 12.38 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02300890 Eh 14.44 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42630270 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.42535849 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 3.026502 0.416785 0.368529 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00061032 Eh 0.38 kcal/mol +Rotational entropy ... 0.00987244 Eh 6.20 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02828507 Eh 17.75 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00987244 Eh 6.20 kcal/mol| +| sn= 2 | S(rot)= 0.00921798 Eh 5.78 kcal/mol| +| sn= 3 | S(rot)= 0.00883515 Eh 5.54 kcal/mol| +| sn= 4 | S(rot)= 0.00856352 Eh 5.37 kcal/mol| +| sn= 5 | S(rot)= 0.00835284 Eh 5.24 kcal/mol| +| sn= 6 | S(rot)= 0.00818069 Eh 5.13 kcal/mol| +| sn= 7 | S(rot)= 0.00803515 Eh 5.04 kcal/mol| +| sn= 8 | S(rot)= 0.00790907 Eh 4.96 kcal/mol| +| sn= 9 | S(rot)= 0.00779786 Eh 4.89 kcal/mol| +| sn=10 | S(rot)= 0.00769838 Eh 4.83 kcal/mol| +| sn=11 | S(rot)= 0.00760839 Eh 4.77 kcal/mol| +| sn=12 | S(rot)= 0.00752624 Eh 4.72 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.42535849 Eh +Total entropy correction ... -0.02828507 Eh -17.75 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.45364356 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00433196 Eh -2.72 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.449311601 Eh +Current gradient norm .... 0.014806205 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.025692128 0.134272000 0.186237871 0.490535094 0.525487212 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999917323 +Lowest eigenvalues of augmented Hessian: + -0.000042027 0.133243722 0.185822274 0.490524050 0.525476953 +Length of the computed step .... 0.012859786 +The final length of the internal step .... 0.012859786 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0052499857 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0024657580 RMS(Int)= 0.0052504219 + Iter 1: RMS(Cart)= 0.0000047090 RMS(Int)= 0.0000071430 + Iter 2: RMS(Cart)= 0.0000000089 RMS(Int)= 0.0000000174 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0017116822 0.0001000000 NO + MAX gradient 0.0031487516 0.0003000000 NO + RMS step 0.0052499857 0.0020000000 NO + MAX step 0.0104748624 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0055 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4373 -0.001157 0.0055 1.4428 + 2. B(O 2,N 1) 1.1753 0.003149 -0.0029 1.1724 + 3. B(H 3,O 0) 0.9717 0.002499 -0.0027 0.9690 + 4. A(N 1,O 0,H 3) 102.02 -0.000221 -0.00 102.02 + 5. A(O 0,N 1,O 2) 110.54 -0.000172 0.00 110.54 + 6. D(O 2,N 1,O 0,H 3) -155.45 0.012997 -0.00 -155.45 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.767657 -0.030518 0.147416 + N 0.654236 -0.173360 -0.051474 + O 0.930266 -0.011306 -1.179380 + H -0.816844 0.215185 1.083437 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.450661 -0.057671 0.278576 + 1 N 7.0000 0 14.007 1.236327 -0.327603 -0.097272 + 2 O 8.0000 0 15.999 1.757947 -0.021366 -2.228704 + 3 H 1.0000 0 1.008 -1.543611 0.406640 2.047400 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.442823970687 0.00000000 0.00000000 + O 2 1 0 1.172443866241 110.54498898 0.00000000 + H 1 2 3 0.968981646474 102.02201363 204.54545428 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.726542164055 0.00000000 0.00000000 + O 2 1 0 2.215597814591 110.54498898 0.00000000 + H 1 2 3 1.831109940631 102.02201363 204.54545428 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.327062289423 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.971e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7205403760 0.000000000000 0.00018282 0.00000566 0.0012115 0.7000 + 1 -204.7205479710 -0.000007594978 0.00014358 0.00000469 0.0010010 0.7000 + ***Turning on DIIS*** + 2 -204.7205541741 -0.000006203128 0.00036071 0.00001235 0.0008043 0.0000 + 3 -204.7202296603 0.000324513800 0.00014194 0.00000463 0.0002439 0.0000 + 4 -204.7206247095 -0.000395049211 0.00004532 0.00000154 0.0000684 0.0000 + 5 -204.7207036135 -0.000078903967 0.00001784 0.00000051 0.0000330 0.0000 + 6 -204.7204956817 0.000207931851 0.00001623 0.00000032 0.0000214 0.0000 + 7 -204.7205855074 -0.000089825752 0.00000312 0.00000013 0.0000048 0.0000 + 8 -204.7205822016 0.000003305802 0.00000197 0.00000008 0.0000026 0.0000 + 9 -204.7205642524 0.000017949178 0.00000177 0.00000007 0.0000020 0.0000 + 10 -204.7205784398 -0.000014187384 0.00000157 0.00000006 0.0000013 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + +Total Energy : -204.72057286 Eh -5570.73000 eV + Last Energy change ... 5.5761e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.7487e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.203 sec +Reference energy ... -204.720573887 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.410 sec +AO-integral generation ... 0.143 sec +Half transformation ... 0.080 sec +K-integral sorting ... 5.418 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.026 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.025 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.028 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.040 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.041 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.025 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.364 sec +AO-integral generation ... 0.246 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.055 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.151 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.251 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090516801 +EMP2(bb)= -0.090516801 +EMP2(ab)= -0.516592792 + +Initial guess performed in 0.132 sec +E(0) ... -204.720573887 +E(MP2) ... -0.697626395 +Initial E(tot) ... -205.418200282 + ... 0.188173195 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.418200282 -0.697626395 -0.000000000 0.025198004 2.79 0.000001027 + *** Turning on DIIS *** + 1 -205.389088130 -0.668514242 0.029112152 0.010703810 2.94 0.057776215 + 2 -205.408586650 -0.688012763 -0.019498521 0.005474725 2.76 0.060712636 + 3 -205.412306642 -0.691732755 -0.003719991 0.002255090 2.74 0.075071049 + 4 -205.413875046 -0.693301159 -0.001568405 0.001683678 2.79 0.081907101 + 5 -205.414435387 -0.693861500 -0.000560341 0.000918620 2.82 0.087676474 + 6 -205.414549389 -0.693975502 -0.000114002 0.000546516 2.80 0.090571768 + 7 -205.414595691 -0.694021804 -0.000046302 0.000217840 2.85 0.091889098 + 8 -205.414608178 -0.694034291 -0.000012487 0.000112104 3.18 0.092376645 + 9 -205.414603863 -0.694029976 0.000004315 0.000029970 2.79 0.092518548 + 10 -205.414608582 -0.694034695 -0.000004719 0.000014850 3.07 0.092560544 + 11 -205.414605992 -0.694032105 0.000002590 0.000011927 2.81 0.092553405 + 12 -205.414607030 -0.694033143 -0.000001038 0.000009287 3.20 0.092562704 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.720573887 +E(CORR) ... -0.694033143 +E(TOT) ... -205.414607030 +Singles norm **1/2 ... 0.092562704 ( 0.046281352, 0.046281352) +T1 diagnostic ... 0.021817239 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.060023 + 10a-> 13a 10b-> 13b 0.046743 + 8a-> 13a -1a-> -1a 0.040973 + 8b-> 13b -1b-> -1b 0.040973 + 10a-> 13a -1a-> -1a 0.034506 + 10b-> 13b -1b-> -1b 0.034506 + 10a-> 13a 8b-> 13b 0.032157 + 8a-> 13a 10b-> 13b 0.032157 + 11a-> 13a 11b-> 13b 0.028023 + 5a-> 13a 5b-> 13b 0.026163 + 11a-> 26a -1a-> -1a 0.025850 + 11b-> 26b -1b-> -1b 0.025850 + 11a-> 26a 11b-> 26b 0.025544 + 9a-> 13a 8b-> 13b 0.025116 + 8a-> 13a 9b-> 13b 0.025116 + 8a-> 22a 8b-> 13b 0.021065 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034725708 + alpha-alpha-alpha ... -0.000896692 ( 2.6%) + alpha-alpha-beta ... -0.016466162 ( 47.4%) + alpha-beta -beta ... -0.016466162 ( 47.4%) + beta -beta -beta ... -0.000896692 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034725708 + +Final correlation energy ... -0.728758851 +E(CCSD) ... -205.414607030 +E(CCSD(T)) ... -205.449332738 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210077471 sqrt= 1.100035214 +W(HF) = 0.826393370 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 52.795 sec + +Fock Matrix Formation ... 0.203 sec ( 0.4%) +Initial Guess ... 0.132 sec ( 0.3%) +DIIS Solver ... 1.610 sec ( 3.0%) +State Vector Update ... 0.077 sec ( 0.1%) +Sigma-vector construction ... 35.854 sec ( 67.9%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.024 sec ( 0.1% of sigma) + (0-ext) ... 0.066 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.024 sec ( 0.1% of sigma) + (2-ext) ... 0.878 sec ( 2.4% of sigma) + (4-ext) ... 19.778 sec ( 55.2% of sigma) + ... 1.314 sec ( 3.7% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.103 sec ( 0.3% of sigma) + Fock-dressing ... 1.951 sec ( 5.4% of sigma) + (ik|jl)-dressing ... 0.073 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.124 sec ( 25.4% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 7.115 sec ( 13.5% of ALL) + I/O of integral and amplitudes ... 0.950 sec ( 13.3% of (T)) + External N**7 contributions ... 3.963 sec ( 55.7% of (T)) + Internal N**7 contributions ... 0.324 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.786 sec ( 25.1% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.449332738151 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.000253722 -0.006172345 0.002353580 + 2 N : -0.000931086 -0.006811377 -0.001626238 + 3 O : 0.000738616 0.006055619 0.001089118 + 4 H : 0.000446192 0.006928103 -0.001816459 + +Norm of the cartesian gradient ... 0.013546493 +RMS gradient ... 0.003910536 +MAX gradient ... 0.006928103 + +------- +TIMINGS +------- + +Total numerical gradient time ... 345.986 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.449332738 Eh +Current gradient norm .... 0.013546493 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999970 +Lowest eigenvalues of augmented Hessian: + -0.000000011 0.131592892 0.185327721 0.492507874 0.525580252 +Length of the computed step .... 0.000243588 +The final length of the internal step .... 0.000243588 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0000994444 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0000633146 RMS(Int)= 0.0000994448 + Iter 1: RMS(Cart)= 0.0000000011 RMS(Int)= 0.0000000019 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000211368 0.0000050000 NO + RMS gradient 0.0000257954 0.0001000000 YES + MAX gradient 0.0000414099 0.0003000000 YES + RMS step 0.0000994444 0.0020000000 YES + MAX step 0.0002327820 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4428 -0.000041 0.0001 1.4429 + 2. B(O 2,N 1) 1.1724 -0.000036 0.0000 1.1724 + 3. B(H 3,O 0) 0.9690 -0.000020 0.0000 0.9690 + 4. A(N 1,O 0,H 3) 102.02 -0.000001 -0.00 102.02 + 5. A(O 0,N 1,O 2) 110.54 -0.000023 0.00 110.55 + 6. D(O 2,N 1,O 0,H 3) -155.45 0.012854 0.00 -155.45 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.767734 -0.030520 0.147431 + N 0.654278 -0.173359 -0.051499 + O 0.930314 -0.011312 -1.179407 + H -0.816857 0.215191 1.083476 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.450808 -0.057674 0.278604 + 1 N 7.0000 0 14.007 1.236407 -0.327601 -0.097320 + 2 O 8.0000 0 15.999 1.758039 -0.021376 -2.228757 + 3 H 1.0000 0 1.008 -1.543636 0.406651 2.047473 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.442947153624 0.00000000 0.00000000 + O 2 1 0 1.172446528642 110.54633690 0.00000000 + H 1 2 3 0.969002936295 102.01890151 204.54545428 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.726774946070 0.00000000 0.00000000 + O 2 1 0 2.215602845801 110.54633690 0.00000000 + H 1 2 3 1.831150172563 102.01890151 204.54545428 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.324110575154 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.3241105752 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.972e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7205605916 0.000000000000 0.00000408 0.00000010 0.0000234 0.7000 + 1 -204.7205605938 -0.000000002128 0.00000324 0.00000008 0.0000183 0.7000 + ***Turning on DIIS*** + 2 -204.7205605956 -0.000000001886 0.00000790 0.00000021 0.0000141 0.0000 + 3 -204.7205661131 -0.000005517445 0.00000316 0.00000009 0.0000036 0.0000 + 4 -204.7205594131 0.000006699987 0.00000120 0.00000003 0.0000010 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72055780 Eh -5570.72959 eV + +Components: +Nuclear Repulsion : 69.32411058 Eh 1886.40495 eV +Electronic Energy : -274.04466838 Eh -7457.13454 eV +One Electron Energy: -418.35580363 Eh -11384.04017 eV +Two Electron Energy: 144.31113525 Eh 3926.90563 eV + +Virial components: +Potential Energy : -408.96593957 Eh -11128.52898 eV +Kinetic Energy : 204.24538176 Eh 5557.79939 eV +Virial Ratio : 2.00232650 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.6083e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.8182e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 7.7065e-09 Tolerance : 5.0000e-09 + Last DIIS Error ... 4.0310e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.670666 -562.4774 + 1 1.0000 -20.636222 -561.5401 + 2 1.0000 -15.799627 -429.9297 + 3 1.0000 -1.606419 -43.7129 + 4 1.0000 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2.163413 58.8695 + 79 0.0000 2.179492 59.3070 + 80 0.0000 2.284126 62.1542 + 81 0.0000 2.303834 62.6905 + 82 0.0000 2.313435 62.9518 + 83 0.0000 2.375504 64.6408 + 84 0.0000 2.445462 66.5444 + 85 0.0000 2.468105 67.1605 + 86 0.0000 2.491523 67.7978 + 87 0.0000 2.502122 68.0862 + 88 0.0000 2.520291 68.5806 + 89 0.0000 2.533606 68.9429 + 90 0.0000 2.573742 70.0351 + 91 0.0000 2.601949 70.8026 + 92 0.0000 2.646596 72.0175 + 93 0.0000 2.705797 73.6285 + 94 0.0000 2.736519 74.4645 + 95 0.0000 2.755879 74.9913 + 96 0.0000 2.862486 77.8922 + 97 0.0000 2.897107 78.8343 + 98 0.0000 2.944369 80.1204 + 99 0.0000 3.095291 84.2272 + 100 0.0000 3.151939 85.7686 + 101 0.0000 3.181058 86.5610 + 102 0.0000 3.260074 88.7111 + 103 0.0000 3.464448 94.2724 + 104 0.0000 3.773503 102.6822 + 105 0.0000 3.890763 105.8730 + 106 0.0000 4.029306 109.6430 + 107 0.0000 4.163287 113.2888 + 108 0.0000 4.182631 113.8152 + 109 0.0000 4.260555 115.9356 + 110 0.0000 4.362082 118.6983 + 111 0.0000 4.400011 119.7304 + 112 0.0000 4.558170 124.0341 + 113 0.0000 4.626516 125.8939 + 114 0.0000 4.751317 129.2899 + 115 0.0000 4.805443 130.7628 + 116 0.0000 4.821142 131.1899 + 117 0.0000 4.892766 133.1389 + 118 0.0000 4.965858 135.1279 + 119 0.0000 5.001828 136.1067 + 120 0.0000 5.070867 137.9853 + 121 0.0000 5.100639 138.7955 + 122 0.0000 5.173736 140.7845 + 123 0.0000 5.241219 142.6208 + 124 0.0000 5.256497 143.0366 + 125 0.0000 5.326217 144.9337 + 126 0.0000 5.336908 145.2247 + 127 0.0000 5.410306 147.2219 + 128 0.0000 5.562459 151.3622 + 129 0.0000 5.684981 154.6962 + 130 0.0000 5.796679 157.7357 + 131 0.0000 6.001318 163.3042 + 132 0.0000 6.113133 166.3468 + 133 0.0000 6.416462 174.6008 + 134 0.0000 6.502972 176.9549 + 135 0.0000 6.509353 177.1285 + 136 0.0000 6.686653 181.9531 + 137 0.0000 6.708514 182.5479 + 138 0.0000 6.741256 183.4389 + 139 0.0000 6.848083 186.3458 + 140 0.0000 6.913393 188.1230 + 141 0.0000 7.068392 192.3407 + 142 0.0000 7.126298 193.9164 + 143 0.0000 7.181026 195.4057 + 144 0.0000 7.201977 195.9758 + 145 0.0000 7.233572 196.8355 + 146 0.0000 7.263162 197.6407 + 147 0.0000 7.346064 199.8966 + 148 0.0000 7.391107 201.1222 + 149 0.0000 7.438428 202.4099 + 150 0.0000 7.479572 203.5295 + 151 0.0000 7.604916 206.9403 + 152 0.0000 7.634694 207.7506 + 153 0.0000 7.686633 209.1639 + 154 0.0000 7.826302 212.9645 + 155 0.0000 7.943008 216.1402 + 156 0.0000 8.050795 219.0733 + 157 0.0000 8.397685 228.5126 + 158 0.0000 14.135742 384.6531 + 159 0.0000 15.020546 408.7298 + 160 0.0000 16.086211 437.7281 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.348648 0.000000 + 1 N : 0.345225 0.000000 + 2 O : -0.270740 0.000000 + 3 H : 0.274162 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.867258 s : 3.867258 + pz : 1.404744 p : 4.453336 + px : 1.239708 + py : 1.808883 + dz2 : 0.011058 d : 0.023436 + dxz : -0.001906 + dyz : 0.000986 + dx2y2 : 0.006262 + dxy : 0.007037 + f0 : 0.000411 f : 0.004618 + f+1 : 0.001030 + f-1 : 0.000287 + f+2 : 0.000554 + f-2 : -0.000070 + f+3 : 0.001031 + f-3 : 0.001375 + 1 N s : 3.829776 s : 3.829776 + pz : 1.068956 p : 2.653566 + px : 0.831634 + py : 0.752975 + dz2 : 0.031859 d : 0.141491 + dxz : 0.033987 + dyz : 0.029493 + dx2y2 : 0.023698 + dxy : 0.022454 + f0 : 0.005333 f : 0.029942 + f+1 : 0.008940 + f-1 : 0.005324 + f+2 : 0.002622 + f-2 : 0.000601 + f+3 : 0.002177 + f-3 : 0.004944 + 2 O s : 3.878181 s : 3.878181 + pz : 1.203495 p : 4.321128 + px : 1.846472 + py : 1.271161 + dz2 : 0.015516 d : 0.063652 + dxz : 0.016774 + dyz : 0.029050 + dx2y2 : 0.000277 + dxy : 0.002035 + f0 : 0.002248 f : 0.007779 + f+1 : 0.002309 + f-1 : 0.002630 + f+2 : 0.000136 + f-2 : 0.000511 + f+3 : 0.000006 + f-3 : -0.000062 + 3 H s : 0.624032 s : 0.624032 + pz : 0.017717 p : 0.079416 + px : 0.020432 + py : 0.041267 + dz2 : 0.002561 d : 0.022390 + dxz : 0.010949 + dyz : 0.008369 + dx2y2 : 0.000066 + dxy : 0.000444 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.599830 0.000000 + 1 N : -0.263568 0.000000 + 2 O : 0.237650 0.000000 + 3 H : -0.573912 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.116400 s : 3.116400 + pz : 1.297929 p : 3.909997 + px : 1.178014 + py : 1.434055 + dz2 : 0.069440 d : 0.287164 + dxz : 0.070055 + dyz : 0.010916 + dx2y2 : 0.089685 + dxy : 0.047069 + f0 : 0.014556 f : 0.086609 + f+1 : 0.016116 + f-1 : 0.003002 + f+2 : 0.017376 + f-2 : 0.002945 + f+3 : 0.017555 + f-3 : 0.015057 + 1 N s : 3.007048 s : 3.007048 + pz : 1.221113 p : 2.834890 + px : 0.906377 + py : 0.707399 + dz2 : 0.268465 d : 0.965102 + dxz : 0.304445 + dyz : 0.120100 + dx2y2 : 0.147740 + dxy : 0.124352 + f0 : 0.104098 f : 0.456528 + f+1 : 0.132541 + f-1 : 0.063687 + f+2 : 0.051445 + f-2 : 0.013127 + f+3 : 0.037328 + f-3 : 0.054302 + 2 O s : 3.315671 s : 3.315671 + pz : 1.400026 p : 4.002531 + px : 1.508358 + py : 1.094147 + dz2 : 0.146208 d : 0.326003 + dxz : 0.097393 + dyz : 0.055895 + dx2y2 : 0.018255 + dxy : 0.008252 + f0 : 0.045661 f : 0.118145 + f+1 : 0.030747 + f-1 : 0.022532 + f+2 : 0.012353 + f-2 : 0.005401 + f+3 : 0.000999 + f-3 : 0.000453 + 3 H s : 0.622163 s : 0.622163 + pz : 0.258246 p : 0.556959 + px : 0.131874 + py : 0.166839 + dz2 : 0.129131 d : 0.394789 + dxz : 0.113094 + dyz : 0.118184 + dx2y2 : 0.022746 + dxy : 0.011635 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3486 8.0000 -0.3486 1.9239 1.9239 -0.0000 + 1 N 6.6548 7.0000 0.3452 2.5393 2.5393 -0.0000 + 2 O 8.2707 8.0000 -0.2707 1.7371 1.7371 -0.0000 + 3 H 0.7258 1.0000 0.2742 0.9448 0.9448 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.9037 B( 0-O , 3-H ) : 0.9636 B( 1-N , 2-O ) : 1.6674 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.941 sec +Sum of individual times .... 0.758 sec ( 80.5%) + +Fock matrix formation .... 0.611 sec ( 65.0%) +Diagonalization .... 0.068 sec ( 7.2%) +Density matrix formation .... 0.006 sec ( 0.6%) +Population analysis .... 0.016 sec ( 1.7%) +Initial guess .... 0.009 sec ( 1.0%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.5%) +DIIS solution .... 0.048 sec ( 5.0%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.206 sec +Reference energy ... -204.720560600 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.431 sec +AO-integral generation ... 0.143 sec +Half transformation ... 0.080 sec +K-integral sorting ... 5.438 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.026 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.025 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.028 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.040 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.030 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.043 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.038 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.369 sec +AO-integral generation ... 0.262 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.052 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.156 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.252 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090518349 +EMP2(bb)= -0.090518349 +EMP2(ab)= -0.516602993 + +Initial guess performed in 0.135 sec +E(0) ... -204.720560600 +E(MP2) ... -0.697639692 +Initial E(tot) ... -205.418200293 + ... 0.188185873 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.418200293 -0.697639692 -0.000000000 0.025197615 2.68 0.000000589 + *** Turning on DIIS *** + 1 -205.389081933 -0.668521332 0.029118360 0.010703808 2.95 0.057782742 + 2 -205.408582723 -0.688022122 -0.019500790 0.005474558 2.78 0.060718266 + 3 -205.412303141 -0.691742541 -0.003720419 0.002255292 2.78 0.075078940 + 4 -205.413871835 -0.693311235 -0.001568694 0.001684525 2.79 0.081916281 + 5 -205.414432373 -0.693871773 -0.000560538 0.000919069 2.87 0.087687645 + 6 -205.414546425 -0.693985825 -0.000114052 0.000546809 2.87 0.090584334 + 7 -205.414592758 -0.694032158 -0.000046333 0.000217928 2.93 0.091902639 + 8 -205.414605257 -0.694044657 -0.000012499 0.000112154 2.88 0.092390560 + 9 -205.414600940 -0.694040340 0.000004317 0.000029982 2.97 0.092532571 + 10 -205.414605663 -0.694045062 -0.000004722 0.000014828 2.79 0.092574600 + 11 -205.414603071 -0.694042471 0.000002591 0.000011911 2.83 0.092567454 + 12 -205.414604110 -0.694043510 -0.000001039 0.000009276 2.90 0.092576761 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.720560600 +E(CORR) ... -0.694043510 +E(TOT) ... -205.414604110 +Singles norm **1/2 ... 0.092576761 ( 0.046288380, 0.046288380) +T1 diagnostic ... 0.021820552 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.060041 + 10a-> 13a 10b-> 13b 0.046729 + 8b-> 13b -1b-> -1b 0.040973 + 8a-> 13a -1a-> -1a 0.040973 + 10b-> 13b -1b-> -1b 0.034525 + 10a-> 13a -1a-> -1a 0.034525 + 10a-> 13a 8b-> 13b 0.032157 + 8a-> 13a 10b-> 13b 0.032157 + 11a-> 13a 11b-> 13b 0.028021 + 5a-> 13a 5b-> 13b 0.026169 + 11b-> 26b -1b-> -1b 0.025833 + 11a-> 26a -1a-> -1a 0.025833 + 11a-> 26a 11b-> 26b 0.025522 + 9a-> 13a 8b-> 13b 0.025125 + 8a-> 13a 9b-> 13b 0.025125 + 8a-> 22a 8b-> 13b 0.021069 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034728631 + alpha-alpha-alpha ... -0.000896734 ( 2.6%) + alpha-alpha-beta ... -0.016467582 ( 47.4%) + alpha-beta -beta ... -0.016467582 ( 47.4%) + beta -beta -beta ... -0.000896734 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034728631 + +Final correlation energy ... -0.728772141 +E(CCSD) ... -205.414604110 +E(CCSD(T)) ... -205.449332741 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210094780 sqrt= 1.100043081 +W(HF) = 0.826381550 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.262799 -0.000000 + 1 N : 0.156228 0.000000 + 2 O : -0.154905 0.000000 + 3 H : 0.261476 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.846374 s : 3.846374 + pz : 1.386297 p : 4.352351 + px : 1.235814 + py : 1.730240 + dz2 : 0.015842 d : 0.055649 + dxz : 0.006163 + dyz : 0.007877 + dx2y2 : 0.011257 + dxy : 0.014511 + f0 : 0.001115 f : 0.008425 + f+1 : 0.001461 + f-1 : 0.000920 + f+2 : 0.001111 + f-2 : 0.000611 + f+3 : 0.001297 + f-3 : 0.001910 + 1 N s : 3.880910 s : 3.880910 + pz : 1.037646 p : 2.761685 + px : 0.870709 + py : 0.853330 + dz2 : 0.035608 d : 0.171856 + dxz : 0.045434 + dyz : 0.030256 + dx2y2 : 0.029410 + dxy : 0.031148 + f0 : 0.004701 f : 0.029321 + f+1 : 0.008661 + f-1 : 0.004437 + f+2 : 0.002994 + f-2 : 0.001133 + f+3 : 0.002314 + f-3 : 0.005080 + 2 O s : 3.866405 s : 3.866405 + pz : 1.190966 p : 4.193006 + px : 1.764301 + py : 1.237738 + dz2 : 0.017793 d : 0.085170 + dxz : 0.023598 + dyz : 0.028961 + dx2y2 : 0.006676 + dxy : 0.008142 + f0 : 0.002279 f : 0.010325 + f+1 : 0.002728 + f-1 : 0.002454 + f+2 : 0.000740 + f-2 : 0.001035 + f+3 : 0.000581 + f-3 : 0.000509 + 3 H s : 0.635572 s : 0.635572 + pz : 0.012471 p : 0.083726 + px : 0.024101 + py : 0.047154 + dz2 : 0.001347 d : 0.019226 + dxz : 0.009860 + dyz : 0.006888 + dx2y2 : 0.000552 + dxy : 0.000579 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.615797 -0.000000 + 1 N : -0.313268 -0.000000 + 2 O : 0.271656 0.000000 + 3 H : -0.574185 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.123391 s : 3.123391 + pz : 1.285452 p : 3.848951 + px : 1.186566 + py : 1.376933 + dz2 : 0.076110 d : 0.318306 + dxz : 0.075364 + dyz : 0.016857 + dx2y2 : 0.096474 + dxy : 0.053502 + f0 : 0.015487 f : 0.093555 + f+1 : 0.016882 + f-1 : 0.004006 + f+2 : 0.017738 + f-2 : 0.003429 + f+3 : 0.019044 + f-3 : 0.016970 + 1 N s : 3.012205 s : 3.012205 + pz : 1.193394 p : 2.882065 + px : 0.919671 + py : 0.768999 + dz2 : 0.273425 d : 0.974205 + dxz : 0.302216 + dyz : 0.117668 + dx2y2 : 0.155057 + dxy : 0.125839 + f0 : 0.101124 f : 0.444793 + f+1 : 0.129482 + f-1 : 0.063260 + f+2 : 0.049166 + f-2 : 0.013448 + f+3 : 0.038264 + f-3 : 0.050048 + 2 O s : 3.317543 s : 3.317543 + pz : 1.390689 p : 3.926979 + px : 1.455499 + py : 1.080792 + dz2 : 0.150869 d : 0.357054 + dxz : 0.100245 + dyz : 0.066787 + dx2y2 : 0.023797 + dxy : 0.015357 + f0 : 0.046195 f : 0.126767 + f+1 : 0.031799 + f-1 : 0.026476 + f+2 : 0.012612 + f-2 : 0.007079 + f+3 : 0.001560 + f-3 : 0.001044 + 3 H s : 0.624041 s : 0.624041 + pz : 0.261639 p : 0.565793 + px : 0.132828 + py : 0.171327 + dz2 : 0.127833 d : 0.384351 + dxz : 0.109302 + dyz : 0.112225 + dx2y2 : 0.023148 + dxy : 0.011844 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2628 8.0000 -0.2628 2.2898 1.8287 0.4611 + 1 N 6.8438 7.0000 0.1562 2.8274 2.3497 0.4777 + 2 O 8.1549 8.0000 -0.1549 2.1374 1.6406 0.4968 + 3 H 0.7385 1.0000 0.2615 0.9664 0.8957 0.0707 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8377 B( 0-O , 3-H ) : 0.8921 B( 1-N , 2-O ) : 1.5250 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 52.426 sec + +Fock Matrix Formation ... 0.206 sec ( 0.4%) +Initial Guess ... 0.135 sec ( 0.3%) +DIIS Solver ... 1.770 sec ( 3.4%) +State Vector Update ... 0.083 sec ( 0.2%) +Sigma-vector construction ... 35.156 sec ( 67.1%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.023 sec ( 0.1% of sigma) + (0-ext) ... 0.065 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.024 sec ( 0.1% of sigma) + (2-ext) ... 0.865 sec ( 2.5% of sigma) + (4-ext) ... 19.307 sec ( 54.9% of sigma) + ... 1.355 sec ( 3.9% of sigma) + ... 0.005 sec ( 0.0% of sigma) + (1-ext) ... 0.007 sec ( 0.0% of sigma) + (1-ext) ... 0.108 sec ( 0.3% of sigma) + Fock-dressing ... 1.952 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.070 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 8.916 sec ( 25.4% of sigma) + Pair energies ... 0.007 sec ( 0.0% of sigma) +Total Time for computing (T) ... 7.151 sec ( 13.6% of ALL) + I/O of integral and amplitudes ... 0.802 sec ( 11.2% of (T)) + External N**7 contributions ... 3.903 sec ( 54.6% of (T)) + Internal N**7 contributions ... 0.316 sec ( 4.4% of (T)) + N**6 triples energy contributions ... 1.707 sec ( 23.9% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.449332741136 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.004.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.004.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.439830, -0.115788 -0.648752) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.90087 -0.11851 -0.50739 +Nuclear contribution : -0.98687 0.25995 1.33507 + ----------------------------------------- +Total Dipole Moment : -0.08601 0.14144 0.82768 + ----------------------------------------- +Magnitude (a.u.) : 0.84407 +Magnitude (Debye) : 2.14546 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.026518 0.415672 0.367647 +Rotational constants in MHz : 90732.715715 12461.547527 11021.785447 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.573169 0.570826 -0.241028 +x,y,z [Debye]: 1.456881 1.450925 -0.612644 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.439830, -0.115788 -0.648752) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.88457 -0.11027 -0.68230 +Nuclear contribution : -0.98687 0.25995 1.33507 + ----------------------------------------- +Total Dipole Moment : -0.10230 0.14967 0.65277 + ----------------------------------------- +Magnitude (a.u.) : 0.67748 +Magnitude (Debye) : 1.72202 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.026518 0.415672 0.367647 +Rotational constants in MHz : 90732.715715 12461.547527 11021.785447 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.479789 0.422831 -0.223598 +x,y,z [Debye]: 1.219527 1.074752 -0.568340 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 5 * + * * + * Dihedral ( 2, 1, 0, 3) : -147.27272727 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0397160626 RMS(Int)= 0.0002566147 + Iter 1: RMS(Cart)= 0.0000713708 RMS(Int)= 0.0000013704 + Iter 2: RMS(Cart)= 0.0000003811 RMS(Int)= 0.0000000073 + Iter 3: RMS(Cart)= 0.0000000020 RMS(Int)= 0.0000000000 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4430 0.000000 + 2. B(O 2,N 1) 1.1746 0.000000 + 3. B(H 3,O 0) 0.9718 0.000000 + 4. A(N 1,O 0,H 3) 101.9872 0.000000 + 5. A(O 0,N 1,O 2) 110.4949 0.000000 + 6. D(O 2,N 1,O 0,H 3) -147.2727 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.770247 -0.064141 0.153600 + N 0.650228 -0.210190 -0.054013 + O 0.928591 0.022123 -1.171256 + H -0.808572 0.252208 1.071669 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.455556 -0.121209 0.290262 + 1 N 7.0000 0 14.007 1.228754 -0.397202 -0.102070 + 2 O 8.0000 0 15.999 1.754783 0.041806 -2.213353 + 3 H 1.0000 0 1.008 -1.527979 0.476605 2.025161 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.442947153624 0.00000000 0.00000000 + O 2 1 0 1.172446528642 110.54633690 0.00000000 + H 1 2 3 0.969002936295 102.01890151 204.54545428 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.726774946070 0.00000000 0.00000000 + O 2 1 0 2.215602845801 110.54633690 0.00000000 + H 1 2 3 1.831150172563 102.01890151 204.54545428 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.266769903201 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.2667699032 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.965e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7140102372 0.000000000000 0.00173304 0.00005404 0.0198361 0.7000 + 1 -204.7149161688 -0.000905931599 0.00165870 0.00004880 0.0164252 0.7000 + ***Turning on DIIS*** + 2 -204.7156888707 -0.000772701980 0.00454406 0.00013190 0.0133528 0.0000 + 3 -204.7199712839 -0.004282413157 0.00182373 0.00005344 0.0053597 0.0000 + 4 -204.7173988743 0.002572409578 0.00087568 0.00002424 0.0021318 0.0000 + 5 -204.7190484326 -0.001649558232 0.00054896 0.00001895 0.0010494 0.0000 + 6 -204.7184784604 0.000569972157 0.00063163 0.00002204 0.0006832 0.0000 + 7 -204.7179676639 0.000510796500 0.00033377 0.00001113 0.0003099 0.0000 + 8 -204.7187086220 -0.000740958062 0.00018136 0.00000702 0.0001984 0.0000 + 9 -204.7183286753 0.000379946696 0.00015123 0.00000514 0.0001371 0.0000 + 10 -204.7184813958 -0.000152720567 0.00007298 0.00000220 0.0000616 0.0000 + 11 -204.7185987961 -0.000117400230 0.00002798 0.00000079 0.0000287 0.0000 + 12 -204.7184840059 0.000114790127 0.00000846 0.00000024 0.0000077 0.0000 + 13 -204.7185173579 -0.000033351988 0.00000226 0.00000007 0.0000031 0.0000 + 14 -204.7185058655 0.000011492417 0.00000091 0.00000003 0.0000017 0.0000 + 15 -204.7185085305 -0.000002664951 0.00000052 0.00000002 0.0000011 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 16 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71851014 Eh -5570.67387 eV + +Components: +Nuclear Repulsion : 69.26676990 Eh 1884.84463 eV +Electronic Energy : -273.98528004 Eh -7455.51850 eV +One Electron Energy: -418.24852633 Eh -11381.12101 eV +Two Electron Energy: 144.26324629 Eh 3925.60251 eV + +Virial components: +Potential Energy : -408.95514335 Eh -11128.23520 eV +Kinetic Energy : 204.23663321 Eh 5557.56133 eV +Virial Ratio : 2.00235940 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.6107e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.2602e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.1933e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.7979e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.671813 -562.5086 + 1 1.0000 -20.635307 -561.5152 + 2 1.0000 -15.799381 -429.9230 + 3 1.0000 -1.605056 -43.6758 + 4 1.0000 -1.395266 -37.9671 + 5 1.0000 -0.949312 -25.8321 + 6 1.0000 -0.779901 -21.2222 + 7 1.0000 -0.728842 -19.8328 + 8 1.0000 -0.688544 -18.7362 + 9 1.0000 -0.616657 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4.547320 123.7389 + 113 0.0000 4.629327 125.9704 + 114 0.0000 4.745459 129.1305 + 115 0.0000 4.787902 130.2854 + 116 0.0000 4.803621 130.7132 + 117 0.0000 4.887602 132.9984 + 118 0.0000 4.960872 134.9922 + 119 0.0000 4.999065 136.0315 + 120 0.0000 5.070207 137.9673 + 121 0.0000 5.097976 138.7230 + 122 0.0000 5.175084 140.8212 + 123 0.0000 5.222636 142.1151 + 124 0.0000 5.259703 143.1238 + 125 0.0000 5.323295 144.8542 + 126 0.0000 5.342096 145.3658 + 127 0.0000 5.410141 147.2174 + 128 0.0000 5.561672 151.3408 + 129 0.0000 5.688590 154.7944 + 130 0.0000 5.792914 157.6332 + 131 0.0000 6.001075 163.2976 + 132 0.0000 6.122191 166.5933 + 133 0.0000 6.412978 174.5060 + 134 0.0000 6.500848 176.8971 + 135 0.0000 6.511775 177.1944 + 136 0.0000 6.693484 182.1390 + 137 0.0000 6.703590 182.4140 + 138 0.0000 6.741739 183.4521 + 139 0.0000 6.845881 186.2859 + 140 0.0000 6.909804 188.0253 + 141 0.0000 7.068595 192.3462 + 142 0.0000 7.124620 193.8708 + 143 0.0000 7.175893 195.2660 + 144 0.0000 7.185316 195.5224 + 145 0.0000 7.227996 196.6838 + 146 0.0000 7.264005 197.6636 + 147 0.0000 7.344675 199.8588 + 148 0.0000 7.391958 201.1454 + 149 0.0000 7.443548 202.5492 + 150 0.0000 7.481991 203.5953 + 151 0.0000 7.585186 206.4034 + 152 0.0000 7.629054 207.5971 + 153 0.0000 7.673294 208.8009 + 154 0.0000 7.851434 213.6484 + 155 0.0000 7.932399 215.8516 + 156 0.0000 8.042415 218.8452 + 157 0.0000 8.383769 228.1339 + 158 0.0000 14.093078 383.4921 + 159 0.0000 14.953636 406.9091 + 160 0.0000 16.037535 436.4035 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.671813 -562.5086 + 1 1.0000 -20.635307 -561.5152 + 2 1.0000 -15.799381 -429.9230 + 3 1.0000 -1.605056 -43.6758 + 4 1.0000 -1.395266 -37.9671 + 5 1.0000 -0.949312 -25.8321 + 6 1.0000 -0.779901 -21.2222 + 7 1.0000 -0.728842 -19.8328 + 8 1.0000 -0.688544 -18.7362 + 9 1.0000 -0.616657 -16.7801 + 10 1.0000 -0.529485 -14.4080 + 11 1.0000 -0.461452 -12.5567 + 12 0.0000 0.028588 0.7779 + 13 0.0000 0.077138 2.0990 + 14 0.0000 0.093415 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0.0000 2.445177 66.5367 + 85 0.0000 2.466397 67.1141 + 86 0.0000 2.487514 67.6887 + 87 0.0000 2.502721 68.1025 + 88 0.0000 2.516519 68.4780 + 89 0.0000 2.528532 68.8049 + 90 0.0000 2.573579 70.0306 + 91 0.0000 2.602749 70.8244 + 92 0.0000 2.654396 72.2298 + 93 0.0000 2.717381 73.9437 + 94 0.0000 2.732716 74.3610 + 95 0.0000 2.761844 75.1536 + 96 0.0000 2.836096 77.1741 + 97 0.0000 2.909306 79.1662 + 98 0.0000 2.954322 80.3912 + 99 0.0000 3.087984 84.0283 + 100 0.0000 3.148273 85.6689 + 101 0.0000 3.176376 86.4336 + 102 0.0000 3.262186 88.7686 + 103 0.0000 3.470711 94.4428 + 104 0.0000 3.752982 102.1238 + 105 0.0000 3.894667 105.9793 + 106 0.0000 4.030136 109.6656 + 107 0.0000 4.154893 113.0604 + 108 0.0000 4.187580 113.9499 + 109 0.0000 4.279720 116.4571 + 110 0.0000 4.361626 118.6859 + 111 0.0000 4.400079 119.7322 + 112 0.0000 4.547320 123.7389 + 113 0.0000 4.629327 125.9704 + 114 0.0000 4.745459 129.1305 + 115 0.0000 4.787902 130.2854 + 116 0.0000 4.803621 130.7132 + 117 0.0000 4.887602 132.9984 + 118 0.0000 4.960872 134.9922 + 119 0.0000 4.999065 136.0315 + 120 0.0000 5.070207 137.9673 + 121 0.0000 5.097976 138.7230 + 122 0.0000 5.175084 140.8212 + 123 0.0000 5.222636 142.1151 + 124 0.0000 5.259703 143.1238 + 125 0.0000 5.323295 144.8542 + 126 0.0000 5.342096 145.3658 + 127 0.0000 5.410141 147.2174 + 128 0.0000 5.561672 151.3408 + 129 0.0000 5.688590 154.7944 + 130 0.0000 5.792914 157.6332 + 131 0.0000 6.001075 163.2976 + 132 0.0000 6.122191 166.5933 + 133 0.0000 6.412978 174.5060 + 134 0.0000 6.500848 176.8971 + 135 0.0000 6.511775 177.1944 + 136 0.0000 6.693484 182.1390 + 137 0.0000 6.703590 182.4140 + 138 0.0000 6.741739 183.4521 + 139 0.0000 6.845881 186.2859 + 140 0.0000 6.909804 188.0253 + 141 0.0000 7.068595 192.3462 + 142 0.0000 7.124620 193.8708 + 143 0.0000 7.175893 195.2660 + 144 0.0000 7.185316 195.5224 + 145 0.0000 7.227996 196.6838 + 146 0.0000 7.264005 197.6636 + 147 0.0000 7.344675 199.8588 + 148 0.0000 7.391958 201.1454 + 149 0.0000 7.443548 202.5492 + 150 0.0000 7.481991 203.5953 + 151 0.0000 7.585186 206.4034 + 152 0.0000 7.629054 207.5971 + 153 0.0000 7.673294 208.8009 + 154 0.0000 7.851434 213.6484 + 155 0.0000 7.932399 215.8516 + 156 0.0000 8.042415 218.8452 + 157 0.0000 8.383769 228.1339 + 158 0.0000 14.093078 383.4921 + 159 0.0000 14.953636 406.9091 + 160 0.0000 16.037535 436.4035 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.349444 0.000000 + 1 N : 0.344132 0.000000 + 2 O : -0.269059 0.000000 + 3 H : 0.274370 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.867277 s : 3.867277 + pz : 1.425227 p : 4.453918 + px : 1.236984 + py : 1.791706 + dz2 : 0.010510 d : 0.023582 + dxz : -0.001259 + dyz : 0.001148 + dx2y2 : 0.006683 + dxy : 0.006500 + f0 : 0.000362 f : 0.004667 + f+1 : 0.001000 + f-1 : 0.000418 + f+2 : 0.000519 + f-2 : -0.000038 + f+3 : 0.001060 + f-3 : 0.001345 + 1 N s : 3.828875 s : 3.828875 + pz : 1.056795 p : 2.657064 + px : 0.833798 + py : 0.766471 + dz2 : 0.032381 d : 0.139703 + dxz : 0.032901 + dyz : 0.027494 + dx2y2 : 0.024100 + dxy : 0.022825 + f0 : 0.005409 f : 0.030226 + f+1 : 0.008682 + f-1 : 0.004877 + f+2 : 0.002992 + f-2 : 0.000895 + f+3 : 0.002334 + f-3 : 0.005038 + 2 O s : 3.879712 s : 3.879712 + pz : 1.203959 p : 4.318611 + px : 1.845045 + py : 1.269608 + dz2 : 0.016771 d : 0.063043 + dxz : 0.016025 + dyz : 0.027133 + dx2y2 : 0.000827 + dxy : 0.002288 + f0 : 0.002327 f : 0.007692 + f+1 : 0.002173 + f-1 : 0.002378 + f+2 : 0.000250 + f-2 : 0.000549 + f+3 : 0.000046 + f-3 : -0.000031 + 3 H s : 0.623750 s : 0.623750 + pz : 0.019478 p : 0.079866 + px : 0.020227 + py : 0.040161 + dz2 : 0.003580 d : 0.022014 + dxz : 0.010334 + dyz : 0.006768 + dx2y2 : 0.000364 + dxy : 0.000968 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.594690 0.000000 + 1 N : -0.264345 0.000000 + 2 O : 0.237727 0.000000 + 3 H : -0.568072 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.117655 s : 3.117655 + pz : 1.305233 p : 3.914226 + px : 1.177919 + py : 1.431074 + dz2 : 0.065778 d : 0.286778 + dxz : 0.069134 + dyz : 0.014270 + dx2y2 : 0.089335 + dxy : 0.048261 + f0 : 0.012808 f : 0.086651 + f+1 : 0.016460 + f-1 : 0.004002 + f+2 : 0.017503 + f-2 : 0.002930 + f+3 : 0.017302 + f-3 : 0.015645 + 1 N s : 3.008605 s : 3.008605 + pz : 1.205288 p : 2.836880 + px : 0.907548 + py : 0.724044 + dz2 : 0.259963 d : 0.962686 + dxz : 0.300582 + dyz : 0.125088 + dx2y2 : 0.150225 + dxy : 0.126829 + f0 : 0.099335 f : 0.456174 + f+1 : 0.127626 + f-1 : 0.063757 + f+2 : 0.054379 + f-2 : 0.017507 + f+3 : 0.038254 + f-3 : 0.055314 + 2 O s : 3.317294 s : 3.317294 + pz : 1.391501 p : 4.001745 + px : 1.509073 + py : 1.101171 + dz2 : 0.138363 d : 0.325393 + dxz : 0.095694 + dyz : 0.061637 + dx2y2 : 0.020276 + dxy : 0.009423 + f0 : 0.042206 f : 0.117841 + f+1 : 0.029408 + f-1 : 0.023983 + f+2 : 0.013924 + f-2 : 0.006459 + f+3 : 0.001135 + f-3 : 0.000725 + 3 H s : 0.620564 s : 0.620564 + pz : 0.252669 p : 0.554464 + px : 0.131091 + py : 0.170704 + dz2 : 0.126850 d : 0.393044 + dxz : 0.108413 + dyz : 0.114255 + dx2y2 : 0.026843 + dxy : 0.016683 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3494 8.0000 -0.3494 1.9073 1.9073 0.0000 + 1 N 6.6559 7.0000 0.3441 2.5426 2.5426 -0.0000 + 2 O 8.2691 8.0000 -0.2691 1.7415 1.7415 -0.0000 + 3 H 0.7256 1.0000 0.2744 0.9474 0.9474 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8913 B( 0-O , 3-H ) : 0.9607 B( 1-N , 2-O ) : 1.6754 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.378 sec +Sum of individual times .... 2.199 sec ( 92.5%) + +Fock matrix formation .... 1.804 sec ( 75.9%) +Diagonalization .... 0.199 sec ( 8.4%) +Density matrix formation .... 0.014 sec ( 0.6%) +Population analysis .... 0.016 sec ( 0.7%) +Initial guess .... 0.009 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.2%) +DIIS solution .... 0.158 sec ( 6.6%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.202 sec +Reference energy ... -204.718508590 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.397 sec +AO-integral generation ... 0.142 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.402 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.024 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.030 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.032 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.041 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.030 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.025 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.360 sec +AO-integral generation ... 0.254 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.051 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.155 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.251 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090445174 +EMP2(bb)= -0.090445174 +EMP2(ab)= -0.516611783 + +Initial guess performed in 0.133 sec +E(0) ... -204.718508590 +E(MP2) ... -0.697502132 +Initial E(tot) ... -205.416010721 + ... 0.188221326 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.416010721 -0.697502132 -0.000000000 0.024205318 2.75 0.000001792 + *** Turning on DIIS *** + 1 -205.387107676 -0.668599086 0.028903045 0.009850477 2.76 0.057385974 + 2 -205.406581089 -0.688072499 -0.019473413 0.005217290 2.81 0.060377333 + 3 -205.410318300 -0.691809710 -0.003737211 0.002086075 2.85 0.074591394 + 4 -205.411882351 -0.693373761 -0.001564051 0.001653504 2.83 0.081332272 + 5 -205.412435535 -0.693926945 -0.000553184 0.000929370 2.92 0.086975383 + 6 -205.412547417 -0.694038827 -0.000111882 0.000560740 2.84 0.089821491 + 7 -205.412593281 -0.694084692 -0.000045864 0.000236140 2.90 0.091138253 + 8 -205.412605704 -0.694097115 -0.000012423 0.000121287 2.89 0.091644080 + 9 -205.412601398 -0.694092808 0.000004307 0.000033806 2.80 0.091794330 + 10 -205.412606304 -0.694097714 -0.000004906 0.000020487 2.77 0.091841951 + 11 -205.412603556 -0.694094966 0.000002748 0.000016235 2.78 0.091834580 + 12 -205.412604748 -0.694096158 -0.000001192 0.000012290 2.82 0.091845253 + 13 -205.412604509 -0.694095919 0.000000239 0.000008012 2.87 0.091841115 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.718508590 +E(CORR) ... -0.694095919 +E(TOT) ... -205.412604509 +Singles norm **1/2 ... 0.091841115 ( 0.045920558, 0.045920558) +T1 diagnostic ... 0.021647158 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.055872 + 10a-> 13a 10b-> 13b 0.042987 + 8b-> 13b -1b-> -1b 0.038937 + 8a-> 13a -1a-> -1a 0.038937 + 10a-> 13a -1a-> -1a 0.033531 + 10b-> 13b -1b-> -1b 0.033531 + 8a-> 13a 9b-> 13b 0.030513 + 9a-> 13a 8b-> 13b 0.030513 + 10a-> 13a 8b-> 13b 0.029675 + 8a-> 13a 10b-> 13b 0.029675 + 11a-> 13a 11b-> 13b 0.028334 + 9a-> 13a 9b-> 13b 0.026696 + 5a-> 13a 5b-> 13b 0.026557 + 11a-> 26a 11b-> 26b 0.025729 + 11b-> 26b -1b-> -1b 0.025618 + 11a-> 26a -1a-> -1a 0.025618 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034651438 + alpha-alpha-alpha ... -0.000892390 ( 2.6%) + alpha-alpha-beta ... -0.016433329 ( 47.4%) + alpha-beta -beta ... -0.016433329 ( 47.4%) + beta -beta -beta ... -0.000892390 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034651438 + +Final correlation energy ... -0.728747358 +E(CCSD) ... -205.412604509 +E(CCSD(T)) ... -205.447255947 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210152448 sqrt= 1.100069292 +W(HF) = 0.826342170 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.265824 -0.000000 + 1 N : 0.156550 0.000000 + 2 O : -0.151960 -0.000000 + 3 H : 0.261234 -0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.845162 s : 3.845162 + pz : 1.405999 p : 4.356587 + px : 1.232686 + py : 1.717902 + dz2 : 0.015499 d : 0.055618 + dxz : 0.006680 + dyz : 0.007921 + dx2y2 : 0.011511 + dxy : 0.014007 + f0 : 0.001052 f : 0.008457 + f+1 : 0.001430 + f-1 : 0.001052 + f+2 : 0.001081 + f-2 : 0.000646 + f+3 : 0.001323 + f-3 : 0.001872 + 1 N s : 3.881234 s : 3.881234 + pz : 1.029146 p : 2.762360 + px : 0.872941 + py : 0.860272 + dz2 : 0.035665 d : 0.170283 + dxz : 0.044432 + dyz : 0.028816 + dx2y2 : 0.029965 + dxy : 0.031405 + f0 : 0.004616 f : 0.029573 + f+1 : 0.008453 + f-1 : 0.004216 + f+2 : 0.003293 + f-2 : 0.001362 + f+3 : 0.002468 + f-3 : 0.005167 + 2 O s : 3.867038 s : 3.867038 + pz : 1.190753 p : 4.190183 + px : 1.763243 + py : 1.236187 + dz2 : 0.018743 d : 0.084509 + dxz : 0.022829 + dyz : 0.027405 + dx2y2 : 0.007167 + dxy : 0.008364 + f0 : 0.002314 f : 0.010231 + f+1 : 0.002603 + f-1 : 0.002279 + f+2 : 0.000819 + f-2 : 0.001057 + f+3 : 0.000620 + f-3 : 0.000539 + 3 H s : 0.635215 s : 0.635215 + pz : 0.014905 p : 0.084577 + px : 0.023829 + py : 0.045843 + dz2 : 0.002328 d : 0.018975 + dxz : 0.009343 + dyz : 0.005469 + dx2y2 : 0.000804 + dxy : 0.001031 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.609593 -0.000000 + 1 N : -0.313151 0.000000 + 2 O : 0.272696 0.000000 + 3 H : -0.569138 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.124367 s : 3.124367 + pz : 1.291987 p : 3.854671 + px : 1.185946 + py : 1.376737 + dz2 : 0.072309 d : 0.317777 + dxz : 0.074540 + dyz : 0.020412 + dx2y2 : 0.096041 + dxy : 0.054475 + f0 : 0.013683 f : 0.093591 + f+1 : 0.017182 + f-1 : 0.005091 + f+2 : 0.017934 + f-2 : 0.003444 + f+3 : 0.018832 + f-3 : 0.017424 + 1 N s : 3.013793 s : 3.013793 + pz : 1.180161 p : 2.882632 + px : 0.920991 + py : 0.781480 + dz2 : 0.264000 d : 0.972047 + dxz : 0.298988 + dyz : 0.123257 + dx2y2 : 0.157499 + dxy : 0.128302 + f0 : 0.096319 f : 0.444679 + f+1 : 0.124807 + f-1 : 0.063409 + f+2 : 0.052064 + f-2 : 0.017577 + f+3 : 0.039235 + f-3 : 0.051268 + 2 O s : 3.319251 s : 3.319251 + pz : 1.382180 p : 3.925598 + px : 1.456234 + py : 1.087185 + dz2 : 0.143575 d : 0.356074 + dxz : 0.098556 + dyz : 0.071552 + dx2y2 : 0.025921 + dxy : 0.016471 + f0 : 0.043377 f : 0.126381 + f+1 : 0.030419 + f-1 : 0.027118 + f+2 : 0.014296 + f-2 : 0.008133 + f+3 : 0.001739 + f-3 : 0.001300 + 3 H s : 0.622346 s : 0.622346 + pz : 0.256413 p : 0.563992 + px : 0.132072 + py : 0.175506 + dz2 : 0.124933 d : 0.382800 + dxz : 0.104782 + dyz : 0.109320 + dx2y2 : 0.027192 + dxy : 0.016572 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2658 8.0000 -0.2658 2.2713 1.8117 0.4596 + 1 N 6.8434 7.0000 0.1566 2.8285 2.3486 0.4798 + 2 O 8.1520 8.0000 -0.1520 2.1401 1.6419 0.4983 + 3 H 0.7388 1.0000 0.2612 0.9696 0.8984 0.0713 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8244 B( 0-O , 3-H ) : 0.8908 B( 1-N , 2-O ) : 1.5311 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 54.664 sec + +Fock Matrix Formation ... 0.202 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 1.974 sec ( 3.6%) +State Vector Update ... 0.091 sec ( 0.2%) +Sigma-vector construction ... 37.510 sec ( 68.6%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.022 sec ( 0.1% of sigma) + (0-ext) ... 0.069 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (2-ext) ... 0.934 sec ( 2.5% of sigma) + (4-ext) ... 20.672 sec ( 55.1% of sigma) + ... 1.374 sec ( 3.7% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.107 sec ( 0.3% of sigma) + Fock-dressing ... 2.092 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.074 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.526 sec ( 25.4% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.861 sec ( 12.6% of ALL) + I/O of integral and amplitudes ... 0.809 sec ( 11.8% of (T)) + External N**7 contributions ... 3.919 sec ( 57.1% of (T)) + Internal N**7 contributions ... 0.321 sec ( 4.7% of (T)) + N**6 triples energy contributions ... 1.733 sec ( 25.3% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.447255947236 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.001344314 -0.008437968 0.000693249 + 2 N : -0.003490612 -0.008772779 0.001030307 + 3 O : 0.001508145 0.008037331 -0.001274476 + 4 H : 0.000638152 0.009173416 -0.000449081 + +Norm of the cartesian gradient ... 0.017803162 +RMS gradient ... 0.005139330 +MAX gradient ... 0.009173416 + +------- +TIMINGS +------- + +Total numerical gradient time ... 362.151 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 429.52 cm**-1 + 7: 620.60 cm**-1 + 8: 821.42 cm**-1 + 9: 1276.62 cm**-1 + 10: 1695.77 cm**-1 + 11: 3711.43 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 -0.067154 0.395474 -0.186296 -0.051185 -0.104053 0.003583 + 1 -0.048824 -0.010100 0.089303 -0.004841 0.007390 -0.019977 + 2 0.042405 -0.248144 -0.090965 -0.068237 -0.033156 -0.059429 + 3 0.048241 -0.069826 0.494500 0.042504 -0.036899 -0.000130 + 4 -0.071781 -0.096430 -0.077587 0.019778 -0.137927 0.000790 + 5 -0.032407 0.196832 0.071618 0.008179 0.647395 -0.001500 + 6 0.021049 -0.321137 -0.200650 -0.048414 0.105808 -0.000469 + 7 0.052050 0.057907 0.000336 -0.008606 0.114775 -0.000700 + 8 0.003835 0.106007 0.026336 0.060939 -0.535925 0.001199 + 9 0.061438 -0.209587 -0.729875 0.990216 0.484876 -0.047622 + 10 0.946256 0.581190 -0.344613 -0.061407 -0.022389 0.317207 + 11 -0.283613 -0.479143 0.030592 0.002179 0.036376 0.945073 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 429.52 0.034508 174.39 0.025071 ( 0.084061 0.106232 -0.081975) + 7: 620.60 0.016540 83.59 0.008317 (-0.077908 0.024979 0.040294) + 8: 821.42 0.022730 114.87 0.008635 ( 0.080638 -0.018763 -0.042197) + 9: 1276.62 0.028425 143.65 0.006948 ( 0.077761 -0.012307 -0.027391) + 10: 1695.77 0.024267 122.64 0.004466 (-0.048123 -0.003828 0.046209) + 11: 3711.43 0.014489 73.22 0.001218 (-0.015109 0.010387 0.029699) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 429.52 E(vib) ... 0.18 +freq. 620.60 E(vib) ... 0.09 +freq. 821.42 E(vib) ... 0.05 +freq. 1276.62 E(vib) ... 0.01 +freq. 1695.77 E(vib) ... 0.00 +freq. 3711.43 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.44725595 Eh +Zero point energy ... 0.01949054 Eh 12.23 kcal/mol +Thermal vibrational correction ... 0.00051765 Eh 0.32 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42441521 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00335019 Eh 2.10 kcal/mol +Non-thermal (ZPE) correction 0.01949054 Eh 12.23 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02284073 Eh 14.33 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42441521 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.42347101 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.987051 0.415313 0.368354 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00071449 Eh 0.45 kcal/mol +Rotational entropy ... 0.00988053 Eh 6.20 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02839734 Eh 17.82 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00988053 Eh 6.20 kcal/mol| +| sn= 2 | S(rot)= 0.00922607 Eh 5.79 kcal/mol| +| sn= 3 | S(rot)= 0.00884324 Eh 5.55 kcal/mol| +| sn= 4 | S(rot)= 0.00857161 Eh 5.38 kcal/mol| +| sn= 5 | S(rot)= 0.00836093 Eh 5.25 kcal/mol| +| sn= 6 | S(rot)= 0.00818878 Eh 5.14 kcal/mol| +| sn= 7 | S(rot)= 0.00804324 Eh 5.05 kcal/mol| +| sn= 8 | S(rot)= 0.00791716 Eh 4.97 kcal/mol| +| sn= 9 | S(rot)= 0.00780595 Eh 4.90 kcal/mol| +| sn=10 | S(rot)= 0.00770647 Eh 4.84 kcal/mol| +| sn=11 | S(rot)= 0.00761648 Eh 4.78 kcal/mol| +| sn=12 | S(rot)= 0.00753432 Eh 4.73 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.42347101 Eh +Total entropy correction ... -0.02839734 Eh -17.82 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.45186834 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00461239 Eh -2.89 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.447255948 Eh +Current gradient norm .... 0.017803162 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.018162174 0.130771848 0.180298213 0.490177164 0.517372798 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999854936 +Lowest eigenvalues of augmented Hessian: + -0.000061221 0.129295126 0.179595163 0.490166560 0.517342924 +Length of the computed step .... 0.017035009 +The final length of the internal step .... 0.017035009 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0069545134 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0035657932 RMS(Int)= 0.0069562743 + Iter 1: RMS(Cart)= 0.0000080090 RMS(Int)= 0.0000119930 + Iter 2: RMS(Cart)= 0.0000000196 RMS(Int)= 0.0000000388 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0018471968 0.0001000000 NO + MAX gradient 0.0031596778 0.0003000000 NO + RMS step 0.0069545134 0.0020000000 NO + MAX step 0.0149345233 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0079 Max(Angles) 0.06 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4430 -0.001842 0.0079 1.4509 + 2. B(O 2,N 1) 1.1746 0.003160 -0.0033 1.1713 + 3. B(H 3,O 0) 0.9718 0.002537 -0.0027 0.9691 + 4. A(N 1,O 0,H 3) 101.99 -0.000547 0.06 102.04 + 5. A(O 0,N 1,O 2) 110.49 -0.000599 0.02 110.52 + 6. D(O 2,N 1,O 0,H 3) -147.27 0.015892 0.00 -147.27 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.773454 -0.063197 0.156008 + N 0.654212 -0.210344 -0.056528 + O 0.929416 0.021646 -1.171148 + H -0.810172 0.251895 1.071668 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.461617 -0.119425 0.294812 + 1 N 7.0000 0 14.007 1.236281 -0.397493 -0.106822 + 2 O 8.0000 0 15.999 1.756341 0.040905 -2.213148 + 3 H 1.0000 0 1.008 -1.531003 0.476013 2.025158 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.450880675240 0.00000000 0.00000000 + O 2 1 0 1.171295789438 110.51846491 0.00000000 + H 1 2 3 0.969052916683 102.04484161 212.72727269 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.741767129202 0.00000000 0.00000000 + O 2 1 0 2.213428263853 110.51846491 0.00000000 + H 1 2 3 1.831244621809 102.04484161 212.72727269 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.1 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2225 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2690 + la=0 lb=0: 549 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.198882758164 Eh + +SHARK setup successfully completed in 0.5 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.967e-04 +Time for diagonalization ... 0.023 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.071 sec +Total time needed ... 0.100 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7184097056 0.000000000000 0.00021946 0.00000700 0.0015133 0.7000 + 1 -204.7184222259 -0.000012520273 0.00018051 0.00000586 0.0012564 0.7000 + ***Turning on DIIS*** + 2 -204.7184325231 -0.000010297224 0.00046258 0.00001522 0.0010139 0.0000 + 3 -204.7180895487 0.000342974378 0.00020469 0.00000660 0.0003423 0.0000 + 4 -204.7185070138 -0.000417465081 0.00007129 0.00000227 0.0001064 0.0000 + 5 -204.7186331182 -0.000126104379 0.00002932 0.00000079 0.0000678 0.0000 + 6 -204.7184044090 0.000228709229 0.00002353 0.00000058 0.0000329 0.0000 + 7 -204.7184836074 -0.000079198484 0.00000672 0.00000028 0.0000082 0.0000 + 8 -204.7184589728 0.000024634662 0.00000554 0.00000023 0.0000061 0.0000 + 9 -204.7184558231 0.000003149711 0.00000435 0.00000017 0.0000040 0.0000 + 10 -204.7184738877 -0.000018064623 0.00000268 0.00000010 0.0000021 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + +Total Energy : -204.71846249 Eh -5570.67257 eV + Last Energy change ... 1.1402e-05 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.0520e-06 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 5 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.668 sec +Reference energy ... -204.718465741 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 11.201 sec +AO-integral generation ... 0.382 sec +Half transformation ... 0.196 sec +K-integral sorting ... 8.649 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.058 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.064 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.095 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.137 s ( 0.001 ms/b) +: 159120 b 0 skpd 0.097 s ( 0.001 ms/b) + 218790 b 0 skpd 0.107 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.100 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.069 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.122 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.069 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 1.051 sec +AO-integral generation ... 0.823 sec +Half transformation ... 0.101 sec +J-integral sorting ... 0.098 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.272 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.503 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090441252 +EMP2(bb)= -0.090441252 +EMP2(ab)= -0.516669318 + +Initial guess performed in 0.194 sec +E(0) ... -204.718465741 +E(MP2) ... -0.697551822 +Initial E(tot) ... -205.416017563 + ... 0.188322636 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.416017563 -0.697551822 -0.000000000 0.023945325 6.93 0.000001236 + *** Turning on DIIS *** + 1 -205.387056999 -0.668591259 0.028960563 0.009705416 5.98 0.057513720 + 2 -205.406553212 -0.688087471 -0.019496213 0.005133792 7.07 0.060467285 + 3 -205.410293009 -0.691827268 -0.003739797 0.002058779 6.22 0.074733738 + 4 -205.411859881 -0.693394140 -0.001566872 0.001710623 6.51 0.081505729 + 5 -205.412418060 -0.693952319 -0.000558179 0.000956126 6.83 0.087230193 + 6 -205.412532168 -0.694066427 -0.000114108 0.000575814 6.76 0.090151794 + 7 -205.412579636 -0.694113895 -0.000047468 0.000238180 6.02 0.091524600 + 8 -205.412592627 -0.694126886 -0.000012991 0.000122551 6.79 0.092048181 + 9 -205.412588235 -0.694122494 0.000004392 0.000033935 6.51 0.092203655 + 10 -205.412593279 -0.694127539 -0.000005045 0.000020157 7.25 0.092252666 + 11 -205.412590447 -0.694124706 0.000002833 0.000015946 7.61 0.092244961 + 12 -205.412591672 -0.694125932 -0.000001226 0.000012083 5.84 0.092256303 + 13 -205.412591426 -0.694125685 0.000000247 0.000007967 6.57 0.092251927 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.718465741 +E(CORR) ... -0.694125685 +E(TOT) ... -205.412591426 +Singles norm **1/2 ... 0.092251927 ( 0.046125964, 0.046125964) +T1 diagnostic ... 0.021743988 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.057086 + 10a-> 13a 10b-> 13b 0.041081 + 8b-> 13b -1b-> -1b 0.038290 + 8a-> 13a -1a-> -1a 0.038290 + 10b-> 13b -1b-> -1b 0.034933 + 10a-> 13a -1a-> -1a 0.034933 + 9a-> 13a 8b-> 13b 0.030812 + 8a-> 13a 9b-> 13b 0.030812 + 10a-> 13a 8b-> 13b 0.029198 + 8a-> 13a 10b-> 13b 0.029198 + 11a-> 13a 11b-> 13b 0.028043 + 5a-> 13a 5b-> 13b 0.026736 + 9a-> 13a 9b-> 13b 0.026320 + 9a-> 13a 10b-> 13b 0.024600 + 10a-> 13a 9b-> 13b 0.024600 + 11a-> 26a 11b-> 26b 0.024410 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034695278 + alpha-alpha-alpha ... -0.000892730 ( 2.6%) + alpha-alpha-beta ... -0.016454909 ( 47.4%) + alpha-beta -beta ... -0.016454909 ( 47.4%) + beta -beta -beta ... -0.000892730 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034695278 + +Final correlation energy ... -0.728820962 +E(CCSD) ... -205.412591426 +E(CCSD(T)) ... -205.447286703 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210413895 sqrt= 1.100188118 +W(HF) = 0.826163682 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 126.645 sec + +Fock Matrix Formation ... 0.668 sec ( 0.5%) +Initial Guess ... 0.194 sec ( 0.2%) +DIIS Solver ... 5.689 sec ( 4.5%) +State Vector Update ... 0.335 sec ( 0.3%) +Sigma-vector construction ... 86.858 sec ( 68.6%) + <0|H|D> ... 0.008 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.050 sec ( 0.1% of sigma) + (0-ext) ... 0.149 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.062 sec ( 0.1% of sigma) + (2-ext) ... 2.166 sec ( 2.5% of sigma) + (4-ext) ... 49.896 sec ( 57.4% of sigma) + ... 4.748 sec ( 5.5% of sigma) + ... 0.007 sec ( 0.0% of sigma) + (1-ext) ... 0.022 sec ( 0.0% of sigma) + (1-ext) ... 0.260 sec ( 0.3% of sigma) + Fock-dressing ... 5.682 sec ( 6.5% of sigma) + (ik|jl)-dressing ... 0.178 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 19.326 sec ( 22.3% of sigma) + Pair energies ... 0.039 sec ( 0.0% of sigma) +Total Time for computing (T) ... 18.083 sec ( 14.3% of ALL) + I/O of integral and amplitudes ... 1.682 sec ( 9.3% of (T)) + External N**7 contributions ... 8.980 sec ( 49.7% of (T)) + Internal N**7 contributions ... 0.851 sec ( 4.7% of (T)) + N**6 triples energy contributions ... 3.033 sec ( 16.8% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.447286703240 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.000138025 -0.007339310 0.003721384 + 2 N : -0.001277581 -0.008151963 -0.002710943 + 3 O : 0.000991499 0.007250058 0.001828227 + 4 H : 0.000424107 0.008241214 -0.002838669 + +Norm of the cartesian gradient ... 0.016619672 +RMS gradient ... 0.004797686 +MAX gradient ... 0.008241214 + +------- +TIMINGS +------- + +Total numerical gradient time ... 864.045 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.447286703 Eh +Current gradient norm .... 0.016619672 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999922 +Lowest eigenvalues of augmented Hessian: + -0.000000027 0.126997943 0.179251353 0.492985195 0.517336948 +Length of the computed step .... 0.000395485 +The final length of the internal step .... 0.000395485 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0001614561 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0000884110 RMS(Int)= 0.0001614564 + Iter 1: RMS(Cart)= 0.0000000045 RMS(Int)= 0.0000000071 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000307548 0.0000050000 NO + RMS gradient 0.0000393090 0.0001000000 YES + MAX gradient 0.0000704346 0.0003000000 YES + RMS step 0.0001614561 0.0020000000 YES + MAX step 0.0003660243 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0002 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4509 -0.000061 0.0002 1.4511 + 2. B(O 2,N 1) 1.1713 -0.000070 0.0000 1.1713 + 3. B(H 3,O 0) 0.9691 -0.000018 0.0000 0.9691 + 4. A(N 1,O 0,H 3) 102.04 0.000012 -0.01 102.04 + 5. A(O 0,N 1,O 2) 110.52 -0.000009 -0.00 110.52 + 6. D(O 2,N 1,O 0,H 3) -147.27 0.015631 0.00 -147.27 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.773580 -0.063202 0.156021 + N 0.654279 -0.210344 -0.056542 + O 0.929469 0.021643 -1.171183 + H -0.810168 0.251903 1.071704 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.461855 -0.119435 0.294838 + 1 N 7.0000 0 14.007 1.236409 -0.397492 -0.106849 + 2 O 8.0000 0 15.999 1.756442 0.040900 -2.213214 + 3 H 1.0000 0 1.008 -1.530995 0.476027 2.025226 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.451074366937 0.00000000 0.00000000 + O 2 1 0 1.171311518767 110.51784174 0.00000000 + H 1 2 3 0.969073657248 102.03675972 212.72727269 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.742133153463 0.00000000 0.00000000 + O 2 1 0 2.213457987977 110.51784174 0.00000000 + H 1 2 3 1.831283815796 102.03675972 212.72727269 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.1 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2225 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2690 + la=0 lb=0: 549 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.194355065547 Eh + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.1943550655 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.968e-04 +Time for diagonalization ... 0.005 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.004 sec +Total time needed ... 0.010 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7184434442 0.000000000000 0.00000663 0.00000014 0.0000352 0.7000 + 1 -204.7184434487 -0.000000004559 0.00000491 0.00000012 0.0000279 0.7000 + ***Turning on DIIS*** + 2 -204.7184434525 -0.000000003816 0.00001275 0.00000032 0.0000217 0.0000 + 3 -204.7184520133 -0.000008560771 0.00000495 0.00000013 0.0000058 0.0000 + 4 -204.7184416521 0.000010361223 0.00000190 0.00000004 0.0000016 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71843969 Eh -5570.67195 eV + +Components: +Nuclear Repulsion : 69.19435507 Eh 1882.87412 eV +Electronic Energy : -273.91279476 Eh -7453.54608 eV +One Electron Energy: -418.09963014 Eh -11377.06934 eV +Two Electron Energy: 144.18683539 Eh 3923.52326 eV + +Virial components: +Potential Energy : -408.96177924 Eh -11128.41577 eV +Kinetic Energy : 204.24333955 Eh 5557.74382 eV +Virial Ratio : 2.00232615 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.9590e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.1289e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.2642e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.7461e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.673735 -562.5609 + 1 1.0000 -20.633111 -561.4555 + 2 1.0000 -15.800138 -429.9436 + 3 1.0000 -1.607662 -43.7467 + 4 1.0000 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0.0000 0.804102 21.8807 + 45 0.0000 0.820211 22.3191 + 46 0.0000 0.852872 23.2078 + 47 0.0000 0.862634 23.4735 + 48 0.0000 0.925597 25.1868 + 49 0.0000 0.944234 25.6939 + 50 0.0000 0.958250 26.0753 + 51 0.0000 1.008896 27.4535 + 52 0.0000 1.031181 28.0599 + 53 0.0000 1.043835 28.4042 + 54 0.0000 1.051421 28.6106 + 55 0.0000 1.087405 29.5898 + 56 0.0000 1.157198 31.4890 + 57 0.0000 1.201484 32.6940 + 58 0.0000 1.252839 34.0915 + 59 0.0000 1.308019 35.5930 + 60 0.0000 1.375899 37.4401 + 61 0.0000 1.405947 38.2578 + 62 0.0000 1.478976 40.2450 + 63 0.0000 1.511851 41.1396 + 64 0.0000 1.519057 41.3356 + 65 0.0000 1.541521 41.9469 + 66 0.0000 1.573414 42.8148 + 67 0.0000 1.616533 43.9881 + 68 0.0000 1.669462 45.4284 + 69 0.0000 1.723884 46.9093 + 70 0.0000 1.779959 48.4351 + 71 0.0000 1.800588 48.9965 + 72 0.0000 1.875830 51.0439 + 73 0.0000 1.933049 52.6009 + 74 0.0000 1.960615 53.3511 + 75 0.0000 2.028478 55.1977 + 76 0.0000 2.057663 55.9918 + 77 0.0000 2.103584 57.2414 + 78 0.0000 2.158860 58.7456 + 79 0.0000 2.189601 59.5821 + 80 0.0000 2.280209 62.0476 + 81 0.0000 2.297735 62.5245 + 82 0.0000 2.310939 62.8839 + 83 0.0000 2.374946 64.6256 + 84 0.0000 2.444167 66.5092 + 85 0.0000 2.465382 67.0865 + 86 0.0000 2.487606 67.6912 + 87 0.0000 2.502093 68.0854 + 88 0.0000 2.515406 68.4477 + 89 0.0000 2.528979 68.8170 + 90 0.0000 2.574378 70.0524 + 91 0.0000 2.603794 70.8528 + 92 0.0000 2.653502 72.2055 + 93 0.0000 2.719320 73.9965 + 94 0.0000 2.731250 74.3211 + 95 0.0000 2.760266 75.1106 + 96 0.0000 2.835750 77.1647 + 97 0.0000 2.903450 79.0069 + 98 0.0000 2.948366 80.2291 + 99 0.0000 3.083968 83.9190 + 100 0.0000 3.144795 85.5742 + 101 0.0000 3.176569 86.4388 + 102 0.0000 3.263178 88.7956 + 103 0.0000 3.469183 94.4013 + 104 0.0000 3.754458 102.1640 + 105 0.0000 3.892554 105.9218 + 106 0.0000 4.031552 109.7041 + 107 0.0000 4.159376 113.1824 + 108 0.0000 4.190162 114.0201 + 109 0.0000 4.278652 116.4281 + 110 0.0000 4.364983 118.7772 + 111 0.0000 4.401071 119.7592 + 112 0.0000 4.548286 123.7652 + 113 0.0000 4.630429 126.0004 + 114 0.0000 4.750896 129.2785 + 115 0.0000 4.787179 130.2658 + 116 0.0000 4.800067 130.6165 + 117 0.0000 4.888946 133.0350 + 118 0.0000 4.960205 134.9740 + 119 0.0000 4.998191 136.0077 + 120 0.0000 5.070645 137.9793 + 121 0.0000 5.100144 138.7820 + 122 0.0000 5.177099 140.8760 + 123 0.0000 5.224821 142.1746 + 124 0.0000 5.257462 143.0628 + 125 0.0000 5.326720 144.9474 + 126 0.0000 5.343939 145.4160 + 127 0.0000 5.409967 147.2127 + 128 0.0000 5.555622 151.1762 + 129 0.0000 5.691941 154.8856 + 130 0.0000 5.795480 157.7030 + 131 0.0000 6.000658 163.2862 + 132 0.0000 6.117621 166.4689 + 133 0.0000 6.409196 174.4031 + 134 0.0000 6.499177 176.8516 + 135 0.0000 6.509704 177.1380 + 136 0.0000 6.693281 182.1334 + 137 0.0000 6.705109 182.4553 + 138 0.0000 6.742096 183.4618 + 139 0.0000 6.844297 186.2428 + 140 0.0000 6.907158 187.9533 + 141 0.0000 7.068149 192.3341 + 142 0.0000 7.125038 193.8821 + 143 0.0000 7.177594 195.3123 + 144 0.0000 7.188333 195.6045 + 145 0.0000 7.229956 196.7371 + 146 0.0000 7.265698 197.7097 + 147 0.0000 7.350826 200.0262 + 148 0.0000 7.396213 201.2612 + 149 0.0000 7.440830 202.4753 + 150 0.0000 7.480663 203.5592 + 151 0.0000 7.589377 206.5175 + 152 0.0000 7.626075 207.5160 + 153 0.0000 7.670986 208.7382 + 154 0.0000 7.855519 213.7595 + 155 0.0000 7.921381 215.5517 + 156 0.0000 8.032987 218.5887 + 157 0.0000 8.386637 228.2120 + 158 0.0000 14.103270 383.7695 + 159 0.0000 14.960964 407.1085 + 160 0.0000 16.114674 438.5026 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.352413 0.000000 + 1 N : 0.346741 0.000000 + 2 O : -0.265341 0.000000 + 3 H : 0.271014 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.867963 s : 3.867963 + pz : 1.423458 p : 4.456709 + px : 1.239668 + py : 1.793583 + dz2 : 0.010317 d : 0.023148 + dxz : -0.001238 + dyz : 0.001106 + dx2y2 : 0.006645 + dxy : 0.006317 + f0 : 0.000343 f : 0.004593 + f+1 : 0.000995 + f-1 : 0.000412 + f+2 : 0.000507 + f-2 : -0.000036 + f+3 : 0.001054 + f-3 : 0.001318 + 1 N s : 3.829127 s : 3.829127 + pz : 1.055761 p : 2.654762 + px : 0.832967 + py : 0.766034 + dz2 : 0.032191 d : 0.139286 + dxz : 0.033108 + dyz : 0.027434 + dx2y2 : 0.024156 + dxy : 0.022396 + f0 : 0.005376 f : 0.030084 + f+1 : 0.008719 + f-1 : 0.004839 + f+2 : 0.002941 + f-2 : 0.000901 + f+3 : 0.002339 + f-3 : 0.004970 + 2 O s : 3.878768 s : 3.878768 + pz : 1.204235 p : 4.315111 + px : 1.842286 + py : 1.268590 + dz2 : 0.016900 d : 0.063731 + dxz : 0.016341 + dyz : 0.027353 + dx2y2 : 0.000845 + dxy : 0.002293 + f0 : 0.002329 f : 0.007731 + f+1 : 0.002198 + f-1 : 0.002392 + f+2 : 0.000250 + f-2 : 0.000546 + f+3 : 0.000045 + f-3 : -0.000030 + 3 H s : 0.626174 s : 0.626174 + pz : 0.019408 p : 0.080663 + px : 0.020584 + py : 0.040671 + dz2 : 0.003613 d : 0.022150 + dxz : 0.010378 + dyz : 0.006839 + dx2y2 : 0.000360 + dxy : 0.000960 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.596107 0.000000 + 1 N : -0.259599 0.000000 + 2 O : 0.239637 0.000000 + 3 H : -0.576145 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.119116 s : 3.119116 + pz : 1.306977 p : 3.916984 + px : 1.176602 + py : 1.433406 + dz2 : 0.065221 d : 0.282802 + dxz : 0.067596 + dyz : 0.014136 + dx2y2 : 0.088627 + dxy : 0.047223 + f0 : 0.012476 f : 0.084990 + f+1 : 0.016282 + f-1 : 0.003971 + f+2 : 0.016990 + f-2 : 0.002892 + f+3 : 0.017113 + f-3 : 0.015267 + 1 N s : 3.011136 s : 3.011136 + pz : 1.207678 p : 2.835995 + px : 0.903176 + py : 0.725141 + dz2 : 0.259648 d : 0.958793 + dxz : 0.299913 + dyz : 0.125202 + dx2y2 : 0.149321 + dxy : 0.124709 + f0 : 0.098749 f : 0.453675 + f+1 : 0.127976 + f-1 : 0.063719 + f+2 : 0.053445 + f-2 : 0.017479 + f+3 : 0.037877 + f-3 : 0.054430 + 2 O s : 3.315940 s : 3.315940 + pz : 1.393670 p : 3.999400 + px : 1.505638 + py : 1.100092 + dz2 : 0.139002 d : 0.326833 + dxz : 0.096165 + dyz : 0.062073 + dx2y2 : 0.020245 + dxy : 0.009348 + f0 : 0.042386 f : 0.118190 + f+1 : 0.029515 + f-1 : 0.024204 + f+2 : 0.013845 + f-2 : 0.006410 + f+3 : 0.001115 + f-3 : 0.000716 + 3 H s : 0.622844 s : 0.622844 + pz : 0.254122 p : 0.559020 + px : 0.132329 + py : 0.172569 + dz2 : 0.127241 d : 0.394282 + dxz : 0.108906 + dyz : 0.114840 + dx2y2 : 0.026706 + dxy : 0.016589 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3524 8.0000 -0.3524 1.9080 1.9080 -0.0000 + 1 N 6.6533 7.0000 0.3467 2.5445 2.5445 -0.0000 + 2 O 8.2653 8.0000 -0.2653 1.7465 1.7465 0.0000 + 3 H 0.7290 1.0000 0.2710 0.9503 0.9503 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8882 B( 0-O , 3-H ) : 0.9632 B( 1-N , 2-O ) : 1.6795 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.372 sec +Sum of individual times .... 2.028 sec ( 85.5%) + +Fock matrix formation .... 1.738 sec ( 73.3%) +Diagonalization .... 0.136 sec ( 5.7%) +Density matrix formation .... 0.012 sec ( 0.5%) +Population analysis .... 0.036 sec ( 1.5%) +Initial guess .... 0.020 sec ( 0.8%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.013 sec ( 0.5%) +DIIS solution .... 0.086 sec ( 3.6%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.934 sec +Reference energy ... -204.718443465 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 10.648 sec +AO-integral generation ... 0.351 sec +Half transformation ... 0.174 sec +K-integral sorting ... 8.254 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.060 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.066 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.093 s ( 0.000 ms/b) +: : 151164 b 0 skpd 0.130 s ( 0.001 ms/b) + 159120 b 0 skpd 0.047 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.093 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.081 s ( 0.001 ms/b) +: : 87516 b 0 skpd 0.064 s ( 0.001 ms/b) + 87516 b 0 skpd 0.111 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.062 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.916 sec +AO-integral generation ... 0.714 sec +Half transformation ... 0.095 sec +J-integral sorting ... 0.081 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.250 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.402 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090443870 +EMP2(bb)= -0.090443870 +EMP2(ab)= -0.516686609 + +Initial guess performed in 0.239 sec +E(0) ... -204.718443465 +E(MP2) ... -0.697574350 +Initial E(tot) ... -205.416017814 + ... 0.188343837 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.416017814 -0.697574350 -0.000000000 0.023945183 6.30 0.000001110 + *** Turning on DIIS *** + 1 -205.387046937 -0.668603473 0.028970877 0.009709430 6.05 0.057523773 + 2 -205.406546871 -0.688103406 -0.019499934 0.005133680 6.36 0.060475848 + 3 -205.410287357 -0.691843892 -0.003740486 0.002059077 8.29 0.074745665 + 4 -205.411854680 -0.693411215 -0.001567323 0.001711779 7.24 0.081519499 + 5 -205.412413152 -0.693969688 -0.000558472 0.000956770 7.42 0.087246794 + 6 -205.412527331 -0.694083867 -0.000114179 0.000576260 8.50 0.090170369 + 7 -205.412574845 -0.694131381 -0.000047514 0.000238334 6.85 0.091544652 + 8 -205.412587854 -0.694144390 -0.000013009 0.000122641 6.64 0.092068835 + 9 -205.412583460 -0.694139995 0.000004394 0.000033962 6.49 0.092224491 + 10 -205.412588510 -0.694145045 -0.000005050 0.000020131 6.01 0.092273562 + 11 -205.412585675 -0.694142210 0.000002835 0.000015927 6.78 0.092265844 + 12 -205.412586901 -0.694143436 -0.000001226 0.000012073 6.12 0.092277200 + 13 -205.412586654 -0.694143190 0.000000247 0.000007965 6.22 0.092272820 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.718443465 +E(CORR) ... -0.694143190 +E(TOT) ... -205.412586654 +Singles norm **1/2 ... 0.092272820 ( 0.046136410, 0.046136410) +T1 diagnostic ... 0.021748912 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.057110 + 10a-> 13a 10b-> 13b 0.041064 + 8b-> 13b -1b-> -1b 0.038290 + 8a-> 13a -1a-> -1a 0.038290 + 10b-> 13b -1b-> -1b 0.034959 + 10a-> 13a -1a-> -1a 0.034959 + 8a-> 13a 9b-> 13b 0.030828 + 9a-> 13a 8b-> 13b 0.030828 + 8a-> 13a 10b-> 13b 0.029198 + 10a-> 13a 8b-> 13b 0.029198 + 11a-> 13a 11b-> 13b 0.028039 + 5a-> 13a 5b-> 13b 0.026746 + 9a-> 13a 9b-> 13b 0.026328 + 10a-> 13a 9b-> 13b 0.024598 + 9a-> 13a 10b-> 13b 0.024598 + 11a-> 26a 11b-> 26b 0.024359 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034700057 + alpha-alpha-alpha ... -0.000892794 ( 2.6%) + alpha-alpha-beta ... -0.016457234 ( 47.4%) + alpha-beta -beta ... -0.016457234 ( 47.4%) + beta -beta -beta ... -0.000892794 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034700057 + +Final correlation energy ... -0.728843247 +E(CCSD) ... -205.412586654 +E(CCSD(T)) ... -205.447286712 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210441739 sqrt= 1.100200772 +W(HF) = 0.826144678 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.269419 0.000000 + 1 N : 0.159133 0.000000 + 2 O : -0.148066 -0.000000 + 3 H : 0.258353 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.846257 s : 3.846257 + pz : 1.404568 p : 4.359534 + px : 1.235217 + py : 1.719749 + dz2 : 0.015333 d : 0.055237 + dxz : 0.006657 + dyz : 0.007879 + dx2y2 : 0.011529 + dxy : 0.013838 + f0 : 0.001033 f : 0.008392 + f+1 : 0.001424 + f-1 : 0.001046 + f+2 : 0.001070 + f-2 : 0.000647 + f+3 : 0.001317 + f-3 : 0.001853 + 1 N s : 3.881140 s : 3.881140 + pz : 1.028105 p : 2.760545 + px : 0.873915 + py : 0.858526 + dz2 : 0.035412 d : 0.169758 + dxz : 0.044558 + dyz : 0.028769 + dx2y2 : 0.029970 + dxy : 0.031049 + f0 : 0.004584 f : 0.029424 + f+1 : 0.008467 + f-1 : 0.004181 + f+2 : 0.003243 + f-2 : 0.001365 + f+3 : 0.002476 + f-3 : 0.005107 + 2 O s : 3.866223 s : 3.866223 + pz : 1.190982 p : 4.186500 + px : 1.759242 + py : 1.236277 + dz2 : 0.018837 d : 0.085093 + dxz : 0.023151 + dyz : 0.027568 + dx2y2 : 0.007176 + dxy : 0.008362 + f0 : 0.002312 f : 0.010250 + f+1 : 0.002625 + f-1 : 0.002286 + f+2 : 0.000818 + f-2 : 0.001054 + f+3 : 0.000618 + f-3 : 0.000538 + 3 H s : 0.637262 s : 0.637262 + pz : 0.014800 p : 0.085356 + px : 0.024152 + py : 0.046404 + dz2 : 0.002339 d : 0.019029 + dxz : 0.009360 + dyz : 0.005514 + dx2y2 : 0.000796 + dxy : 0.001021 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.610999 -0.000000 + 1 N : -0.308643 0.000000 + 2 O : 0.274499 0.000000 + 3 H : -0.576856 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.125743 s : 3.125743 + pz : 1.293799 p : 3.857455 + px : 1.184828 + py : 1.378828 + dz2 : 0.071760 d : 0.313879 + dxz : 0.073045 + dyz : 0.020287 + dx2y2 : 0.095410 + dxy : 0.053377 + f0 : 0.013370 f : 0.091925 + f+1 : 0.017007 + f-1 : 0.005048 + f+2 : 0.017458 + f-2 : 0.003408 + f+3 : 0.018652 + f-3 : 0.016982 + 1 N s : 3.016255 s : 3.016255 + pz : 1.182550 p : 2.882010 + px : 0.917981 + py : 0.781480 + dz2 : 0.263620 d : 0.968087 + dxz : 0.298049 + dyz : 0.123566 + dx2y2 : 0.156437 + dxy : 0.126414 + f0 : 0.095807 f : 0.442290 + f+1 : 0.125014 + f-1 : 0.063427 + f+2 : 0.051181 + f-2 : 0.017539 + f+3 : 0.038877 + f-3 : 0.050445 + 2 O s : 3.317897 s : 3.317897 + pz : 1.384331 p : 3.923435 + px : 1.452126 + py : 1.086978 + dz2 : 0.144171 d : 0.357410 + dxz : 0.099030 + dyz : 0.071946 + dx2y2 : 0.025868 + dxy : 0.016395 + f0 : 0.043546 f : 0.126758 + f+1 : 0.030582 + f-1 : 0.027325 + f+2 : 0.014214 + f-2 : 0.008085 + f+3 : 0.001717 + f-3 : 0.001289 + 3 H s : 0.624438 s : 0.624438 + pz : 0.257904 p : 0.568542 + px : 0.133189 + py : 0.177449 + dz2 : 0.125291 d : 0.383876 + dxz : 0.105194 + dyz : 0.109850 + dx2y2 : 0.027069 + dxy : 0.016472 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2694 8.0000 -0.2694 2.2727 1.8115 0.4612 + 1 N 6.8409 7.0000 0.1591 2.8300 2.3500 0.4800 + 2 O 8.1481 8.0000 -0.1481 2.1449 1.6476 0.4973 + 3 H 0.7416 1.0000 0.2584 0.9721 0.9008 0.0713 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8205 B( 0-O , 3-H ) : 0.8930 B( 1-N , 2-O ) : 1.5356 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 127.248 sec + +Fock Matrix Formation ... 0.934 sec ( 0.7%) +Initial Guess ... 0.239 sec ( 0.2%) +DIIS Solver ... 6.404 sec ( 5.0%) +State Vector Update ... 0.344 sec ( 0.3%) +Sigma-vector construction ... 88.522 sec ( 69.6%) + <0|H|D> ... 0.009 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.054 sec ( 0.1% of sigma) + (0-ext) ... 0.173 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.062 sec ( 0.1% of sigma) + (2-ext) ... 2.265 sec ( 2.6% of sigma) + (4-ext) ... 50.822 sec ( 57.4% of sigma) + ... 4.722 sec ( 5.3% of sigma) + ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.022 sec ( 0.0% of sigma) + (1-ext) ... 0.240 sec ( 0.3% of sigma) + Fock-dressing ... 5.953 sec ( 6.7% of sigma) + (ik|jl)-dressing ... 0.208 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 19.733 sec ( 22.3% of sigma) + Pair energies ... 0.027 sec ( 0.0% of sigma) +Total Time for computing (T) ... 16.653 sec ( 13.1% of ALL) + I/O of integral and amplitudes ... 1.370 sec ( 8.2% of (T)) + External N**7 contributions ... 9.746 sec ( 58.5% of (T)) + Internal N**7 contributions ... 0.838 sec ( 5.0% of (T)) + N**6 triples energy contributions ... 2.437 sec ( 14.6% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.447286711749 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.005.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.005.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.435800, -0.134948 -0.641255) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.92603 -0.12641 -0.52714 +Nuclear contribution : -0.97862 0.30406 1.32039 + ----------------------------------------- +Total Dipole Moment : -0.05259 0.17765 0.79324 + ----------------------------------------- +Magnitude (a.u.) : 0.81459 +Magnitude (Debye) : 2.07053 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.986256 0.413375 0.366794 +Rotational constants in MHz : 89525.715141 12392.671733 10996.200546 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.520010 0.540447 -0.317912 +x,y,z [Debye]: 1.321761 1.373708 -0.808069 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.435800, -0.134948 -0.641255) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.91619 -0.11471 -0.70070 +Nuclear contribution : -0.97862 0.30406 1.32039 + ----------------------------------------- +Total Dipole Moment : -0.06243 0.18935 0.61969 + ----------------------------------------- +Magnitude (a.u.) : 0.65097 +Magnitude (Debye) : 1.65464 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.986256 0.413375 0.366794 +Rotational constants in MHz : 89525.715141 12392.671733 10996.200546 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.422501 0.397923 -0.294813 +x,y,z [Debye]: 1.073912 1.011439 -0.749356 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 6 * + * * + * Dihedral ( 2, 1, 0, 3) : -139.09090909 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0398041800 RMS(Int)= 0.0002690872 + Iter 1: RMS(Cart)= 0.0000750058 RMS(Int)= 0.0000014882 + Iter 2: RMS(Cart)= 0.0000004148 RMS(Int)= 0.0000000082 + Iter 3: RMS(Cart)= 0.0000000023 RMS(Int)= 0.0000000000 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4511 0.000000 + 2. B(O 2,N 1) 1.1735 0.000000 + 3. B(H 3,O 0) 0.9719 0.000000 + 4. A(N 1,O 0,H 3) 102.0004 0.000000 + 5. A(O 0,N 1,O 2) 110.4634 0.000000 + 6. D(O 2,N 1,O 0,H 3) -139.0909 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.775777 -0.096109 0.164014 + N 0.649996 -0.246560 -0.060273 + O 0.926310 0.054777 -1.160203 + H -0.800528 0.287892 1.056461 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.466006 -0.181619 0.309942 + 1 N 7.0000 0 14.007 1.228315 -0.465931 -0.113900 + 2 O 8.0000 0 15.999 1.750472 0.103513 -2.192465 + 3 H 1.0000 0 1.008 -1.512779 0.544036 1.996423 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.451074366937 0.00000000 0.00000000 + O 2 1 0 1.171311518767 110.51784174 0.00000000 + H 1 2 3 0.969073657248 102.03675972 212.72727269 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.742133153463 0.00000000 0.00000000 + O 2 1 0 2.213457987977 110.51784174 0.00000000 + H 1 2 3 1.831283815796 102.03675972 212.72727269 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 549 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 391 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.140894009345 Eh + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.1408940093 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.956e-04 +Time for diagonalization ... 0.005 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.003 sec +Total time needed ... 0.010 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7116432808 0.000000000000 0.00166845 0.00005407 0.0198790 0.7000 + 1 -204.7125530152 -0.000909734429 0.00160737 0.00004894 0.0164644 0.7000 + ***Turning on DIIS*** + 2 -204.7133297372 -0.000776721943 0.00442324 0.00013255 0.0133889 0.0000 + 3 -204.7177488547 -0.004419117502 0.00181180 0.00005445 0.0053627 0.0000 + 4 -204.7150362926 0.002712562089 0.00087030 0.00002521 0.0021391 0.0000 + 5 -204.7167202964 -0.001684003791 0.00055072 0.00002003 0.0010691 0.0000 + 6 -204.7161712653 0.000549031102 0.00064998 0.00002316 0.0007179 0.0000 + 7 -204.7156383746 0.000532890679 0.00033738 0.00001141 0.0003425 0.0000 + 8 -204.7163780170 -0.000739642369 0.00018119 0.00000719 0.0002018 0.0000 + 9 -204.7159976868 0.000380330204 0.00015434 0.00000540 0.0001410 0.0000 + 10 -204.7161715162 -0.000173829405 0.00007507 0.00000232 0.0000632 0.0000 + 11 -204.7162760457 -0.000104529476 0.00002672 0.00000078 0.0000304 0.0000 + 12 -204.7161567000 0.000119345697 0.00000878 0.00000025 0.0000087 0.0000 + 13 -204.7161940573 -0.000037357368 0.00000248 0.00000008 0.0000035 0.0000 + 14 -204.7161813022 0.000012755159 0.00000096 0.00000003 0.0000018 0.0000 + 15 -204.7161842575 -0.000002955319 0.00000055 0.00000002 0.0000013 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 16 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71618604 Eh -5570.61063 eV + +Components: +Nuclear Repulsion : 69.14089401 Eh 1881.41938 eV +Electronic Energy : -273.85708005 Eh -7452.03000 eV +One Electron Energy: -417.99972812 Eh -11374.35086 eV +Two Electron Energy: 144.14264807 Eh 3922.32086 eV + +Virial components: +Potential Energy : -408.95190672 Eh -11128.14713 eV +Kinetic Energy : 204.23572068 Eh 5557.53650 eV +Virial Ratio : 2.00235250 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.7863e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.5757e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.3088e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.6389e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.675053 -562.5968 + 1 1.0000 -20.631993 -561.4251 + 2 1.0000 -15.799829 -429.9352 + 3 1.0000 -1.606399 -43.7123 + 4 1.0000 -1.391762 -37.8718 + 5 1.0000 -0.949804 -25.8455 + 6 1.0000 -0.777850 -21.1664 + 7 1.0000 -0.728634 -19.8271 + 8 1.0000 -0.691327 -18.8120 + 9 1.0000 -0.613525 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4.549437 123.7965 + 113 0.0000 4.628264 125.9415 + 114 0.0000 4.743802 129.0854 + 115 0.0000 4.757910 129.4693 + 116 0.0000 4.793211 130.4299 + 117 0.0000 4.883715 132.8926 + 118 0.0000 4.955517 134.8465 + 119 0.0000 4.992796 135.8609 + 120 0.0000 5.071256 137.9959 + 121 0.0000 5.095065 138.6438 + 122 0.0000 5.175511 140.8328 + 123 0.0000 5.206435 141.6743 + 124 0.0000 5.258803 143.0993 + 125 0.0000 5.325470 144.9134 + 126 0.0000 5.359463 145.8384 + 127 0.0000 5.406019 147.1053 + 128 0.0000 5.555619 151.1761 + 129 0.0000 5.695752 154.9893 + 130 0.0000 5.791956 157.6071 + 131 0.0000 5.997379 163.1970 + 132 0.0000 6.129896 166.8029 + 133 0.0000 6.408707 174.3898 + 134 0.0000 6.497740 176.8125 + 135 0.0000 6.511425 177.1849 + 136 0.0000 6.698768 182.2828 + 137 0.0000 6.701332 182.3525 + 138 0.0000 6.745800 183.5626 + 139 0.0000 6.839873 186.1224 + 140 0.0000 6.898853 187.7273 + 141 0.0000 7.069176 192.3621 + 142 0.0000 7.121471 193.7851 + 143 0.0000 7.160779 194.8547 + 144 0.0000 7.184634 195.5038 + 145 0.0000 7.232100 196.7955 + 146 0.0000 7.267400 197.7560 + 147 0.0000 7.348951 199.9751 + 148 0.0000 7.396725 201.2751 + 149 0.0000 7.446817 202.6382 + 150 0.0000 7.483749 203.6432 + 151 0.0000 7.561833 205.7679 + 152 0.0000 7.623797 207.4541 + 153 0.0000 7.653175 208.2535 + 154 0.0000 7.875213 214.2954 + 155 0.0000 7.909905 215.2395 + 156 0.0000 8.026242 218.4051 + 157 0.0000 8.379386 228.0147 + 158 0.0000 14.075132 383.0038 + 159 0.0000 14.903086 405.5336 + 160 0.0000 16.059940 437.0132 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.675053 -562.5968 + 1 1.0000 -20.631993 -561.4251 + 2 1.0000 -15.799829 -429.9352 + 3 1.0000 -1.606399 -43.7123 + 4 1.0000 -1.391762 -37.8718 + 5 1.0000 -0.949804 -25.8455 + 6 1.0000 -0.777850 -21.1664 + 7 1.0000 -0.728634 -19.8271 + 8 1.0000 -0.691327 -18.8120 + 9 1.0000 -0.613525 -16.6949 + 10 1.0000 -0.529866 -14.4184 + 11 1.0000 -0.461173 -12.5492 + 12 0.0000 0.028901 0.7864 + 13 0.0000 0.075488 2.0541 + 14 0.0000 0.093115 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0.0000 2.440661 66.4138 + 85 0.0000 2.464777 67.0700 + 86 0.0000 2.483158 67.5702 + 87 0.0000 2.498671 67.9923 + 88 0.0000 2.509999 68.3006 + 89 0.0000 2.532578 68.9150 + 90 0.0000 2.572099 69.9904 + 91 0.0000 2.603503 70.8449 + 92 0.0000 2.660271 72.3897 + 93 0.0000 2.705584 73.6227 + 94 0.0000 2.735079 74.4253 + 95 0.0000 2.790250 75.9266 + 96 0.0000 2.815826 76.6225 + 97 0.0000 2.910735 79.2051 + 98 0.0000 2.960840 80.5686 + 99 0.0000 3.075177 83.6798 + 100 0.0000 3.133388 85.2638 + 101 0.0000 3.170957 86.2861 + 102 0.0000 3.261702 88.7554 + 103 0.0000 3.476247 94.5935 + 104 0.0000 3.740471 101.7834 + 105 0.0000 3.886287 105.7512 + 106 0.0000 4.033749 109.7639 + 107 0.0000 4.153627 113.0259 + 108 0.0000 4.196798 114.2007 + 109 0.0000 4.295088 116.8753 + 110 0.0000 4.368349 118.8688 + 111 0.0000 4.389517 119.4448 + 112 0.0000 4.549437 123.7965 + 113 0.0000 4.628264 125.9415 + 114 0.0000 4.743802 129.0854 + 115 0.0000 4.757910 129.4693 + 116 0.0000 4.793211 130.4299 + 117 0.0000 4.883715 132.8926 + 118 0.0000 4.955517 134.8465 + 119 0.0000 4.992796 135.8609 + 120 0.0000 5.071256 137.9959 + 121 0.0000 5.095065 138.6438 + 122 0.0000 5.175511 140.8328 + 123 0.0000 5.206435 141.6743 + 124 0.0000 5.258803 143.0993 + 125 0.0000 5.325470 144.9134 + 126 0.0000 5.359463 145.8384 + 127 0.0000 5.406019 147.1053 + 128 0.0000 5.555619 151.1761 + 129 0.0000 5.695752 154.9893 + 130 0.0000 5.791956 157.6071 + 131 0.0000 5.997379 163.1970 + 132 0.0000 6.129896 166.8029 + 133 0.0000 6.408707 174.3898 + 134 0.0000 6.497740 176.8125 + 135 0.0000 6.511425 177.1849 + 136 0.0000 6.698768 182.2828 + 137 0.0000 6.701332 182.3525 + 138 0.0000 6.745800 183.5626 + 139 0.0000 6.839873 186.1224 + 140 0.0000 6.898853 187.7273 + 141 0.0000 7.069176 192.3621 + 142 0.0000 7.121471 193.7851 + 143 0.0000 7.160779 194.8547 + 144 0.0000 7.184634 195.5038 + 145 0.0000 7.232100 196.7955 + 146 0.0000 7.267400 197.7560 + 147 0.0000 7.348951 199.9751 + 148 0.0000 7.396725 201.2751 + 149 0.0000 7.446817 202.6382 + 150 0.0000 7.483749 203.6432 + 151 0.0000 7.561833 205.7679 + 152 0.0000 7.623797 207.4541 + 153 0.0000 7.653175 208.2535 + 154 0.0000 7.875213 214.2954 + 155 0.0000 7.909905 215.2395 + 156 0.0000 8.026242 218.4051 + 157 0.0000 8.379386 228.0147 + 158 0.0000 14.075132 383.0038 + 159 0.0000 14.903086 405.5336 + 160 0.0000 16.059940 437.0132 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.353207 0.000000 + 1 N : 0.345633 0.000000 + 2 O : -0.263160 0.000000 + 3 H : 0.270734 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.867948 s : 3.867948 + pz : 1.448512 p : 4.457271 + px : 1.236694 + py : 1.772065 + dz2 : 0.009561 d : 0.023336 + dxz : -0.000501 + dyz : 0.001314 + dx2y2 : 0.007257 + dxy : 0.005705 + f0 : 0.000313 f : 0.004652 + f+1 : 0.000962 + f-1 : 0.000534 + f+2 : 0.000479 + f-2 : -0.000003 + f+3 : 0.001093 + f-3 : 0.001272 + 1 N s : 3.827713 s : 3.827713 + pz : 1.040140 p : 2.658535 + px : 0.835389 + py : 0.783006 + dz2 : 0.032912 d : 0.137733 + dxz : 0.031977 + dyz : 0.025152 + dx2y2 : 0.024881 + dxy : 0.022811 + f0 : 0.005448 f : 0.030386 + f+1 : 0.008386 + f-1 : 0.004356 + f+2 : 0.003312 + f-2 : 0.001265 + f+3 : 0.002530 + f-3 : 0.005089 + 2 O s : 3.880029 s : 3.880029 + pz : 1.204487 p : 4.312479 + px : 1.841287 + py : 1.266705 + dz2 : 0.018430 d : 0.063014 + dxz : 0.015380 + dyz : 0.024947 + dx2y2 : 0.001553 + dxy : 0.002704 + f0 : 0.002424 f : 0.007638 + f+1 : 0.002027 + f-1 : 0.002086 + f+2 : 0.000390 + f-2 : 0.000608 + f+3 : 0.000091 + f-3 : 0.000012 + 3 H s : 0.626343 s : 0.626343 + pz : 0.021567 p : 0.081196 + px : 0.020388 + py : 0.039241 + dz2 : 0.004698 d : 0.021727 + dxz : 0.009626 + dyz : 0.005119 + dx2y2 : 0.000732 + dxy : 0.001551 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.590773 0.000000 + 1 N : -0.260509 0.000000 + 2 O : 0.239973 0.000000 + 3 H : -0.570237 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.120367 s : 3.120367 + pz : 1.315865 p : 3.921564 + px : 1.176380 + py : 1.429320 + dz2 : 0.061034 d : 0.282293 + dxz : 0.066600 + dyz : 0.017718 + dx2y2 : 0.088319 + dxy : 0.048622 + f0 : 0.010710 f : 0.085003 + f+1 : 0.016682 + f-1 : 0.004839 + f+2 : 0.017105 + f-2 : 0.002906 + f+3 : 0.016850 + f-3 : 0.015911 + 1 N s : 3.012754 s : 3.012754 + pz : 1.187091 p : 2.838214 + px : 0.904515 + py : 0.746608 + dz2 : 0.249118 d : 0.956106 + dxz : 0.295046 + dyz : 0.131357 + dx2y2 : 0.152634 + dxy : 0.127951 + f0 : 0.092990 f : 0.453436 + f+1 : 0.121885 + f-1 : 0.063658 + f+2 : 0.056997 + f-2 : 0.023073 + f+3 : 0.039077 + f-3 : 0.055757 + 2 O s : 3.317480 s : 3.317480 + pz : 1.382126 p : 3.998355 + px : 1.506400 + py : 1.109828 + dz2 : 0.129287 d : 0.326285 + dxz : 0.094010 + dyz : 0.069117 + dx2y2 : 0.022848 + dxy : 0.011023 + f0 : 0.038297 f : 0.117907 + f+1 : 0.027836 + f-1 : 0.025756 + f+2 : 0.015771 + f-2 : 0.007825 + f+3 : 0.001283 + f-3 : 0.001139 + 3 H s : 0.621187 s : 0.621187 + pz : 0.247567 p : 0.556637 + px : 0.131634 + py : 0.177436 + dz2 : 0.124349 d : 0.392413 + dxz : 0.103297 + dyz : 0.110498 + dx2y2 : 0.031659 + dxy : 0.022610 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3532 8.0000 -0.3532 1.8890 1.8890 -0.0000 + 1 N 6.6544 7.0000 0.3456 2.5491 2.5491 -0.0000 + 2 O 8.2632 8.0000 -0.2632 1.7517 1.7517 0.0000 + 3 H 0.7293 1.0000 0.2707 0.9538 0.9538 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8744 B( 0-O , 3-H ) : 0.9598 B( 1-N , 2-O ) : 1.6888 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 7 sec + +Total time .... 7.301 sec +Sum of individual times .... 6.744 sec ( 92.4%) + +Fock matrix formation .... 5.620 sec ( 77.0%) +Diagonalization .... 0.550 sec ( 7.5%) +Density matrix formation .... 0.029 sec ( 0.4%) +Population analysis .... 0.041 sec ( 0.6%) +Initial guess .... 0.039 sec ( 0.5%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.028 sec ( 0.4%) +DIIS solution .... 0.465 sec ( 6.4%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.566 sec +Reference energy ... -204.716184269 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 11.762 sec +AO-integral generation ... 0.386 sec +Half transformation ... 0.188 sec +K-integral sorting ... 8.805 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.065 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.094 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.090 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.099 s ( 0.001 ms/b) + 159120 b 0 skpd 0.044 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.101 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.098 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.111 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.132 s ( 0.002 ms/b) +: 27846 b 0 skpd 0.079 s ( 0.003 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 1.090 sec +AO-integral generation ... 0.810 sec +Half transformation ... 0.109 sec +J-integral sorting ... 0.108 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.438 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.412 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090344161 +EMP2(bb)= -0.090344161 +EMP2(ab)= -0.516626426 + +Initial guess performed in 0.201 sec +E(0) ... -204.716184269 +E(MP2) ... -0.697314747 +Initial E(tot) ... -205.413499016 + ... 0.188298316 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.413499016 -0.697314747 -0.000000000 0.022905554 6.18 0.000001929 + *** Turning on DIIS *** + 1 -205.384821111 -0.668636841 0.028677906 0.009180818 7.16 0.056994838 + 2 -205.404274020 -0.688089751 -0.019452910 0.004862657 6.97 0.060001402 + 3 -205.408029797 -0.691845528 -0.003755777 0.001952829 5.41 0.074052060 + 4 -205.409588437 -0.693404168 -0.001558640 0.001647112 5.34 0.080677180 + 5 -205.410134577 -0.693950308 -0.000546140 0.000953233 6.63 0.086196501 + 6 -205.410244525 -0.694060256 -0.000109948 0.000584475 7.44 0.089012952 + 7 -205.410290604 -0.694106335 -0.000046079 0.000258990 6.51 0.090356176 + 8 -205.410303219 -0.694118950 -0.000012615 0.000133178 6.32 0.090892820 + 9 -205.410298940 -0.694114671 0.000004278 0.000038919 5.76 0.091057133 + 10 -205.410304132 -0.694119863 -0.000005192 0.000026125 6.49 0.091113081 + 11 -205.410301181 -0.694116912 0.000002950 0.000020377 7.00 0.091105522 + 12 -205.410302567 -0.694118297 -0.000001385 0.000015029 7.91 0.091118324 + 13 -205.410302313 -0.694118044 0.000000253 0.000009452 8.38 0.091113529 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.716184269 +E(CORR) ... -0.694118044 +E(TOT) ... -205.410302313 +Singles norm **1/2 ... 0.091113529 ( 0.045556765, 0.045556765) +T1 diagnostic ... 0.021475665 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.053252 + 10a-> 13a 10b-> 13b 0.036199 + 8b-> 13b -1b-> -1b 0.036165 + 8a-> 13a -1a-> -1a 0.036165 + 9a-> 13a 8b-> 13b 0.035092 + 8a-> 13a 9b-> 13b 0.035092 + 9a-> 13a 9b-> 13b 0.035089 + 10a-> 13a -1a-> -1a 0.033268 + 10b-> 13b -1b-> -1b 0.033268 + 11a-> 13a 11b-> 13b 0.028387 + 9a-> 13a 10b-> 13b 0.027775 + 10a-> 13a 9b-> 13b 0.027775 + 5a-> 13a 5b-> 13b 0.027192 + 10a-> 13a 8b-> 13b 0.026440 + 8a-> 13a 10b-> 13b 0.026440 + 11a-> 26a 11b-> 26b 0.025299 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034586558 + alpha-alpha-alpha ... -0.000887056 ( 2.6%) + alpha-alpha-beta ... -0.016406223 ( 47.4%) + alpha-beta -beta ... -0.016406223 ( 47.4%) + beta -beta -beta ... -0.000887056 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034586558 + +Final correlation energy ... -0.728704602 +E(CCSD) ... -205.410302313 +E(CCSD(T)) ... -205.444888871 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210306768 sqrt= 1.100139431 +W(HF) = 0.826236808 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.273326 -0.000000 + 1 N : 0.160253 -0.000000 + 2 O : -0.144598 0.000000 + 3 H : 0.257671 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.844920 s : 3.844920 + pz : 1.428866 p : 4.364763 + px : 1.231629 + py : 1.704268 + dz2 : 0.014816 d : 0.055215 + dxz : 0.007241 + dyz : 0.007959 + dx2y2 : 0.011947 + dxy : 0.013252 + f0 : 0.000984 f : 0.008428 + f+1 : 0.001391 + f-1 : 0.001171 + f+2 : 0.001047 + f-2 : 0.000683 + f+3 : 0.001353 + f-3 : 0.001799 + 1 N s : 3.880997 s : 3.880997 + pz : 1.016983 p : 2.760638 + px : 0.876310 + py : 0.867345 + dz2 : 0.035563 d : 0.168415 + dxz : 0.043549 + dyz : 0.027125 + dx2y2 : 0.030831 + dxy : 0.031347 + f0 : 0.004487 f : 0.029696 + f+1 : 0.008193 + f-1 : 0.003940 + f+2 : 0.003537 + f-2 : 0.001657 + f+3 : 0.002663 + f-3 : 0.005218 + 2 O s : 3.866833 s : 3.866833 + pz : 1.190425 p : 4.183273 + px : 1.758619 + py : 1.234229 + dz2 : 0.020004 d : 0.084343 + dxz : 0.022198 + dyz : 0.025605 + dx2y2 : 0.007802 + dxy : 0.008733 + f0 : 0.002359 f : 0.010149 + f+1 : 0.002468 + f-1 : 0.002068 + f+2 : 0.000914 + f-2 : 0.001098 + f+3 : 0.000664 + f-3 : 0.000578 + 3 H s : 0.637203 s : 0.637203 + pz : 0.017778 p : 0.086386 + px : 0.023882 + py : 0.044725 + dz2 : 0.003409 d : 0.018741 + dxz : 0.008721 + dyz : 0.003979 + dx2y2 : 0.001100 + dxy : 0.001531 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.604236 -0.000000 + 1 N : -0.308384 -0.000000 + 2 O : 0.276036 0.000000 + 3 H : -0.571888 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.126643 s : 3.126643 + pz : 1.301849 p : 3.864006 + px : 1.183876 + py : 1.378281 + dz2 : 0.067414 d : 0.313193 + dxz : 0.072152 + dyz : 0.024093 + dx2y2 : 0.095005 + dxy : 0.054529 + f0 : 0.011555 f : 0.091922 + f+1 : 0.017359 + f-1 : 0.005978 + f+2 : 0.017666 + f-2 : 0.003460 + f+3 : 0.018425 + f-3 : 0.017480 + 1 N s : 3.017916 s : 3.017916 + pz : 1.165262 p : 2.882482 + px : 0.919449 + py : 0.797772 + dz2 : 0.251976 d : 0.965656 + dxz : 0.293897 + dyz : 0.130508 + dx2y2 : 0.159671 + dxy : 0.129604 + f0 : 0.090038 f : 0.442331 + f+1 : 0.119203 + f-1 : 0.063449 + f+2 : 0.054700 + f-2 : 0.022779 + f+3 : 0.040132 + f-3 : 0.052030 + 2 O s : 3.319557 s : 3.319557 + pz : 1.372798 p : 3.921625 + px : 1.452981 + py : 1.095846 + dz2 : 0.135038 d : 0.356407 + dxz : 0.096913 + dyz : 0.077904 + dx2y2 : 0.028598 + dxy : 0.017954 + f0 : 0.040132 f : 0.126375 + f+1 : 0.028855 + f-1 : 0.028029 + f+2 : 0.016261 + f-2 : 0.009465 + f+3 : 0.001944 + f-3 : 0.001691 + 3 H s : 0.622654 s : 0.622654 + pz : 0.251792 p : 0.566992 + px : 0.132494 + py : 0.182706 + dz2 : 0.121780 d : 0.382242 + dxz : 0.099770 + dyz : 0.106601 + dx2y2 : 0.031931 + dxy : 0.022160 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2733 8.0000 -0.2733 2.2505 1.7912 0.4593 + 1 N 6.8397 7.0000 0.1603 2.8316 2.3492 0.4823 + 2 O 8.1446 8.0000 -0.1446 2.1479 1.6492 0.4987 + 3 H 0.7423 1.0000 0.2577 0.9762 0.9043 0.0718 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8052 B( 0-O , 3-H ) : 0.8915 B( 1-N , 2-O ) : 1.5429 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 126.998 sec + +Fock Matrix Formation ... 0.566 sec ( 0.4%) +Initial Guess ... 0.201 sec ( 0.2%) +DIIS Solver ... 5.191 sec ( 4.1%) +State Vector Update ... 0.214 sec ( 0.2%) +Sigma-vector construction ... 88.102 sec ( 69.4%) + <0|H|D> ... 0.008 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.054 sec ( 0.1% of sigma) + (0-ext) ... 0.179 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.063 sec ( 0.1% of sigma) + (2-ext) ... 2.285 sec ( 2.6% of sigma) + (4-ext) ... 50.674 sec ( 57.5% of sigma) + ... 4.428 sec ( 5.0% of sigma) + ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.022 sec ( 0.0% of sigma) + (1-ext) ... 0.237 sec ( 0.3% of sigma) + Fock-dressing ... 5.883 sec ( 6.7% of sigma) + (ik|jl)-dressing ... 0.202 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 19.866 sec ( 22.5% of sigma) + Pair energies ... 0.024 sec ( 0.0% of sigma) +Total Time for computing (T) ... 17.200 sec ( 13.5% of ALL) + I/O of integral and amplitudes ... 1.311 sec ( 7.6% of (T)) + External N**7 contributions ... 9.554 sec ( 55.5% of (T)) + Internal N**7 contributions ... 0.810 sec ( 4.7% of (T)) + N**6 triples energy contributions ... 2.331 sec ( 13.6% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.444888871014 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.001777880 -0.009209527 0.001936859 + 2 N : -0.004068398 -0.009633531 0.000078466 + 3 O : 0.001640852 0.008865858 -0.000486062 + 4 H : 0.000649665 0.009977200 -0.001529263 + +Norm of the cartesian gradient ... 0.019619580 +RMS gradient ... 0.005663685 +MAX gradient ... 0.009977200 + +------- +TIMINGS +------- + +Total numerical gradient time ... 938.229 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 326.48 cm**-1 + 7: 612.60 cm**-1 + 8: 816.67 cm**-1 + 9: 1253.53 cm**-1 + 10: 1694.74 cm**-1 + 11: 3712.38 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 0.058481 0.427963 0.182737 -0.052375 -0.103412 0.002745 + 1 0.047296 0.006913 -0.103204 -0.007066 0.007838 -0.024263 + 2 -0.043517 -0.261718 0.099187 -0.065106 -0.026623 -0.057849 + 3 -0.045554 -0.093361 -0.505728 0.040912 -0.040639 -0.000090 + 4 0.071728 -0.107154 0.097058 0.022867 -0.185037 0.000851 + 5 0.033868 0.201865 -0.070692 0.013882 0.658298 -0.001340 + 6 -0.015607 -0.334761 0.214751 -0.045913 0.112459 -0.000489 + 7 -0.051981 0.054024 -0.002490 -0.009956 0.154791 -0.000798 + 8 -0.008680 0.116700 -0.033211 0.053566 -0.551638 0.001075 + 9 -0.047482 -0.181975 0.718569 0.991536 0.421121 -0.034547 + 10 -0.922357 0.521796 0.328887 -0.047577 -0.010005 0.385940 + 11 0.357861 -0.503356 -0.064843 -0.009741 0.030580 0.919733 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 326.48 0.036038 182.12 0.034447 (-0.094304 -0.121893 0.103419) + 7: 612.60 0.017477 88.32 0.008903 (-0.081721 0.020184 0.042628) + 8: 816.67 0.021048 106.37 0.008043 (-0.078992 0.017119 0.038858) + 9: 1253.53 0.026573 134.29 0.006615 ( 0.075732 -0.013232 -0.026548) + 10: 1694.74 0.025668 129.71 0.004726 (-0.050111 -0.005598 0.046732) + 11: 3712.38 0.014367 72.60 0.001208 (-0.014968 0.012065 0.028950) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 326.48 E(vib) ... 0.24 +freq. 612.60 E(vib) ... 0.10 +freq. 816.67 E(vib) ... 0.05 +freq. 1253.53 E(vib) ... 0.01 +freq. 1694.74 E(vib) ... 0.00 +freq. 3712.38 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.44488887 Eh +Zero point energy ... 0.01917397 Eh 12.03 kcal/mol +Thermal vibrational correction ... 0.00063068 Eh 0.40 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42225168 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00346323 Eh 2.17 kcal/mol +Non-thermal (ZPE) correction 0.01917397 Eh 12.03 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02263720 Eh 14.21 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42225168 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.42130747 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.941813 0.413101 0.367738 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00092296 Eh 0.58 kcal/mol +Rotational entropy ... 0.00989104 Eh 6.21 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02861632 Eh 17.96 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00989104 Eh 6.21 kcal/mol| +| sn= 2 | S(rot)= 0.00923659 Eh 5.80 kcal/mol| +| sn= 3 | S(rot)= 0.00885375 Eh 5.56 kcal/mol| +| sn= 4 | S(rot)= 0.00858213 Eh 5.39 kcal/mol| +| sn= 5 | S(rot)= 0.00837144 Eh 5.25 kcal/mol| +| sn= 6 | S(rot)= 0.00819930 Eh 5.15 kcal/mol| +| sn= 7 | S(rot)= 0.00805375 Eh 5.05 kcal/mol| +| sn= 8 | S(rot)= 0.00792767 Eh 4.97 kcal/mol| +| sn= 9 | S(rot)= 0.00781646 Eh 4.90 kcal/mol| +| sn=10 | S(rot)= 0.00771698 Eh 4.84 kcal/mol| +| sn=11 | S(rot)= 0.00762699 Eh 4.79 kcal/mol| +| sn=12 | S(rot)= 0.00754484 Eh 4.73 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.42130747 Eh +Total entropy correction ... -0.02861632 Eh -17.96 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44992378 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00503491 Eh -3.16 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.444888872 Eh +Current gradient norm .... 0.019619579 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.009271788 0.125809797 0.174482415 0.490611845 0.512150477 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999800711 +Lowest eigenvalues of augmented Hessian: + -0.000075506 0.124070534 0.173571620 0.490606539 0.512099871 +Length of the computed step .... 0.019967412 +The final length of the internal step .... 0.019967412 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0081516619 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0043653298 RMS(Int)= 0.0081543562 + Iter 1: RMS(Cart)= 0.0000104114 RMS(Int)= 0.0000154795 + Iter 2: RMS(Cart)= 0.0000000309 RMS(Int)= 0.0000000585 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0019223018 0.0001000000 NO + MAX gradient 0.0031190633 0.0003000000 NO + RMS step 0.0081516619 0.0020000000 NO + MAX step 0.0180467474 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0095 Max(Angles) 0.08 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4511 -0.002243 0.0095 1.4607 + 2. B(O 2,N 1) 1.1735 0.003119 -0.0035 1.1699 + 3. B(H 3,O 0) 0.9719 0.002522 -0.0027 0.9691 + 4. A(N 1,O 0,H 3) 102.00 -0.000684 0.08 102.08 + 5. A(O 0,N 1,O 2) 110.46 -0.000765 0.02 110.49 + 6. D(O 2,N 1,O 0,H 3) -139.09 0.017587 0.00 -139.09 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.779613 -0.094901 0.166806 + N 0.654809 -0.246753 -0.063306 + O 0.927603 0.054110 -1.160486 + H -0.802799 0.287543 1.056986 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.473255 -0.179336 0.315217 + 1 N 7.0000 0 14.007 1.237410 -0.466295 -0.119631 + 2 O 8.0000 0 15.999 1.752916 0.102254 -2.193000 + 3 H 1.0000 0 1.008 -1.517070 0.543378 1.997414 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.460676931497 0.00000000 0.00000000 + O 2 1 0 1.169931104845 110.48647756 0.00000000 + H 1 2 3 0.969134474516 102.07681888 220.90909109 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.760279370666 0.00000000 0.00000000 + O 2 1 0 2.210849383714 110.48647756 0.00000000 + H 1 2 3 1.831398743777 102.07681888 220.90909109 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2224 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2689 + la=0 lb=0: 547 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 391 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.044834222306 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.960e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.003 sec +Total time needed ... 0.006 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7159570185 0.000000000000 0.00026089 0.00000784 0.0017122 0.7000 + 1 -204.7159733807 -0.000016362181 0.00021459 0.00000660 0.0014137 0.7000 + ***Turning on DIIS*** + 2 -204.7159868872 -0.000013506447 0.00054991 0.00001722 0.0011433 0.0000 + 3 -204.7156439871 0.000342900100 0.00024041 0.00000777 0.0003922 0.0000 + 4 -204.7160771104 -0.000433123357 0.00008184 0.00000272 0.0001084 0.0000 + 5 -204.7161935931 -0.000116482722 0.00003611 0.00000099 0.0000812 0.0000 + 6 -204.7159712192 0.000222373983 0.00002650 0.00000076 0.0000334 0.0000 + 7 -204.7160582124 -0.000086993271 0.00000970 0.00000042 0.0000119 0.0000 + 8 -204.7160167028 0.000041509609 0.00000846 0.00000036 0.0000087 0.0000 + 9 -204.7160261165 -0.000009413736 0.00000594 0.00000023 0.0000052 0.0000 + 10 -204.7160402848 -0.000014168268 0.00000299 0.00000011 0.0000025 0.0000 + 11 -204.7160254947 0.000014790070 0.00000119 0.00000004 0.0000011 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + +Total Energy : -204.71603126 Eh -5570.60641 eV + Last Energy change ... -5.7615e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.5713e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 2 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.237 sec +Reference energy ... -204.716030869 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.455 sec +AO-integral generation ... 0.166 sec +Half transformation ... 0.091 sec +K-integral sorting ... 5.456 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.026 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.029 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.032 s ( 0.000 ms/b) + 151164 b 0 skpd 0.043 s ( 0.000 ms/b) +: 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.039 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.035 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.028 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.042 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.025 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.381 sec +AO-integral generation ... 0.273 sec +Half transformation ... 0.045 sec +J-integral sorting ... 0.048 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.159 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.254 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090355265 +EMP2(bb)= -0.090355265 +EMP2(ab)= -0.516781801 + +Initial guess performed in 0.135 sec +E(0) ... -204.716030869 +E(MP2) ... -0.697492330 +Initial E(tot) ... -205.413523199 + ... 0.188521395 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.413523199 -0.697492330 -0.000000000 0.022685222 3.07 0.000000579 + *** Turning on DIIS *** + 1 -205.384722394 -0.668691525 0.028800805 0.009371384 3.14 0.057181652 + 2 -205.404219148 -0.688188279 -0.019496754 0.004785179 3.17 0.060135893 + 3 -205.407980383 -0.691949513 -0.003761234 0.002015587 3.19 0.074250690 + 4 -205.409543909 -0.693513040 -0.001563527 0.001703606 3.23 0.080911032 + 5 -205.410095826 -0.694064957 -0.000551917 0.000980432 3.23 0.086516176 + 6 -205.410208000 -0.694177131 -0.000112174 0.000600688 3.34 0.089411671 + 7 -205.410255835 -0.694224965 -0.000047835 0.000261645 4.16 0.090817084 + 8 -205.410269078 -0.694238209 -0.000013243 0.000135160 4.27 0.091373959 + 9 -205.410264699 -0.694233829 0.000004379 0.000039377 3.33 0.091544690 + 10 -205.410270077 -0.694239208 -0.000005379 0.000025834 3.08 0.091602630 + 11 -205.410267020 -0.694236151 0.000003057 0.000020099 3.35 0.091594731 + 12 -205.410268446 -0.694237576 -0.000001426 0.000014839 3.17 0.091608411 + 13 -205.410268182 -0.694237312 0.000000264 0.000009458 3.19 0.091603272 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.716030869 +E(CORR) ... -0.694237312 +E(TOT) ... -205.410268182 +Singles norm **1/2 ... 0.091603272 ( 0.045801636, 0.045801636) +T1 diagnostic ... 0.021591098 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.054814 + 8a-> 13a -1a-> -1a 0.035567 + 8b-> 13b -1b-> -1b 0.035567 + 9a-> 13a 8b-> 13b 0.035459 + 8a-> 13a 9b-> 13b 0.035459 + 10a-> 13a -1a-> -1a 0.034663 + 10b-> 13b -1b-> -1b 0.034663 + 9a-> 13a 9b-> 13b 0.034408 + 10a-> 13a 10b-> 13b 0.034207 + 11a-> 13a 11b-> 13b 0.028016 + 5a-> 13a 5b-> 13b 0.027416 + 9a-> 13a 10b-> 13b 0.026630 + 10a-> 13a 9b-> 13b 0.026630 + 10a-> 13a 8b-> 13b 0.025897 + 8a-> 13a 10b-> 13b 0.025897 + 11a-> 26a 11b-> 26b 0.023087 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034658704 + alpha-alpha-alpha ... -0.000887644 ( 2.6%) + alpha-alpha-beta ... -0.016441708 ( 47.4%) + alpha-beta -beta ... -0.016441708 ( 47.4%) + beta -beta -beta ... -0.000887644 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034658704 + +Final correlation energy ... -0.728896016 +E(CCSD) ... -205.410268182 +E(CCSD(T)) ... -205.444926885 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210700424 sqrt= 1.100318329 +W(HF) = 0.825968159 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 62.827 sec + +Fock Matrix Formation ... 0.237 sec ( 0.4%) +Initial Guess ... 0.135 sec ( 0.2%) +DIIS Solver ... 2.427 sec ( 3.9%) +State Vector Update ... 0.109 sec ( 0.2%) +Sigma-vector construction ... 44.379 sec ( 70.6%) + <0|H|D> ... 0.005 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.029 sec ( 0.1% of sigma) + (0-ext) ... 0.083 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.029 sec ( 0.1% of sigma) + (2-ext) ... 1.044 sec ( 2.4% of sigma) + (4-ext) ... 25.331 sec ( 57.1% of sigma) + ... 1.977 sec ( 4.5% of sigma) + ... 0.004 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.123 sec ( 0.3% of sigma) + Fock-dressing ... 2.303 sec ( 5.2% of sigma) + (ik|jl)-dressing ... 0.088 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.716 sec ( 24.1% of sigma) + Pair energies ... 0.007 sec ( 0.0% of sigma) +Total Time for computing (T) ... 7.481 sec ( 11.9% of ALL) + I/O of integral and amplitudes ... 0.763 sec ( 10.2% of (T)) + External N**7 contributions ... 4.157 sec ( 55.6% of (T)) + Internal N**7 contributions ... 0.330 sec ( 4.4% of (T)) + N**6 triples energy contributions ... 1.679 sec ( 22.4% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.444926885473 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.000056510 -0.007860046 0.005005206 + 2 N : -0.001579489 -0.008805141 -0.003737403 + 3 O : 0.001199787 0.007835196 0.002538882 + 4 H : 0.000323193 0.008829991 -0.003806685 + +Norm of the cartesian gradient ... 0.018511317 +RMS gradient ... 0.005343757 +MAX gradient ... 0.008829991 + +------- +TIMINGS +------- + +Total numerical gradient time ... 399.352 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.444926885 Eh +Current gradient norm .... 0.018511317 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999848 +Lowest eigenvalues of augmented Hessian: + -0.000000048 0.121445518 0.172995320 0.493364734 0.512080043 +Length of the computed step .... 0.000551378 +The final length of the internal step .... 0.000551378 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0002250992 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001251795 RMS(Int)= 0.0002251000 + Iter 1: RMS(Cart)= 0.0000000062 RMS(Int)= 0.0000000105 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000380132 0.0000050000 NO + RMS gradient 0.0000502492 0.0001000000 YES + MAX gradient 0.0000859398 0.0003000000 YES + RMS step 0.0002250992 0.0020000000 YES + MAX step 0.0005246611 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0003 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4607 -0.000084 0.0003 1.4610 + 2. B(O 2,N 1) 1.1699 -0.000086 0.0000 1.1699 + 3. B(H 3,O 0) 0.9691 -0.000020 0.0000 0.9692 + 4. A(N 1,O 0,H 3) 102.08 0.000010 -0.01 102.07 + 5. A(O 0,N 1,O 2) 110.49 -0.000017 -0.00 110.49 + 6. D(O 2,N 1,O 0,H 3) -139.09 0.017233 0.00 -139.09 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.779782 -0.094907 0.166836 + N 0.654914 -0.246753 -0.063336 + O 0.927678 0.054106 -1.160538 + H -0.802809 0.287555 1.057037 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.473574 -0.179349 0.315275 + 1 N 7.0000 0 14.007 1.237608 -0.466296 -0.119688 + 2 O 8.0000 0 15.999 1.753058 0.102245 -2.193098 + 3 H 1.0000 0 1.008 -1.517090 0.543400 1.997511 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.460954570209 0.00000000 0.00000000 + O 2 1 0 1.169943742088 110.48599900 0.00000000 + H 1 2 3 0.969156697727 102.06751914 220.90909109 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.760804031796 0.00000000 0.00000000 + O 2 1 0 2.210873264641 110.48599900 0.00000000 + H 1 2 3 1.831440739559 102.06751914 220.90909109 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2224 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2689 + la=0 lb=0: 547 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 391 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.038640448402 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.0386404484 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.961e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7160011128 0.000000000000 0.00000904 0.00000020 0.0000487 0.7000 + 1 -204.7160011215 -0.000000008756 0.00000679 0.00000016 0.0000385 0.7000 + ***Turning on DIIS*** + 2 -204.7160011288 -0.000000007243 0.00001764 0.00000044 0.0000301 0.0000 + 3 -204.7160115453 -0.000010416544 0.00000683 0.00000018 0.0000079 0.0000 + 4 -204.7159985152 0.000013030149 0.00000254 0.00000006 0.0000022 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71599639 Eh -5570.60547 eV + +Components: +Nuclear Repulsion : 69.03864045 Eh 1878.63691 eV +Electronic Energy : -273.75463684 Eh -7449.24238 eV +One Electron Energy: -417.79149214 Eh -11368.68447 eV +Two Electron Energy: 144.03685530 Eh 3919.44209 eV + +Virial components: +Potential Energy : -408.95684916 Eh -11128.28162 eV +Kinetic Energy : 204.24085277 Eh 5557.67615 eV +Virial Ratio : 2.00232639 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.1212e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.6785e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.8086e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.3996e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.677301 -562.6580 + 1 1.0000 -20.629543 -561.3584 + 2 1.0000 -15.800825 -429.9623 + 3 1.0000 -1.609298 -43.7912 + 4 1.0000 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0.0000 0.801488 21.8096 + 45 0.0000 0.823206 22.4006 + 46 0.0000 0.848305 23.0836 + 47 0.0000 0.860781 23.4231 + 48 0.0000 0.923983 25.1429 + 49 0.0000 0.946424 25.7535 + 50 0.0000 0.961070 26.1521 + 51 0.0000 1.010573 27.4991 + 52 0.0000 1.020936 27.7811 + 53 0.0000 1.031955 28.0809 + 54 0.0000 1.047830 28.5129 + 55 0.0000 1.088153 29.6101 + 56 0.0000 1.152956 31.3735 + 57 0.0000 1.206491 32.8303 + 58 0.0000 1.255017 34.1507 + 59 0.0000 1.310437 35.6588 + 60 0.0000 1.373259 37.3683 + 61 0.0000 1.406174 38.2639 + 62 0.0000 1.461410 39.7670 + 63 0.0000 1.511303 41.1246 + 64 0.0000 1.529622 41.6231 + 65 0.0000 1.544000 42.0144 + 66 0.0000 1.567141 42.6441 + 67 0.0000 1.627363 44.2828 + 68 0.0000 1.668882 45.4126 + 69 0.0000 1.716643 46.7122 + 70 0.0000 1.783679 48.5364 + 71 0.0000 1.796444 48.8837 + 72 0.0000 1.880752 51.1779 + 73 0.0000 1.930242 52.5245 + 74 0.0000 1.960474 53.3472 + 75 0.0000 2.032769 55.3145 + 76 0.0000 2.051929 55.8358 + 77 0.0000 2.102342 57.2076 + 78 0.0000 2.158678 58.7406 + 79 0.0000 2.193074 59.6766 + 80 0.0000 2.280678 62.0604 + 81 0.0000 2.285595 62.1942 + 82 0.0000 2.311561 62.9008 + 83 0.0000 2.375232 64.6333 + 84 0.0000 2.439564 66.3839 + 85 0.0000 2.463413 67.0329 + 86 0.0000 2.483195 67.5712 + 87 0.0000 2.497298 67.9549 + 88 0.0000 2.509400 68.2842 + 89 0.0000 2.532027 68.9000 + 90 0.0000 2.572798 70.0094 + 91 0.0000 2.604885 70.8825 + 92 0.0000 2.659497 72.3686 + 93 0.0000 2.707101 73.6640 + 94 0.0000 2.733940 74.3943 + 95 0.0000 2.788010 75.8656 + 96 0.0000 2.814248 76.5796 + 97 0.0000 2.902064 78.9692 + 98 0.0000 2.956331 80.4459 + 99 0.0000 3.070021 83.5395 + 100 0.0000 3.128314 85.1257 + 101 0.0000 3.171087 86.2897 + 102 0.0000 3.263172 88.7954 + 103 0.0000 3.474761 94.5531 + 104 0.0000 3.741861 101.8212 + 105 0.0000 3.883351 105.6713 + 106 0.0000 4.035525 109.8122 + 107 0.0000 4.158337 113.1541 + 108 0.0000 4.198935 114.2588 + 109 0.0000 4.293371 116.8286 + 110 0.0000 4.371212 118.9467 + 111 0.0000 4.390946 119.4837 + 112 0.0000 4.549922 123.8097 + 113 0.0000 4.629679 125.9800 + 114 0.0000 4.748668 129.2178 + 115 0.0000 4.757830 129.4671 + 116 0.0000 4.788551 130.3031 + 117 0.0000 4.885396 132.9384 + 118 0.0000 4.953860 134.8014 + 119 0.0000 4.992258 135.8462 + 120 0.0000 5.070899 137.9862 + 121 0.0000 5.096735 138.6892 + 122 0.0000 5.177785 140.8947 + 123 0.0000 5.208898 141.7413 + 124 0.0000 5.255265 143.0030 + 125 0.0000 5.328789 145.0037 + 126 0.0000 5.360745 145.8733 + 127 0.0000 5.405681 147.0961 + 128 0.0000 5.548524 150.9830 + 129 0.0000 5.698832 155.0731 + 130 0.0000 5.793096 157.6382 + 131 0.0000 5.992770 163.0716 + 132 0.0000 6.127191 166.7294 + 133 0.0000 6.404413 174.2729 + 134 0.0000 6.495763 176.7587 + 135 0.0000 6.508994 177.1187 + 136 0.0000 6.699500 182.3027 + 137 0.0000 6.702324 182.3795 + 138 0.0000 6.746594 183.5842 + 139 0.0000 6.837549 186.0592 + 140 0.0000 6.895305 187.6308 + 141 0.0000 7.067865 192.3264 + 142 0.0000 7.121730 193.7921 + 143 0.0000 7.159743 194.8265 + 144 0.0000 7.189830 195.6452 + 145 0.0000 7.234312 196.8556 + 146 0.0000 7.268836 197.7951 + 147 0.0000 7.355085 200.1420 + 148 0.0000 7.400658 201.3821 + 149 0.0000 7.443748 202.5547 + 150 0.0000 7.480557 203.5563 + 151 0.0000 7.566662 205.8993 + 152 0.0000 7.619855 207.3468 + 153 0.0000 7.649858 208.1632 + 154 0.0000 7.881961 214.4791 + 155 0.0000 7.896701 214.8802 + 156 0.0000 8.012142 218.0215 + 157 0.0000 8.381404 228.0696 + 158 0.0000 14.083834 383.2406 + 159 0.0000 14.905500 405.5993 + 160 0.0000 16.139683 439.1831 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.357120 0.000000 + 1 N : 0.348811 0.000000 + 2 O : -0.258891 0.000000 + 3 H : 0.267201 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.868872 s : 3.868872 + pz : 1.446756 p : 4.460802 + px : 1.239937 + py : 1.774109 + dz2 : 0.009371 d : 0.022880 + dxz : -0.000489 + dyz : 0.001269 + dx2y2 : 0.007213 + dxy : 0.005516 + f0 : 0.000296 f : 0.004566 + f+1 : 0.000952 + f-1 : 0.000526 + f+2 : 0.000466 + f-2 : -0.000000 + f+3 : 0.001085 + f-3 : 0.001241 + 1 N s : 3.827950 s : 3.827950 + pz : 1.038958 p : 2.655787 + px : 0.834330 + py : 0.782499 + dz2 : 0.032690 d : 0.137237 + dxz : 0.032224 + dyz : 0.025076 + dx2y2 : 0.024928 + dxy : 0.022319 + f0 : 0.005403 f : 0.030215 + f+1 : 0.008423 + f-1 : 0.004326 + f+2 : 0.003246 + f-2 : 0.001277 + f+3 : 0.002533 + f-3 : 0.005008 + 2 O s : 3.879014 s : 3.879014 + pz : 1.204605 p : 4.308430 + px : 1.837780 + py : 1.266046 + dz2 : 0.018586 d : 0.063767 + dxz : 0.015721 + dyz : 0.025159 + dx2y2 : 0.001581 + dxy : 0.002720 + f0 : 0.002429 f : 0.007680 + f+1 : 0.002053 + f-1 : 0.002098 + f+2 : 0.000390 + f-2 : 0.000607 + f+3 : 0.000090 + f-3 : 0.000013 + 3 H s : 0.628959 s : 0.628959 + pz : 0.021514 p : 0.082002 + px : 0.020765 + py : 0.039723 + dz2 : 0.004730 d : 0.021838 + dxz : 0.009653 + dyz : 0.005184 + dx2y2 : 0.000731 + dxy : 0.001539 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.591798 0.000000 + 1 N : -0.254702 0.000000 + 2 O : 0.241866 0.000000 + 3 H : -0.578962 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.122425 s : 3.122425 + pz : 1.317915 p : 3.925149 + px : 1.174980 + py : 1.432254 + dz2 : 0.060371 d : 0.277598 + dxz : 0.064874 + dyz : 0.017533 + dx2y2 : 0.087452 + dxy : 0.047368 + f0 : 0.010359 f : 0.083030 + f+1 : 0.016438 + f-1 : 0.004801 + f+2 : 0.016512 + f-2 : 0.002854 + f+3 : 0.016623 + f-3 : 0.015443 + 1 N s : 3.016031 s : 3.016031 + pz : 1.189746 p : 2.837126 + px : 0.899390 + py : 0.747990 + dz2 : 0.248597 d : 0.951215 + dxz : 0.294157 + dyz : 0.131461 + dx2y2 : 0.151567 + dxy : 0.125434 + f0 : 0.092297 f : 0.450330 + f+1 : 0.122160 + f-1 : 0.063616 + f+2 : 0.055912 + f-2 : 0.023067 + f+3 : 0.038618 + f-3 : 0.054662 + 2 O s : 3.316145 s : 3.316145 + pz : 1.384330 p : 3.995931 + px : 1.502424 + py : 1.109177 + dz2 : 0.129951 d : 0.327826 + dxz : 0.094479 + dyz : 0.069640 + dx2y2 : 0.022821 + dxy : 0.010936 + f0 : 0.038470 f : 0.118232 + f+1 : 0.027925 + f-1 : 0.025998 + f+2 : 0.015684 + f-2 : 0.007772 + f+3 : 0.001258 + f-3 : 0.001125 + 3 H s : 0.623723 s : 0.623723 + pz : 0.249189 p : 0.561563 + px : 0.132963 + py : 0.179411 + dz2 : 0.124845 d : 0.393675 + dxz : 0.103773 + dyz : 0.111070 + dx2y2 : 0.031506 + dxy : 0.022481 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3571 8.0000 -0.3571 1.8901 1.8901 0.0000 + 1 N 6.6512 7.0000 0.3488 2.5516 2.5516 -0.0000 + 2 O 8.2589 8.0000 -0.2589 1.7579 1.7579 0.0000 + 3 H 0.7328 1.0000 0.2672 0.9569 0.9569 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8712 B( 0-O , 3-H ) : 0.9624 B( 1-N , 2-O ) : 1.6937 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.008 sec +Sum of individual times .... 0.839 sec ( 83.2%) + +Fock matrix formation .... 0.680 sec ( 67.5%) +Diagonalization .... 0.079 sec ( 7.8%) +Density matrix formation .... 0.005 sec ( 0.5%) +Population analysis .... 0.018 sec ( 1.8%) +Initial guess .... 0.010 sec ( 1.0%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.5%) +DIIS solution .... 0.046 sec ( 4.6%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.233 sec +Reference energy ... -204.716001153 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.984 sec +AO-integral generation ... 0.151 sec +Half transformation ... 0.083 sec +K-integral sorting ... 5.941 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.024 s ( 0.000 ms/b) +: : 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.031 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.040 s ( 0.000 ms/b) + 159120 b 0 skpd 0.017 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.036 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.036 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.024 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.039 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.027 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.381 sec +AO-integral generation ... 0.260 sec +Half transformation ... 0.042 sec +J-integral sorting ... 0.055 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.164 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.258 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090358772 +EMP2(bb)= -0.090358772 +EMP2(ab)= -0.516805083 + +Initial guess performed in 0.136 sec +E(0) ... -204.716001153 +E(MP2) ... -0.697522627 +Initial E(tot) ... -205.413523780 + ... 0.188550058 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.413523780 -0.697522627 -0.000000000 0.022685021 3.13 0.000001582 + *** Turning on DIIS *** + 1 -205.384708905 -0.668707753 0.028814875 0.009376999 2.89 0.057194897 + 2 -205.404210666 -0.688209513 -0.019501761 0.004784832 3.01 0.060146895 + 3 -205.407972799 -0.691971646 -0.003762133 0.002017061 2.99 0.074265942 + 4 -205.409536915 -0.693535762 -0.001564116 0.001705036 3.04 0.080928547 + 5 -205.410089204 -0.694088051 -0.000552289 0.000981243 3.31 0.086537181 + 6 -205.410201462 -0.694200309 -0.000112258 0.000601267 3.41 0.089435147 + 7 -205.410249356 -0.694248203 -0.000047894 0.000261857 3.17 0.090842525 + 8 -205.410262624 -0.694261471 -0.000013268 0.000135291 3.12 0.091400225 + 9 -205.410258241 -0.694257088 0.000004383 0.000039419 3.09 0.091571226 + 10 -205.410263628 -0.694262475 -0.000005387 0.000025819 2.99 0.091629262 + 11 -205.410260567 -0.694259414 0.000003061 0.000020089 3.00 0.091621347 + 12 -205.410261994 -0.694260841 -0.000001427 0.000014836 2.99 0.091635053 + 13 -205.410261729 -0.694260577 0.000000264 0.000009462 2.94 0.091629903 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.716001153 +E(CORR) ... -0.694260577 +E(TOT) ... -205.410261729 +Singles norm **1/2 ... 0.091629903 ( 0.045814952, 0.045814952) +T1 diagnostic ... 0.021597375 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.054849 + 8b-> 13b -1b-> -1b 0.035565 + 8a-> 13a -1a-> -1a 0.035565 + 8a-> 13a 9b-> 13b 0.035480 + 9a-> 13a 8b-> 13b 0.035480 + 10a-> 13a -1a-> -1a 0.034695 + 10b-> 13b -1b-> -1b 0.034695 + 9a-> 13a 9b-> 13b 0.034415 + 10a-> 13a 10b-> 13b 0.034181 + 11a-> 13a 11b-> 13b 0.028010 + 5a-> 13a 5b-> 13b 0.027429 + 10a-> 13a 9b-> 13b 0.026620 + 9a-> 13a 10b-> 13b 0.026620 + 8a-> 13a 10b-> 13b 0.025894 + 10a-> 13a 8b-> 13b 0.025894 + 11a-> 26a 11b-> 26b 0.023002 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034665175 + alpha-alpha-alpha ... -0.000887727 ( 2.6%) + alpha-alpha-beta ... -0.016444861 ( 47.4%) + alpha-beta -beta ... -0.016444861 ( 47.4%) + beta -beta -beta ... -0.000887727 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034665175 + +Final correlation energy ... -0.728925752 +E(CCSD) ... -205.410261729 +E(CCSD(T)) ... -205.444926905 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210737187 sqrt= 1.100335034 +W(HF) = 0.825943079 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.277879 -0.000000 + 1 N : 0.163307 -0.000000 + 2 O : -0.140011 0.000000 + 3 H : 0.254583 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.846303 s : 3.846303 + pz : 1.427463 p : 4.368402 + px : 1.234630 + py : 1.706309 + dz2 : 0.014654 d : 0.054820 + dxz : 0.007208 + dyz : 0.007914 + dx2y2 : 0.011967 + dxy : 0.013076 + f0 : 0.000967 f : 0.008354 + f+1 : 0.001382 + f-1 : 0.001163 + f+2 : 0.001034 + f-2 : 0.000685 + f+3 : 0.001347 + f-3 : 0.001776 + 1 N s : 3.880802 s : 3.880802 + pz : 1.015723 p : 2.758607 + px : 0.877437 + py : 0.865447 + dz2 : 0.035282 d : 0.167772 + dxz : 0.043693 + dyz : 0.027053 + dx2y2 : 0.030813 + dxy : 0.030931 + f0 : 0.004445 f : 0.029513 + f+1 : 0.008204 + f-1 : 0.003912 + f+2 : 0.003472 + f-2 : 0.001664 + f+3 : 0.002671 + f-3 : 0.005146 + 2 O s : 3.865972 s : 3.865972 + pz : 1.190606 p : 4.178889 + px : 1.753665 + py : 1.234618 + dz2 : 0.020114 d : 0.084980 + dxz : 0.022541 + dyz : 0.025765 + dx2y2 : 0.007819 + dxy : 0.008742 + f0 : 0.002358 f : 0.010169 + f+1 : 0.002491 + f-1 : 0.002074 + f+2 : 0.000912 + f-2 : 0.001096 + f+3 : 0.000660 + f-3 : 0.000577 + 3 H s : 0.639456 s : 0.639456 + pz : 0.017696 p : 0.087199 + px : 0.024225 + py : 0.045277 + dz2 : 0.003416 d : 0.018762 + dxz : 0.008719 + dyz : 0.004019 + dx2y2 : 0.001093 + dxy : 0.001516 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.605235 0.000000 + 1 N : -0.302915 -0.000000 + 2 O : 0.277902 -0.000000 + 3 H : -0.580222 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.128595 s : 3.128595 + pz : 1.303977 p : 3.867616 + px : 1.182674 + py : 1.380965 + dz2 : 0.066767 d : 0.308607 + dxz : 0.070471 + dyz : 0.023918 + dx2y2 : 0.094226 + dxy : 0.053224 + f0 : 0.011223 f : 0.089948 + f+1 : 0.017122 + f-1 : 0.005927 + f+2 : 0.017112 + f-2 : 0.003411 + f+3 : 0.018206 + f-3 : 0.016947 + 1 N s : 3.021100 s : 3.021100 + pz : 1.167855 p : 2.881835 + px : 0.915982 + py : 0.797997 + dz2 : 0.251406 d : 0.960638 + dxz : 0.292687 + dyz : 0.130792 + dx2y2 : 0.158405 + dxy : 0.127348 + f0 : 0.089442 f : 0.439342 + f+1 : 0.119322 + f-1 : 0.063446 + f+2 : 0.053673 + f-2 : 0.022752 + f+3 : 0.039695 + f-3 : 0.051012 + 2 O s : 3.318226 s : 3.318226 + pz : 1.375060 p : 3.919297 + px : 1.448208 + py : 1.096029 + dz2 : 0.135648 d : 0.357833 + dxz : 0.097389 + dyz : 0.078384 + dx2y2 : 0.028543 + dxy : 0.017870 + f0 : 0.040292 f : 0.126741 + f+1 : 0.029008 + f-1 : 0.028257 + f+2 : 0.016170 + f-2 : 0.009422 + f+3 : 0.001916 + f-3 : 0.001676 + 3 H s : 0.624984 s : 0.624984 + pz : 0.253458 p : 0.571923 + px : 0.133674 + py : 0.184792 + dz2 : 0.122228 d : 0.383314 + dxz : 0.100150 + dyz : 0.107122 + dx2y2 : 0.031789 + dxy : 0.022025 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2779 8.0000 -0.2779 2.2526 1.7911 0.4615 + 1 N 6.8367 7.0000 0.1633 2.8338 2.3510 0.4828 + 2 O 8.1400 8.0000 -0.1400 2.1540 1.6562 0.4978 + 3 H 0.7454 1.0000 0.2546 0.9788 0.9069 0.0719 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8007 B( 0-O , 3-H ) : 0.8938 B( 1-N , 2-O ) : 1.5484 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 59.354 sec + +Fock Matrix Formation ... 0.233 sec ( 0.4%) +Initial Guess ... 0.136 sec ( 0.2%) +DIIS Solver ... 2.320 sec ( 3.9%) +State Vector Update ... 0.096 sec ( 0.2%) +Sigma-vector construction ... 40.667 sec ( 68.5%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (0-ext) ... 0.079 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.028 sec ( 0.1% of sigma) + (2-ext) ... 1.002 sec ( 2.5% of sigma) + (4-ext) ... 22.524 sec ( 55.4% of sigma) + ... 1.629 sec ( 4.0% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.116 sec ( 0.3% of sigma) + Fock-dressing ... 2.239 sec ( 5.5% of sigma) + (ik|jl)-dressing ... 0.084 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.248 sec ( 25.2% of sigma) + Pair energies ... 0.007 sec ( 0.0% of sigma) +Total Time for computing (T) ... 7.307 sec ( 12.3% of ALL) + I/O of integral and amplitudes ... 0.805 sec ( 11.0% of (T)) + External N**7 contributions ... 4.139 sec ( 56.6% of (T)) + Internal N**7 contributions ... 0.339 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.779 sec ( 24.3% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.444926904663 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.006.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.006.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.431315, -0.153516 -0.631873) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.95567 -0.13273 -0.55032 +Nuclear contribution : -0.96952 0.34688 1.30207 + ----------------------------------------- +Total Dipole Moment : -0.01385 0.21415 0.75175 + ----------------------------------------- +Magnitude (a.u.) : 0.78178 +Magnitude (Debye) : 1.98714 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.939810 0.410625 0.365710 +Rotational constants in MHz : 88133.294603 12310.236110 10963.706926 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.456375 0.499888 -0.391177 +x,y,z [Debye]: 1.160013 1.270614 -0.994293 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.431315, -0.153516 -0.631873) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.95429 -0.11729 -0.72284 +Nuclear contribution : -0.96952 0.34688 1.30207 + ----------------------------------------- +Total Dipole Moment : -0.01523 0.22959 0.57924 + ----------------------------------------- +Magnitude (a.u.) : 0.62326 +Magnitude (Debye) : 1.58421 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.939810 0.410625 0.365710 +Rotational constants in MHz : 88133.294603 12310.236110 10963.706926 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.352841 0.363997 -0.362584 +x,y,z [Debye]: 0.896852 0.925206 -0.921615 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 7 * + * * + * Dihedral ( 2, 1, 0, 3) : -130.90909091 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0398873197 RMS(Int)= 0.0002887037 + Iter 1: RMS(Cart)= 0.0000806418 RMS(Int)= 0.0000016819 + Iter 2: RMS(Cart)= 0.0000004698 RMS(Int)= 0.0000000098 + Iter 3: RMS(Cart)= 0.0000000027 RMS(Int)= 0.0000000001 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4610 0.000000 + 2. B(O 2,N 1) 1.1721 0.000000 + 3. B(H 3,O 0) 0.9719 0.000000 + 4. A(N 1,O 0,H 3) 102.0251 0.000000 + 5. A(O 0,N 1,O 2) 110.4276 0.000000 + 6. D(O 2,N 1,O 0,H 3) -130.9091 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.781581 -0.126909 0.176681 + N 0.650367 -0.282187 -0.068352 + O 0.923217 0.086784 -1.146856 + H -0.792001 0.322312 1.038527 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.476975 -0.239822 0.333880 + 1 N 7.0000 0 14.007 1.229015 -0.533256 -0.129167 + 2 O 8.0000 0 15.999 1.744627 0.163997 -2.167244 + 3 H 1.0000 0 1.008 -1.496665 0.609081 1.962531 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.460954570209 0.00000000 0.00000000 + O 2 1 0 1.169943742088 110.48599900 0.00000000 + H 1 2 3 0.969156697727 102.06751914 220.90909109 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.760804031796 0.00000000 0.00000000 + O 2 1 0 2.210873264641 110.48599900 0.00000000 + H 1 2 3 1.831440739559 102.06751914 220.90909109 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2225 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2690 + la=0 lb=0: 547 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 392 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.989066099528 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.9890660995 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.945e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7090942702 0.000000000000 0.00158254 0.00005383 0.0199233 0.7000 + 1 -204.7100079245 -0.000913654303 0.00153706 0.00004886 0.0165050 0.7000 + ***Turning on DIIS*** + 2 -204.7107888238 -0.000780899239 0.00425279 0.00013272 0.0134263 0.0000 + 3 -204.7153068892 -0.004518065423 0.00179021 0.00005549 0.0053593 0.0000 + 4 -204.7125003792 0.002806509987 0.00086167 0.00002628 0.0021420 0.0000 + 5 -204.7142184015 -0.001718022261 0.00055501 0.00002122 0.0010893 0.0000 + 6 -204.7136627976 0.000555603894 0.00066705 0.00002443 0.0007489 0.0000 + 7 -204.7131357577 0.000527039830 0.00033762 0.00001168 0.0003732 0.0000 + 8 -204.7138729237 -0.000737165992 0.00017867 0.00000736 0.0002045 0.0000 + 9 -204.7134883651 0.000384558597 0.00015647 0.00000567 0.0001445 0.0000 + 10 -204.7136818516 -0.000193486436 0.00007651 0.00000244 0.0000643 0.0000 + 11 -204.7137708363 -0.000088984692 0.00002525 0.00000076 0.0000317 0.0000 + 12 -204.7136500321 0.000120804206 0.00000897 0.00000027 0.0000099 0.0000 + 13 -204.7136909602 -0.000040928159 0.00000266 0.00000008 0.0000039 0.0000 + 14 -204.7136773141 0.000013646174 0.00000100 0.00000003 0.0000021 0.0000 + 15 -204.7136804698 -0.000003155777 0.00000057 0.00000002 0.0000014 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 16 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71368259 Eh -5570.54250 eV + +Components: +Nuclear Repulsion : 68.98906610 Eh 1877.28793 eV +Electronic Energy : -273.70274869 Eh -7447.83043 eV +One Electron Energy: -417.69874707 Eh -11366.16075 eV +Two Electron Energy: 143.99599838 Eh 3918.33032 eV + +Virial components: +Potential Energy : -408.94753919 Eh -11128.02828 eV +Kinetic Energy : 204.23385661 Eh 5557.48578 eV +Virial Ratio : 2.00234939 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -2.1170e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.8343e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.4262e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.5752e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.678667 -562.6951 + 1 1.0000 -20.628391 -561.3271 + 2 1.0000 -15.800513 -429.9538 + 3 1.0000 -1.608110 -43.7589 + 4 1.0000 -1.387623 -37.7591 + 5 1.0000 -0.950451 -25.8631 + 6 1.0000 -0.775569 -21.1043 + 7 1.0000 -0.728568 -19.8253 + 8 1.0000 -0.693916 -18.8824 + 9 1.0000 -0.610705 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0.800267 21.7764 + 45 0.0000 0.824996 22.4493 + 46 0.0000 0.846580 23.0366 + 47 0.0000 0.861528 23.4434 + 48 0.0000 0.920865 25.0580 + 49 0.0000 0.946350 25.7515 + 50 0.0000 0.959965 26.1220 + 51 0.0000 1.005079 27.3496 + 52 0.0000 1.012608 27.5545 + 53 0.0000 1.024358 27.8742 + 54 0.0000 1.046788 28.4845 + 55 0.0000 1.093415 29.7533 + 56 0.0000 1.148744 31.2589 + 57 0.0000 1.214561 33.0499 + 58 0.0000 1.256376 34.1877 + 59 0.0000 1.306304 35.5463 + 60 0.0000 1.364611 37.1329 + 61 0.0000 1.410762 38.3888 + 62 0.0000 1.443744 39.2863 + 63 0.0000 1.510478 41.1022 + 64 0.0000 1.539159 41.8827 + 65 0.0000 1.550006 42.1778 + 66 0.0000 1.561539 42.4916 + 67 0.0000 1.637000 44.5450 + 68 0.0000 1.667127 45.3648 + 69 0.0000 1.710283 46.5392 + 70 0.0000 1.782102 48.4935 + 71 0.0000 1.798220 48.9321 + 72 0.0000 1.885093 51.2960 + 73 0.0000 1.933072 52.6016 + 74 0.0000 1.960404 53.3453 + 75 0.0000 2.035113 55.3782 + 76 0.0000 2.057237 55.9803 + 77 0.0000 2.098505 57.1032 + 78 0.0000 2.160170 58.7812 + 79 0.0000 2.192265 59.6546 + 80 0.0000 2.274367 61.8887 + 81 0.0000 2.288240 62.2662 + 82 0.0000 2.311059 62.8871 + 83 0.0000 2.375034 64.6280 + 84 0.0000 2.430422 66.1352 + 85 0.0000 2.465404 67.0871 + 86 0.0000 2.478141 67.4336 + 87 0.0000 2.488040 67.7030 + 88 0.0000 2.511917 68.3527 + 89 0.0000 2.537528 69.0496 + 90 0.0000 2.568137 69.8826 + 91 0.0000 2.602564 70.8194 + 92 0.0000 2.666867 72.5691 + 93 0.0000 2.697851 73.4122 + 94 0.0000 2.734549 74.4109 + 95 0.0000 2.805054 76.3294 + 96 0.0000 2.822618 76.8073 + 97 0.0000 2.905253 79.0559 + 98 0.0000 2.965476 80.6947 + 99 0.0000 3.059119 83.2429 + 100 0.0000 3.110275 84.6349 + 101 0.0000 3.166873 86.1750 + 102 0.0000 3.257339 88.6367 + 103 0.0000 3.481641 94.7403 + 104 0.0000 3.734002 101.6073 + 105 0.0000 3.870111 105.3111 + 106 0.0000 4.038529 109.8940 + 107 0.0000 4.155204 113.0689 + 108 0.0000 4.201001 114.3151 + 109 0.0000 4.309108 117.2568 + 110 0.0000 4.360043 118.6428 + 111 0.0000 4.386429 119.3608 + 112 0.0000 4.556222 123.9811 + 113 0.0000 4.622843 125.7940 + 114 0.0000 4.733224 128.7976 + 115 0.0000 4.737900 128.9248 + 116 0.0000 4.786264 130.2409 + 117 0.0000 4.881184 132.8238 + 118 0.0000 4.949422 134.6806 + 119 0.0000 4.983332 135.6034 + 120 0.0000 5.071615 138.0057 + 121 0.0000 5.092304 138.5686 + 122 0.0000 5.170165 140.6873 + 123 0.0000 5.198403 141.4557 + 124 0.0000 5.253232 142.9477 + 125 0.0000 5.328801 145.0040 + 126 0.0000 5.380538 146.4119 + 127 0.0000 5.402786 147.0173 + 128 0.0000 5.548808 150.9907 + 129 0.0000 5.703125 155.1899 + 130 0.0000 5.789725 157.5464 + 131 0.0000 5.987034 162.9155 + 132 0.0000 6.141834 167.1278 + 133 0.0000 6.406855 174.3394 + 134 0.0000 6.495496 176.7514 + 135 0.0000 6.509716 177.1384 + 136 0.0000 6.697829 182.2572 + 137 0.0000 6.706094 182.4821 + 138 0.0000 6.752813 183.7534 + 139 0.0000 6.831307 185.8893 + 140 0.0000 6.882760 187.2894 + 141 0.0000 7.068767 192.3509 + 142 0.0000 7.118655 193.7084 + 143 0.0000 7.143384 194.3814 + 144 0.0000 7.188587 195.6114 + 145 0.0000 7.240769 197.0313 + 146 0.0000 7.271057 197.8555 + 147 0.0000 7.351791 200.0524 + 148 0.0000 7.399604 201.3535 + 149 0.0000 7.450134 202.7284 + 150 0.0000 7.481963 203.5946 + 151 0.0000 7.540838 205.1966 + 152 0.0000 7.618410 207.3075 + 153 0.0000 7.631124 207.6534 + 154 0.0000 7.872550 214.2230 + 155 0.0000 7.897756 214.9089 + 156 0.0000 8.011300 217.9985 + 157 0.0000 8.380882 228.0554 + 158 0.0000 14.070768 382.8851 + 159 0.0000 14.858720 404.3263 + 160 0.0000 16.071229 437.3204 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.678667 -562.6951 + 1 1.0000 -20.628391 -561.3271 + 2 1.0000 -15.800513 -429.9538 + 3 1.0000 -1.608110 -43.7589 + 4 1.0000 -1.387623 -37.7591 + 5 1.0000 -0.950451 -25.8631 + 6 1.0000 -0.775569 -21.1043 + 7 1.0000 -0.728568 -19.8253 + 8 1.0000 -0.693916 -18.8824 + 9 1.0000 -0.610705 -16.6181 + 10 1.0000 -0.530088 -14.4244 + 11 1.0000 -0.460773 -12.5383 + 12 0.0000 0.029254 0.7960 + 13 0.0000 0.073647 2.0040 + 14 0.0000 0.092781 2.5247 + 15 0.0000 0.100078 2.7233 + 16 0.0000 0.118219 3.2169 + 17 0.0000 0.151132 4.1125 + 18 0.0000 0.157351 4.2817 + 19 0.0000 0.172739 4.7005 + 20 0.0000 0.186145 5.0653 + 21 0.0000 0.191507 5.2112 + 22 0.0000 0.203173 5.5286 + 23 0.0000 0.237210 6.4548 + 24 0.0000 0.269666 7.3380 + 25 0.0000 0.286236 7.7889 + 26 0.0000 0.311976 8.4893 + 27 0.0000 0.329247 8.9593 + 28 0.0000 0.345642 9.4054 + 29 0.0000 0.362602 9.8669 + 30 0.0000 0.422600 11.4995 + 31 0.0000 0.514077 13.9887 + 32 0.0000 0.518511 14.1094 + 33 0.0000 0.546358 14.8672 + 34 0.0000 0.571242 15.5443 + 35 0.0000 0.610544 16.6137 + 36 0.0000 0.631321 17.1791 + 37 0.0000 0.647357 17.6155 + 38 0.0000 0.701412 19.0864 + 39 0.0000 0.722762 19.6674 + 40 0.0000 0.735030 20.0012 + 41 0.0000 0.742762 20.2116 + 42 0.0000 0.779168 21.2022 + 43 0.0000 0.793721 21.5982 + 44 0.0000 0.800267 21.7764 + 45 0.0000 0.824996 22.4493 + 46 0.0000 0.846580 23.0366 + 47 0.0000 0.861528 23.4434 + 48 0.0000 0.920865 25.0580 + 49 0.0000 0.946350 25.7515 + 50 0.0000 0.959965 26.1220 + 51 0.0000 1.005079 27.3496 + 52 0.0000 1.012608 27.5545 + 53 0.0000 1.024358 27.8742 + 54 0.0000 1.046788 28.4845 + 55 0.0000 1.093415 29.7533 + 56 0.0000 1.148744 31.2589 + 57 0.0000 1.214561 33.0499 + 58 0.0000 1.256376 34.1877 + 59 0.0000 1.306304 35.5463 + 60 0.0000 1.364611 37.1329 + 61 0.0000 1.410762 38.3888 + 62 0.0000 1.443744 39.2863 + 63 0.0000 1.510478 41.1022 + 64 0.0000 1.539159 41.8827 + 65 0.0000 1.550006 42.1778 + 66 0.0000 1.561539 42.4916 + 67 0.0000 1.637000 44.5450 + 68 0.0000 1.667127 45.3648 + 69 0.0000 1.710283 46.5392 + 70 0.0000 1.782102 48.4935 + 71 0.0000 1.798220 48.9321 + 72 0.0000 1.885093 51.2960 + 73 0.0000 1.933072 52.6016 + 74 0.0000 1.960404 53.3453 + 75 0.0000 2.035113 55.3782 + 76 0.0000 2.057237 55.9803 + 77 0.0000 2.098505 57.1032 + 78 0.0000 2.160170 58.7812 + 79 0.0000 2.192265 59.6546 + 80 0.0000 2.274367 61.8887 + 81 0.0000 2.288240 62.2662 + 82 0.0000 2.311059 62.8871 + 83 0.0000 2.375034 64.6280 + 84 0.0000 2.430422 66.1352 + 85 0.0000 2.465404 67.0871 + 86 0.0000 2.478141 67.4336 + 87 0.0000 2.488040 67.7030 + 88 0.0000 2.511917 68.3527 + 89 0.0000 2.537528 69.0496 + 90 0.0000 2.568137 69.8826 + 91 0.0000 2.602564 70.8194 + 92 0.0000 2.666867 72.5691 + 93 0.0000 2.697851 73.4122 + 94 0.0000 2.734549 74.4109 + 95 0.0000 2.805054 76.3294 + 96 0.0000 2.822618 76.8073 + 97 0.0000 2.905253 79.0559 + 98 0.0000 2.965476 80.6947 + 99 0.0000 3.059119 83.2429 + 100 0.0000 3.110275 84.6349 + 101 0.0000 3.166873 86.1750 + 102 0.0000 3.257339 88.6367 + 103 0.0000 3.481641 94.7403 + 104 0.0000 3.734002 101.6073 + 105 0.0000 3.870111 105.3111 + 106 0.0000 4.038529 109.8940 + 107 0.0000 4.155204 113.0689 + 108 0.0000 4.201001 114.3151 + 109 0.0000 4.309108 117.2568 + 110 0.0000 4.360043 118.6428 + 111 0.0000 4.386429 119.3608 + 112 0.0000 4.556222 123.9811 + 113 0.0000 4.622843 125.7940 + 114 0.0000 4.733224 128.7976 + 115 0.0000 4.737900 128.9248 + 116 0.0000 4.786264 130.2409 + 117 0.0000 4.881184 132.8238 + 118 0.0000 4.949422 134.6806 + 119 0.0000 4.983332 135.6034 + 120 0.0000 5.071615 138.0057 + 121 0.0000 5.092304 138.5686 + 122 0.0000 5.170165 140.6873 + 123 0.0000 5.198403 141.4557 + 124 0.0000 5.253232 142.9477 + 125 0.0000 5.328801 145.0040 + 126 0.0000 5.380538 146.4119 + 127 0.0000 5.402786 147.0173 + 128 0.0000 5.548808 150.9907 + 129 0.0000 5.703125 155.1899 + 130 0.0000 5.789725 157.5464 + 131 0.0000 5.987034 162.9155 + 132 0.0000 6.141834 167.1278 + 133 0.0000 6.406855 174.3394 + 134 0.0000 6.495496 176.7514 + 135 0.0000 6.509716 177.1384 + 136 0.0000 6.697829 182.2572 + 137 0.0000 6.706094 182.4821 + 138 0.0000 6.752813 183.7534 + 139 0.0000 6.831307 185.8893 + 140 0.0000 6.882760 187.2894 + 141 0.0000 7.068767 192.3509 + 142 0.0000 7.118655 193.7084 + 143 0.0000 7.143384 194.3814 + 144 0.0000 7.188587 195.6114 + 145 0.0000 7.240769 197.0313 + 146 0.0000 7.271057 197.8555 + 147 0.0000 7.351791 200.0524 + 148 0.0000 7.399604 201.3535 + 149 0.0000 7.450134 202.7284 + 150 0.0000 7.481963 203.5946 + 151 0.0000 7.540838 205.1966 + 152 0.0000 7.618410 207.3075 + 153 0.0000 7.631124 207.6534 + 154 0.0000 7.872550 214.2230 + 155 0.0000 7.897756 214.9089 + 156 0.0000 8.011300 217.9985 + 157 0.0000 8.380882 228.0554 + 158 0.0000 14.070768 382.8851 + 159 0.0000 14.858720 404.3263 + 160 0.0000 16.071229 437.3204 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.358025 0.000000 + 1 N : 0.347539 0.000000 + 2 O : -0.256181 0.000000 + 3 H : 0.266667 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.868699 s : 3.868699 + pz : 1.475987 p : 4.461517 + px : 1.236994 + py : 1.748536 + dz2 : 0.008436 d : 0.023181 + dxz : 0.000291 + dyz : 0.001537 + dx2y2 : 0.008004 + dxy : 0.004914 + f0 : 0.000295 f : 0.004627 + f+1 : 0.000920 + f-1 : 0.000620 + f+2 : 0.000449 + f-2 : 0.000032 + f+3 : 0.001127 + f-3 : 0.001185 + 1 N s : 3.826096 s : 3.826096 + pz : 1.020147 p : 2.659645 + px : 0.836631 + py : 0.802868 + dz2 : 0.033594 d : 0.136215 + dxz : 0.031235 + dyz : 0.022669 + dx2y2 : 0.025989 + dxy : 0.022729 + f0 : 0.005453 f : 0.030504 + f+1 : 0.008023 + f-1 : 0.003861 + f+2 : 0.003582 + f-2 : 0.001691 + f+3 : 0.002756 + f-3 : 0.005139 + 2 O s : 3.879836 s : 3.879836 + pz : 1.204189 p : 4.305787 + px : 1.836704 + py : 1.264894 + dz2 : 0.020252 d : 0.062969 + dxz : 0.014559 + dyz : 0.022435 + dx2y2 : 0.002392 + dxy : 0.003331 + f0 : 0.002516 f : 0.007590 + f+1 : 0.001851 + f-1 : 0.001782 + f+2 : 0.000537 + f-2 : 0.000696 + f+3 : 0.000141 + f-3 : 0.000067 + 3 H s : 0.629481 s : 0.629481 + pz : 0.023977 p : 0.082480 + px : 0.020555 + py : 0.037947 + dz2 : 0.005769 d : 0.021373 + dxz : 0.008790 + dyz : 0.003487 + dx2y2 : 0.001161 + dxy : 0.002167 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.586451 0.000000 + 1 N : -0.255655 0.000000 + 2 O : 0.242306 0.000000 + 3 H : -0.573103 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.123704 s : 3.123704 + pz : 1.328138 p : 3.929813 + px : 1.174776 + py : 1.426899 + dz2 : 0.055920 d : 0.277025 + dxz : 0.063898 + dyz : 0.021047 + dx2y2 : 0.087194 + dxy : 0.048965 + f0 : 0.008786 f : 0.083007 + f+1 : 0.016857 + f-1 : 0.005382 + f+2 : 0.016610 + f-2 : 0.002902 + f+3 : 0.016344 + f-3 : 0.016127 + 1 N s : 3.017665 s : 3.017665 + pz : 1.164580 p : 2.839378 + px : 0.900642 + py : 0.774156 + dz2 : 0.236506 d : 0.948354 + dxz : 0.288364 + dyz : 0.138381 + dx2y2 : 0.155744 + dxy : 0.129359 + f0 : 0.085912 f : 0.450257 + f+1 : 0.115079 + f-1 : 0.063345 + f+2 : 0.059888 + f-2 : 0.029639 + f+3 : 0.040141 + f-3 : 0.056254 + 2 O s : 3.317539 s : 3.317539 + pz : 1.369565 p : 3.994850 + px : 1.503009 + py : 1.122276 + dz2 : 0.118801 d : 0.327339 + dxz : 0.091869 + dyz : 0.077530 + dx2y2 : 0.026032 + dxy : 0.013108 + f0 : 0.034029 f : 0.117966 + f+1 : 0.025952 + f-1 : 0.027414 + f+2 : 0.017894 + f-2 : 0.009475 + f+3 : 0.001468 + f-3 : 0.001732 + 3 H s : 0.622052 s : 0.622052 + pz : 0.241829 p : 0.559294 + px : 0.132399 + py : 0.185066 + dz2 : 0.121290 d : 0.391757 + dxz : 0.097385 + dyz : 0.106633 + dx2y2 : 0.037124 + dxy : 0.029324 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3580 8.0000 -0.3580 1.8702 1.8702 -0.0000 + 1 N 6.6525 7.0000 0.3475 2.5577 2.5577 -0.0000 + 2 O 8.2562 8.0000 -0.2562 1.7638 1.7638 -0.0000 + 3 H 0.7333 1.0000 0.2667 0.9608 0.9608 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8574 B( 0-O , 3-H ) : 0.9586 B( 1-N , 2-O ) : 1.7038 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.496 sec +Sum of individual times .... 2.311 sec ( 92.6%) + +Fock matrix formation .... 1.918 sec ( 76.8%) +Diagonalization .... 0.190 sec ( 7.6%) +Density matrix formation .... 0.014 sec ( 0.6%) +Population analysis .... 0.019 sec ( 0.7%) +Initial guess .... 0.010 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.2%) +DIIS solution .... 0.160 sec ( 6.4%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.218 sec +Reference energy ... -204.713680545 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.356 sec +AO-integral generation ... 0.151 sec +Half transformation ... 0.084 sec +K-integral sorting ... 5.354 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.024 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.030 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.038 s ( 0.000 ms/b) + 159120 b 0 skpd 0.017 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.030 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.023 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.039 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.023 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.349 sec +AO-integral generation ... 0.242 sec +Half transformation ... 0.042 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.147 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.249 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090243958 +EMP2(bb)= -0.090243958 +EMP2(ab)= -0.516706323 + +Initial guess performed in 0.131 sec +E(0) ... -204.713680545 +E(MP2) ... -0.697194238 +Initial E(tot) ... -205.410874783 + ... 0.188456222 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.410874783 -0.697194238 -0.000000000 0.021672647 2.87 0.000002067 + *** Turning on DIIS *** + 1 -205.382394127 -0.668713582 0.028480656 0.008913914 2.96 0.056571703 + 2 -205.401837511 -0.688156967 -0.019443384 0.004520291 3.01 0.059564919 + 3 -205.405612505 -0.691931960 -0.003774993 0.001870945 2.88 0.073394845 + 4 -205.407164608 -0.693484063 -0.001552103 0.001586811 2.95 0.079854257 + 5 -205.407699564 -0.694019019 -0.000534956 0.000948575 3.09 0.085166626 + 6 -205.407805023 -0.694124478 -0.000105459 0.000594253 2.94 0.087881169 + 7 -205.407850003 -0.694169458 -0.000044979 0.000281059 3.31 0.089206859 + 8 -205.407862365 -0.694181820 -0.000012362 0.000145881 3.06 0.089761174 + 9 -205.407858252 -0.694177707 0.000004113 0.000045487 2.91 0.089939396 + 10 -205.407863662 -0.694183117 -0.000005410 0.000032066 3.12 0.090004809 + 11 -205.407860554 -0.694180009 0.000003108 0.000024558 3.27 0.089997846 + 12 -205.407862146 -0.694181601 -0.000001592 0.000017609 3.03 0.090012888 + 13 -205.407861921 -0.694181376 0.000000225 0.000010794 3.00 0.090007855 + 14 -205.407862287 -0.694181742 -0.000000366 0.000006022 3.42 0.090012864 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.713680545 +E(CORR) ... -0.694181742 +E(TOT) ... -205.407862287 +Singles norm **1/2 ... 0.090012864 ( 0.045006432, 0.045006432) +T1 diagnostic ... 0.021216236 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.051531 + 9a-> 13a 9b-> 13b 0.043415 + 9a-> 13a 8b-> 13b 0.038942 + 8a-> 13a 9b-> 13b 0.038942 + 8b-> 13b -1b-> -1b 0.033511 + 8a-> 13a -1a-> -1a 0.033511 + 10b-> 13b -1b-> -1b 0.031943 + 10a-> 13a -1a-> -1a 0.031943 + 10a-> 13a 10b-> 13b 0.028450 + 11a-> 13a 11b-> 13b 0.028365 + 9a-> 13a 10b-> 13b 0.027913 + 10a-> 13a 9b-> 13b 0.027913 + 5a-> 13a 5b-> 13b 0.027898 + 11a-> 26a 11b-> 26b 0.024113 + 10a-> 13a 8b-> 13b 0.022856 + 8a-> 13a 10b-> 13b 0.022856 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034527152 + alpha-alpha-alpha ... -0.000880926 ( 2.6%) + alpha-alpha-beta ... -0.016382649 ( 47.4%) + alpha-beta -beta ... -0.016382649 ( 47.4%) + beta -beta -beta ... -0.000880926 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034527152 + +Final correlation energy ... -0.728708894 +E(CCSD) ... -205.407862287 +E(CCSD(T)) ... -205.442389439 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210398899 sqrt= 1.100181303 +W(HF) = 0.826173918 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.282664 0.000000 + 1 N : 0.165027 0.000000 + 2 O : -0.136052 -0.000000 + 3 H : 0.253689 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.844887 s : 3.844887 + pz : 1.456000 p : 4.374508 + px : 1.230828 + py : 1.687680 + dz2 : 0.013976 d : 0.054880 + dxz : 0.007818 + dyz : 0.008056 + dx2y2 : 0.012546 + dxy : 0.012484 + f0 : 0.000942 f : 0.008389 + f+1 : 0.001349 + f-1 : 0.001260 + f+2 : 0.001020 + f-2 : 0.000719 + f+3 : 0.001387 + f-3 : 0.001712 + 1 N s : 3.880140 s : 3.880140 + pz : 1.002080 p : 2.758158 + px : 0.879586 + py : 0.876492 + dz2 : 0.035559 d : 0.166902 + dxz : 0.042835 + dyz : 0.025309 + dx2y2 : 0.031984 + dxy : 0.031215 + f0 : 0.004345 f : 0.029774 + f+1 : 0.007866 + f-1 : 0.003668 + f+2 : 0.003733 + f-2 : 0.002002 + f+3 : 0.002891 + f-3 : 0.005270 + 2 O s : 3.866444 s : 3.866444 + pz : 1.189269 p : 4.175366 + px : 1.753001 + py : 1.233096 + dz2 : 0.021385 d : 0.084171 + dxz : 0.021408 + dyz : 0.023547 + dx2y2 : 0.008534 + dxy : 0.009298 + f0 : 0.002399 f : 0.010071 + f+1 : 0.002307 + f-1 : 0.001846 + f+2 : 0.001014 + f-2 : 0.001166 + f+3 : 0.000711 + f-3 : 0.000628 + 3 H s : 0.639626 s : 0.639626 + pz : 0.021114 p : 0.088250 + px : 0.023948 + py : 0.043188 + dz2 : 0.004475 d : 0.018435 + dxz : 0.007976 + dyz : 0.002494 + dx2y2 : 0.001431 + dxy : 0.002059 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.598147 0.000000 + 1 N : -0.302493 0.000000 + 2 O : 0.279764 -0.000000 + 3 H : -0.575418 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.129475 s : 3.129475 + pz : 1.313334 p : 3.874645 + px : 1.181505 + py : 1.379806 + dz2 : 0.062147 d : 0.307832 + dxz : 0.069592 + dyz : 0.027653 + dx2y2 : 0.093864 + dxy : 0.054576 + f0 : 0.009619 f : 0.089901 + f+1 : 0.017491 + f-1 : 0.006532 + f+2 : 0.017319 + f-2 : 0.003502 + f+3 : 0.017956 + f-3 : 0.017483 + 1 N s : 3.022788 s : 3.022788 + pz : 1.146553 p : 2.882160 + px : 0.917321 + py : 0.818286 + dz2 : 0.238088 d : 0.957978 + dxz : 0.287655 + dyz : 0.138628 + dx2y2 : 0.162470 + dxy : 0.131138 + f0 : 0.083103 f : 0.439567 + f+1 : 0.112546 + f-1 : 0.063254 + f+2 : 0.057604 + f-2 : 0.028886 + f+3 : 0.041275 + f-3 : 0.052898 + 2 O s : 3.319771 s : 3.319771 + pz : 1.360253 p : 3.917260 + px : 1.448964 + py : 1.108042 + dz2 : 0.125035 d : 0.356840 + dxz : 0.094846 + dyz : 0.085213 + dx2y2 : 0.031876 + dxy : 0.019869 + f0 : 0.036474 f : 0.126365 + f+1 : 0.026980 + f-1 : 0.028911 + f+2 : 0.018478 + f-2 : 0.011064 + f+3 : 0.002199 + f-3 : 0.002259 + 3 H s : 0.623174 s : 0.623174 + pz : 0.246624 p : 0.570583 + px : 0.133076 + py : 0.190883 + dz2 : 0.118149 d : 0.381661 + dxz : 0.093966 + dyz : 0.103734 + dx2y2 : 0.037276 + dxy : 0.028537 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2827 8.0000 -0.2827 2.2283 1.7689 0.4594 + 1 N 6.8350 7.0000 0.1650 2.8362 2.3510 0.4852 + 2 O 8.1361 8.0000 -0.1361 2.1573 1.6582 0.4991 + 3 H 0.7463 1.0000 0.2537 0.9834 0.9110 0.0724 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7845 B( 0-O , 3-H ) : 0.8921 B( 1-N , 2-O ) : 1.5568 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 61.516 sec + +Fock Matrix Formation ... 0.218 sec ( 0.4%) +Initial Guess ... 0.131 sec ( 0.2%) +DIIS Solver ... 2.418 sec ( 3.9%) +State Vector Update ... 0.104 sec ( 0.2%) +Sigma-vector construction ... 43.280 sec ( 70.4%) + <0|H|D> ... 0.005 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (0-ext) ... 0.078 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.029 sec ( 0.1% of sigma) + (2-ext) ... 1.055 sec ( 2.4% of sigma) + (4-ext) ... 24.354 sec ( 56.3% of sigma) + ... 1.711 sec ( 4.0% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.121 sec ( 0.3% of sigma) + Fock-dressing ... 2.375 sec ( 5.5% of sigma) + (ik|jl)-dressing ... 0.085 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.711 sec ( 24.7% of sigma) + Pair energies ... 0.008 sec ( 0.0% of sigma) +Total Time for computing (T) ... 7.451 sec ( 12.1% of ALL) + I/O of integral and amplitudes ... 0.819 sec ( 11.0% of (T)) + External N**7 contributions ... 3.985 sec ( 53.5% of (T)) + Internal N**7 contributions ... 0.334 sec ( 4.5% of (T)) + N**6 triples energy contributions ... 1.770 sec ( 23.8% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.442389438530 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.002084306 -0.009263801 0.002890141 + 2 N : -0.004353812 -0.009760990 -0.000690724 + 3 O : 0.001688044 0.009020594 0.000176257 + 4 H : 0.000581462 0.010004197 -0.002375673 + +Norm of the cartesian gradient ... 0.020088367 +RMS gradient ... 0.005799012 +MAX gradient ... 0.010004197 + +------- +TIMINGS +------- + +Total numerical gradient time ... 382.376 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 144.03 cm**-1 + 7: 601.96 cm**-1 + 8: 809.84 cm**-1 + 9: 1226.08 cm**-1 + 10: 1694.85 cm**-1 + 11: 3713.10 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 0.048209 0.464726 0.180153 -0.053419 -0.101456 0.001853 + 1 0.045617 0.022072 -0.119386 -0.009742 0.008646 -0.028422 + 2 -0.045531 -0.275741 0.112728 -0.060600 -0.019101 -0.055942 + 3 -0.038909 -0.127312 -0.530743 0.037707 -0.044456 -0.000056 + 4 0.070953 -0.114564 0.123579 0.024812 -0.235052 0.000842 + 5 0.036165 0.206341 -0.071365 0.019215 0.664400 -0.001175 + 6 -0.012101 -0.344936 0.240345 -0.042136 0.118652 -0.000507 + 7 -0.051473 0.049145 -0.006681 -0.010066 0.196994 -0.000846 + 8 -0.013171 0.127668 -0.045033 0.045445 -0.564110 0.000951 + 9 -0.032424 -0.132212 0.700970 0.992676 0.344836 -0.020591 + 10 -0.893004 0.461604 0.283695 -0.030387 0.002318 0.452841 + 11 0.429173 -0.517056 -0.082776 -0.026472 0.024353 0.889138 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 144.03 0.036024 182.05 0.078054 (-0.131372 -0.182334 0.165982) + 7: 601.96 0.019111 96.58 0.009907 (-0.086784 0.015625 0.046170) + 8: 809.84 0.019753 99.82 0.007612 (-0.077952 0.014716 0.036311) + 9: 1226.08 0.024493 123.78 0.006234 ( 0.073278 -0.014014 -0.025842) + 10: 1694.85 0.027191 137.41 0.005007 (-0.052162 -0.007173 0.047267) + 11: 3713.10 0.014086 71.18 0.001184 (-0.014757 0.013488 0.028003) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 144.03 E(vib) ... 0.41 +freq. 601.96 E(vib) ... 0.10 +freq. 809.84 E(vib) ... 0.05 +freq. 1226.08 E(vib) ... 0.01 +freq. 1694.85 E(vib) ... 0.00 +freq. 3713.10 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.44238944 Eh +Zero point energy ... 0.01865789 Eh 11.71 kcal/mol +Thermal vibrational correction ... 0.00090557 Eh 0.57 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.41999344 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00373811 Eh 2.35 kcal/mol +Non-thermal (ZPE) correction 0.01865789 Eh 11.71 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02239600 Eh 14.05 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.41999344 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.41904923 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.892277 0.410483 0.366813 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00161065 Eh 1.01 kcal/mol +Rotational entropy ... 0.00990325 Eh 6.21 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02931622 Eh 18.40 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00990325 Eh 6.21 kcal/mol| +| sn= 2 | S(rot)= 0.00924879 Eh 5.80 kcal/mol| +| sn= 3 | S(rot)= 0.00886596 Eh 5.56 kcal/mol| +| sn= 4 | S(rot)= 0.00859434 Eh 5.39 kcal/mol| +| sn= 5 | S(rot)= 0.00838365 Eh 5.26 kcal/mol| +| sn= 6 | S(rot)= 0.00821150 Eh 5.15 kcal/mol| +| sn= 7 | S(rot)= 0.00806596 Eh 5.06 kcal/mol| +| sn= 8 | S(rot)= 0.00793988 Eh 4.98 kcal/mol| +| sn= 9 | S(rot)= 0.00782867 Eh 4.91 kcal/mol| +| sn=10 | S(rot)= 0.00772919 Eh 4.85 kcal/mol| +| sn=11 | S(rot)= 0.00763920 Eh 4.79 kcal/mol| +| sn=12 | S(rot)= 0.00755705 Eh 4.74 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.41904923 Eh +Total entropy correction ... -0.02931622 Eh -18.40 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44836545 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00597601 Eh -3.75 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.442389440 Eh +Current gradient norm .... 0.020088364 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + -0.000264206 0.120035644 0.169033617 0.490563130 0.506409617 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999759979 +Lowest eigenvalues of augmented Hessian: + -0.000085182 0.118290353 0.168064613 0.490574627 0.506328259 +Length of the computed step .... 0.021913787 +The final length of the internal step .... 0.021913787 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0089462661 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0049838201 RMS(Int)= 0.0089498756 + Iter 1: RMS(Cart)= 0.0000119843 RMS(Int)= 0.0000177416 + Iter 2: RMS(Cart)= 0.0000000387 RMS(Int)= 0.0000000724 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0019705141 0.0001000000 NO + MAX gradient 0.0030708037 0.0003000000 NO + RMS step 0.0089462661 0.0020000000 NO + MAX step 0.0200698694 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0106 Max(Angles) 0.10 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4610 -0.002448 0.0106 1.4717 + 2. B(O 2,N 1) 1.1721 0.003071 -0.0036 1.1684 + 3. B(H 3,O 0) 0.9719 0.002511 -0.0027 0.9692 + 4. A(N 1,O 0,H 3) 102.03 -0.000804 0.10 102.13 + 5. A(O 0,N 1,O 2) 110.43 -0.000961 0.03 110.46 + 6. D(O 2,N 1,O 0,H 3) -130.91 0.017928 0.00 -130.91 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.785788 -0.125467 0.179800 + N 0.655682 -0.282371 -0.071833 + O 0.924976 0.085916 -1.147506 + H -0.794869 0.321921 1.039539 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.484925 -0.237098 0.339773 + 1 N 7.0000 0 14.007 1.239060 -0.533603 -0.135744 + 2 O 8.0000 0 15.999 1.747952 0.162358 -2.168473 + 3 H 1.0000 0 1.008 -1.502085 0.608343 1.964444 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.471657284141 0.00000000 0.00000000 + O 2 1 0 1.168429848202 110.46007412 0.00000000 + H 1 2 3 0.969220780458 102.12600630 229.09090893 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.781029230017 0.00000000 0.00000000 + O 2 1 0 2.208012419801 110.46007412 0.00000000 + H 1 2 3 1.831561838371 102.12600630 229.09090893 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2224 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2688 + la=0 lb=0: 547 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 391 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.874234060206 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.951e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7133642074 0.000000000000 0.00028389 0.00000829 0.0018543 0.7000 + 1 -204.7133830050 -0.000018797620 0.00023348 0.00000702 0.0014951 0.7000 + ***Turning on DIIS*** + 2 -204.7133985627 -0.000015557621 0.00059837 0.00001838 0.0012118 0.0000 + 3 -204.7130443792 0.000354183459 0.00026610 0.00000856 0.0004224 0.0000 + 4 -204.7135025359 -0.000458156715 0.00008604 0.00000307 0.0001095 0.0000 + 5 -204.7136199452 -0.000117409304 0.00004226 0.00000117 0.0000929 0.0000 + 6 -204.7133881336 0.000231811614 0.00002802 0.00000094 0.0000390 0.0000 + 7 -204.7134866210 -0.000098487384 0.00001203 0.00000057 0.0000156 0.0000 + 8 -204.7134321113 0.000054509710 0.00001117 0.00000049 0.0000110 0.0000 + 9 -204.7134487703 -0.000016659011 0.00000719 0.00000028 0.0000061 0.0000 + 10 -204.7134588449 -0.000010074587 0.00000322 0.00000012 0.0000027 0.0000 + 11 -204.7134424477 0.000016397218 0.00000129 0.00000004 0.0000015 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + +Total Energy : -204.71345054 Eh -5570.53619 eV + Last Energy change ... -8.0877e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.7757e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.204 sec +Reference energy ... -204.713449689 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.369 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.381 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.028 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.030 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.045 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.026 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.364 sec +AO-integral generation ... 0.251 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.055 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.153 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.254 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090267403 +EMP2(bb)= -0.090267403 +EMP2(ab)= -0.516934015 + +Initial guess performed in 0.134 sec +E(0) ... -204.713449689 +E(MP2) ... -0.697468821 +Initial E(tot) ... -205.410918510 + ... 0.188768599 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.410918510 -0.697468821 -0.000000000 0.021509931 2.69 0.000000613 + *** Turning on DIIS *** + 1 -205.382262861 -0.668813172 0.028655649 0.009157707 2.71 0.056798537 + 2 -205.401765158 -0.688315468 -0.019502297 0.004454115 2.75 0.059727391 + 3 -205.405547029 -0.692097339 -0.003781871 0.001922206 2.79 0.073623921 + 4 -205.407105275 -0.693655586 -0.001558246 0.001634805 2.79 0.080117124 + 5 -205.407645911 -0.694196222 -0.000540636 0.000971939 2.86 0.085507963 + 6 -205.407753251 -0.694303561 -0.000107339 0.000609048 2.79 0.088294810 + 7 -205.407799896 -0.694350207 -0.000046646 0.000283662 2.85 0.089680950 + 8 -205.407812858 -0.694363168 -0.000012961 0.000148282 2.86 0.090255371 + 9 -205.407808628 -0.694358939 0.000004229 0.000046241 2.78 0.090440165 + 10 -205.407814261 -0.694364572 -0.000005633 0.000031868 2.76 0.090508139 + 11 -205.407811035 -0.694361346 0.000003226 0.000024326 2.81 0.090500843 + 12 -205.407812668 -0.694362978 -0.000001632 0.000017448 2.74 0.090516916 + 13 -205.407812430 -0.694362741 0.000000237 0.000010842 2.82 0.090511439 + 14 -205.407812810 -0.694363120 -0.000000380 0.000006114 2.78 0.090516606 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.713449689 +E(CORR) ... -0.694363120 +E(TOT) ... -205.407812810 +Singles norm **1/2 ... 0.090516606 ( 0.045258303, 0.045258303) +T1 diagnostic ... 0.021334969 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.053420 + 9a-> 13a 9b-> 13b 0.042235 + 8a-> 13a 9b-> 13b 0.039299 + 9a-> 13a 8b-> 13b 0.039299 + 10b-> 13b -1b-> -1b 0.033153 + 10a-> 13a -1a-> -1a 0.033153 + 8b-> 13b -1b-> -1b 0.032998 + 8a-> 13a -1a-> -1a 0.032998 + 5a-> 13a 5b-> 13b 0.028138 + 11a-> 13a 11b-> 13b 0.027927 + 11a-> 25a 11b-> 25b 0.027368 + 10a-> 13a 10b-> 13b 0.026621 + 10a-> 13a 9b-> 13b 0.026464 + 9a-> 13a 10b-> 13b 0.026464 + 11a-> 25a -1a-> -1a 0.024247 + 11b-> 25b -1b-> -1b 0.024247 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034619549 + alpha-alpha-alpha ... -0.000881630 ( 2.5%) + alpha-alpha-beta ... -0.016428144 ( 47.5%) + alpha-beta -beta ... -0.016428144 ( 47.5%) + beta -beta -beta ... -0.000881630 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034619549 + +Final correlation energy ... -0.728982670 +E(CCSD) ... -205.407812810 +E(CCSD(T)) ... -205.442432359 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210863558 sqrt= 1.100392456 +W(HF) = 0.825856880 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 56.775 sec + +Fock Matrix Formation ... 0.204 sec ( 0.4%) +Initial Guess ... 0.134 sec ( 0.2%) +DIIS Solver ... 1.988 sec ( 3.5%) +State Vector Update ... 0.089 sec ( 0.2%) +Sigma-vector construction ... 39.707 sec ( 69.9%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (0-ext) ... 0.073 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (2-ext) ... 0.997 sec ( 2.5% of sigma) + (4-ext) ... 21.875 sec ( 55.1% of sigma) + ... 1.419 sec ( 3.6% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.113 sec ( 0.3% of sigma) + Fock-dressing ... 2.236 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.079 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.041 sec ( 25.3% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.840 sec ( 12.0% of ALL) + I/O of integral and amplitudes ... 0.829 sec ( 12.1% of (T)) + External N**7 contributions ... 3.904 sec ( 57.1% of (T)) + Internal N**7 contributions ... 0.311 sec ( 4.5% of (T)) + N**6 triples energy contributions ... 1.714 sec ( 25.1% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.442432359297 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.000297957 -0.007710154 0.005968812 + 2 N : -0.001794273 -0.008724756 -0.004539139 + 3 O : 0.001341400 0.007767517 0.003102966 + 4 H : 0.000154917 0.008667393 -0.004532639 + +Norm of the cartesian gradient ... 0.019041038 +RMS gradient ... 0.005496674 +MAX gradient ... 0.008724756 + +------- +TIMINGS +------- + +Total numerical gradient time ... 358.526 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.442432359 Eh +Current gradient norm .... 0.019041038 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999792 +Lowest eigenvalues of augmented Hessian: + -0.000000064 0.115700530 0.167300818 0.492940006 0.506454837 +Length of the computed step .... 0.000644490 +The final length of the internal step .... 0.000644490 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0002631120 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001509891 RMS(Int)= 0.0002631134 + Iter 1: RMS(Cart)= 0.0000000062 RMS(Int)= 0.0000000110 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000429196 0.0000050000 NO + RMS gradient 0.0000580201 0.0001000000 YES + MAX gradient 0.0000988436 0.0003000000 YES + RMS step 0.0002631120 0.0020000000 YES + MAX step 0.0006235861 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0003 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4717 -0.000096 0.0003 1.4720 + 2. B(O 2,N 1) 1.1684 -0.000099 0.0000 1.1684 + 3. B(H 3,O 0) 0.9692 -0.000021 0.0000 0.9692 + 4. A(N 1,O 0,H 3) 102.13 0.000004 -0.01 102.12 + 5. A(O 0,N 1,O 2) 110.46 -0.000026 -0.00 110.46 + 6. D(O 2,N 1,O 0,H 3) -130.91 0.017520 0.00 -130.91 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.785980 -0.125473 0.179848 + N 0.655812 -0.282374 -0.071877 + O 0.925069 0.085910 -1.147575 + H -0.794901 0.321936 1.039604 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.485286 -0.237109 0.339864 + 1 N 7.0000 0 14.007 1.239305 -0.533609 -0.135829 + 2 O 8.0000 0 15.999 1.748127 0.162347 -2.168603 + 3 H 1.0000 0 1.008 -1.502144 0.608371 1.964568 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.471987271707 0.00000000 0.00000000 + O 2 1 0 1.168442497798 110.46002068 0.00000000 + H 1 2 3 0.969244735755 102.11715110 229.09090893 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.781652816143 0.00000000 0.00000000 + O 2 1 0 2.208036324073 110.46002068 0.00000000 + H 1 2 3 1.831607107322 102.11715110 229.09090893 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2224 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2688 + la=0 lb=0: 547 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 391 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.866941347365 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.8669413474 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.952e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7134150048 0.000000000000 0.00001049 0.00000023 0.0000561 0.7000 + 1 -204.7134150165 -0.000000011702 0.00000788 0.00000019 0.0000444 0.7000 + ***Turning on DIIS*** + 2 -204.7134150263 -0.000000009755 0.00002026 0.00000050 0.0000346 0.0000 + 3 -204.7134264985 -0.000011472224 0.00000802 0.00000021 0.0000091 0.0000 + 4 -204.7134119722 0.000014526330 0.00000284 0.00000007 0.0000026 0.0000 + 5 -204.7134100257 0.000001946471 0.00000100 0.00000002 0.0000011 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 6 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71341641 Eh -5570.53526 eV + +Components: +Nuclear Repulsion : 68.86694135 Eh 1873.96474 eV +Electronic Energy : -273.58035776 Eh -7444.50001 eV +One Electron Energy: -417.45072356 Eh -11359.41169 eV +Two Electron Energy: 143.87036580 Eh 3914.91168 eV + +Virial components: +Potential Energy : -408.95146319 Eh -11128.13506 eV +Kinetic Energy : 204.23804677 Eh 5557.59980 eV +Virial Ratio : 2.00232753 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -6.3860e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.7326e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.1120e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.8603e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.681099 -562.7613 + 1 1.0000 -20.625815 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0.742284 20.1986 + 42 0.0000 0.779137 21.2014 + 43 0.0000 0.793857 21.6020 + 44 0.0000 0.801294 21.8043 + 45 0.0000 0.824863 22.4457 + 46 0.0000 0.846278 23.0284 + 47 0.0000 0.861228 23.4352 + 48 0.0000 0.921342 25.0710 + 49 0.0000 0.946888 25.7661 + 50 0.0000 0.960907 26.1476 + 51 0.0000 1.005563 27.3628 + 52 0.0000 1.013516 27.5792 + 53 0.0000 1.024636 27.8818 + 54 0.0000 1.046800 28.4849 + 55 0.0000 1.093013 29.7424 + 56 0.0000 1.147690 31.2302 + 57 0.0000 1.213406 33.0185 + 58 0.0000 1.255753 34.1708 + 59 0.0000 1.306085 35.5404 + 60 0.0000 1.365367 37.1535 + 61 0.0000 1.411763 38.4160 + 62 0.0000 1.445455 39.3328 + 63 0.0000 1.510760 41.1099 + 64 0.0000 1.538695 41.8700 + 65 0.0000 1.550162 42.1820 + 66 0.0000 1.560968 42.4761 + 67 0.0000 1.635785 44.5120 + 68 0.0000 1.665682 45.3255 + 69 0.0000 1.709042 46.5054 + 70 0.0000 1.780837 48.4590 + 71 0.0000 1.796542 48.8864 + 72 0.0000 1.883375 51.2492 + 73 0.0000 1.932555 52.5875 + 74 0.0000 1.960946 53.3601 + 75 0.0000 2.031218 55.2722 + 76 0.0000 2.054839 55.9150 + 77 0.0000 2.095985 57.0347 + 78 0.0000 2.159699 58.7684 + 79 0.0000 2.193422 59.6860 + 80 0.0000 2.272210 61.8300 + 81 0.0000 2.286627 62.2223 + 82 0.0000 2.310783 62.8796 + 83 0.0000 2.376523 64.6685 + 84 0.0000 2.429548 66.1114 + 85 0.0000 2.463705 67.0408 + 86 0.0000 2.477715 67.4221 + 87 0.0000 2.486681 67.6660 + 88 0.0000 2.511281 68.3354 + 89 0.0000 2.536152 69.0122 + 90 0.0000 2.568408 69.8899 + 91 0.0000 2.604365 70.8684 + 92 0.0000 2.667251 72.5796 + 93 0.0000 2.697843 73.4120 + 94 0.0000 2.734529 74.4103 + 95 0.0000 2.802538 76.2609 + 96 0.0000 2.819145 76.7128 + 97 0.0000 2.895975 78.8035 + 98 0.0000 2.961581 80.5887 + 99 0.0000 3.053494 83.0898 + 100 0.0000 3.103975 84.4635 + 101 0.0000 3.166694 86.1701 + 102 0.0000 3.259351 88.6915 + 103 0.0000 3.480325 94.7045 + 104 0.0000 3.735577 101.6502 + 105 0.0000 3.866766 105.2201 + 106 0.0000 4.040644 109.9515 + 107 0.0000 4.159947 113.1979 + 108 0.0000 4.203038 114.3705 + 109 0.0000 4.307009 117.1997 + 110 0.0000 4.361999 118.6960 + 111 0.0000 4.388491 119.4169 + 112 0.0000 4.556808 123.9971 + 113 0.0000 4.624663 125.8435 + 114 0.0000 4.730665 128.7280 + 115 0.0000 4.742135 129.0401 + 116 0.0000 4.783500 130.1657 + 117 0.0000 4.883300 132.8813 + 118 0.0000 4.947106 134.6176 + 119 0.0000 4.983741 135.6145 + 120 0.0000 5.070386 137.9722 + 121 0.0000 5.093437 138.5995 + 122 0.0000 5.172599 140.7536 + 123 0.0000 5.201438 141.5383 + 124 0.0000 5.248586 142.8213 + 125 0.0000 5.331645 145.0814 + 126 0.0000 5.381649 146.4421 + 127 0.0000 5.402513 147.0098 + 128 0.0000 5.540913 150.7759 + 129 0.0000 5.705818 155.2632 + 130 0.0000 5.789012 157.5270 + 131 0.0000 5.978459 162.6821 + 132 0.0000 6.140918 167.1029 + 133 0.0000 6.402545 174.2221 + 134 0.0000 6.493323 176.6923 + 135 0.0000 6.507055 177.0660 + 136 0.0000 6.699821 182.3114 + 137 0.0000 6.706207 182.4852 + 138 0.0000 6.754334 183.7948 + 139 0.0000 6.828691 185.8181 + 140 0.0000 6.878570 187.1754 + 141 0.0000 7.066589 192.2917 + 142 0.0000 7.118514 193.7046 + 143 0.0000 7.142466 194.3564 + 144 0.0000 7.193842 195.7544 + 145 0.0000 7.243121 197.0953 + 146 0.0000 7.272421 197.8926 + 147 0.0000 7.357798 200.2159 + 148 0.0000 7.402967 201.4450 + 149 0.0000 7.446958 202.6420 + 150 0.0000 7.476852 203.4555 + 151 0.0000 7.546645 205.3546 + 152 0.0000 7.614310 207.1959 + 153 0.0000 7.627020 207.5418 + 154 0.0000 7.863290 213.9710 + 155 0.0000 7.902518 215.0384 + 156 0.0000 7.993325 217.5094 + 157 0.0000 8.381939 228.0842 + 158 0.0000 14.078188 383.0870 + 159 0.0000 14.860196 404.3665 + 160 0.0000 16.152852 439.5415 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.362501 0.000000 + 1 N : 0.351102 0.000000 + 2 O : -0.251627 0.000000 + 3 H : 0.263026 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.869752 s : 3.869752 + pz : 1.474272 p : 4.465494 + px : 1.240715 + py : 1.750507 + dz2 : 0.008255 d : 0.022723 + dxz : 0.000293 + dyz : 0.001490 + dx2y2 : 0.007947 + dxy : 0.004737 + f0 : 0.000280 f : 0.004533 + f+1 : 0.000906 + f-1 : 0.000610 + f+2 : 0.000434 + f-2 : 0.000033 + f+3 : 0.001118 + f-3 : 0.001151 + 1 N s : 3.826346 s : 3.826346 + pz : 1.018973 p : 2.656562 + px : 0.835295 + py : 0.802294 + dz2 : 0.033350 d : 0.135678 + dxz : 0.031503 + dyz : 0.022589 + dx2y2 : 0.026014 + dxy : 0.022222 + f0 : 0.005396 f : 0.030312 + f+1 : 0.008054 + f-1 : 0.003842 + f+2 : 0.003505 + f-2 : 0.001707 + f+3 : 0.002758 + f-3 : 0.005050 + 2 O s : 3.878746 s : 3.878746 + pz : 1.204195 p : 4.301486 + px : 1.832495 + py : 1.264797 + dz2 : 0.020427 d : 0.063760 + dxz : 0.014907 + dyz : 0.022631 + dx2y2 : 0.002431 + dxy : 0.003364 + f0 : 0.002524 f : 0.007634 + f+1 : 0.001877 + f-1 : 0.001791 + f+2 : 0.000537 + f-2 : 0.000697 + f+3 : 0.000140 + f-3 : 0.000069 + 3 H s : 0.632216 s : 0.632216 + pz : 0.023944 p : 0.083288 + px : 0.020956 + py : 0.038388 + dz2 : 0.005802 d : 0.021469 + dxz : 0.008804 + dyz : 0.003546 + dx2y2 : 0.001165 + dxy : 0.002152 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.587228 0.000000 + 1 N : -0.249134 0.000000 + 2 O : 0.244129 0.000000 + 3 H : -0.582223 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.126116 s : 3.126116 + pz : 1.330322 p : 3.933895 + px : 1.173439 + py : 1.430133 + dz2 : 0.055195 d : 0.271908 + dxz : 0.062125 + dyz : 0.020821 + dx2y2 : 0.086213 + dxy : 0.047554 + f0 : 0.008449 f : 0.080854 + f+1 : 0.016555 + f-1 : 0.005341 + f+2 : 0.015986 + f-2 : 0.002841 + f+3 : 0.016090 + f-3 : 0.015591 + 1 N s : 3.021412 s : 3.021412 + pz : 1.167329 p : 2.838111 + px : 0.895034 + py : 0.775749 + dz2 : 0.235810 d : 0.942883 + dxz : 0.287372 + dyz : 0.138485 + dx2y2 : 0.154603 + dxy : 0.126613 + f0 : 0.085175 f : 0.446728 + f+1 : 0.115234 + f-1 : 0.063301 + f+2 : 0.058738 + f-2 : 0.029658 + f+3 : 0.039622 + f-3 : 0.055000 + 2 O s : 3.316244 s : 3.316244 + pz : 1.371713 p : 3.992467 + px : 1.498562 + py : 1.122193 + dz2 : 0.119437 d : 0.328901 + dxz : 0.092299 + dyz : 0.078122 + dx2y2 : 0.026026 + dxy : 0.013016 + f0 : 0.034188 f : 0.118259 + f+1 : 0.026016 + f-1 : 0.027662 + f+2 : 0.017816 + f-2 : 0.009424 + f+3 : 0.001441 + f-3 : 0.001712 + 3 H s : 0.624759 s : 0.624759 + pz : 0.243578 p : 0.564460 + px : 0.133796 + py : 0.187086 + dz2 : 0.121872 d : 0.393004 + dxz : 0.097822 + dyz : 0.107167 + dx2y2 : 0.036983 + dxy : 0.029160 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3625 8.0000 -0.3625 1.8720 1.8720 0.0000 + 1 N 6.6489 7.0000 0.3511 2.5607 2.5607 0.0000 + 2 O 8.2516 8.0000 -0.2516 1.7708 1.7708 0.0000 + 3 H 0.7370 1.0000 0.2630 0.9640 0.9640 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8542 B( 0-O , 3-H ) : 0.9615 B( 1-N , 2-O ) : 1.7092 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.043 sec +Sum of individual times .... 0.871 sec ( 83.5%) + +Fock matrix formation .... 0.701 sec ( 67.2%) +Diagonalization .... 0.078 sec ( 7.5%) +Density matrix formation .... 0.006 sec ( 0.5%) +Population analysis .... 0.019 sec ( 1.8%) +Initial guess .... 0.010 sec ( 1.0%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.5%) +DIIS solution .... 0.057 sec ( 5.5%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.203 sec +Reference energy ... -204.713415058 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.404 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.080 sec +K-integral sorting ... 5.414 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.028 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.030 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.045 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.353 sec +AO-integral generation ... 0.247 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.156 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.252 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090271540 +EMP2(bb)= -0.090271540 +EMP2(ab)= -0.516961399 + +Initial guess performed in 0.133 sec +E(0) ... -204.713415058 +E(MP2) ... -0.697504480 +Initial E(tot) ... -205.410919538 + ... 0.188802386 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.410919538 -0.697504480 -0.000000000 0.021510359 2.69 0.000000813 + *** Turning on DIIS *** + 1 -205.382247170 -0.668832112 0.028672367 0.009164610 2.68 0.056814111 + 2 -205.401755336 -0.688340278 -0.019508165 0.004453804 2.74 0.059740141 + 3 -205.405538222 -0.692123164 -0.003782886 0.001923592 2.77 0.073641267 + 4 -205.407097143 -0.693682084 -0.001558920 0.001636178 2.78 0.080136809 + 5 -205.407638179 -0.694223121 -0.000541037 0.000972742 2.79 0.085531180 + 6 -205.407745600 -0.694330542 -0.000107421 0.000609645 2.77 0.088320500 + 7 -205.407792307 -0.694377249 -0.000046707 0.000283903 2.84 0.089708716 + 8 -205.407805294 -0.694390236 -0.000012987 0.000148438 2.85 0.090284055 + 9 -205.407801061 -0.694386003 0.000004233 0.000046298 2.77 0.090469164 + 10 -205.407806704 -0.694391646 -0.000005643 0.000031868 2.74 0.090537268 + 11 -205.407803473 -0.694388415 0.000003231 0.000024327 2.73 0.090529954 + 12 -205.407805107 -0.694390049 -0.000001634 0.000017452 2.73 0.090546063 + 13 -205.407804870 -0.694389812 0.000000238 0.000010851 2.74 0.090540571 + 14 -205.407805250 -0.694390192 -0.000000380 0.000006122 2.81 0.090545745 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.713415058 +E(CORR) ... -0.694390192 +E(TOT) ... -205.407805250 +Singles norm **1/2 ... 0.090545745 ( 0.045272873, 0.045272873) +T1 diagnostic ... 0.021341837 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.053462 + 9a-> 13a 9b-> 13b 0.042235 + 8a-> 13a 9b-> 13b 0.039321 + 9a-> 13a 8b-> 13b 0.039321 + 10b-> 13b -1b-> -1b 0.033185 + 10a-> 13a -1a-> -1a 0.033185 + 8a-> 13a -1a-> -1a 0.032996 + 8b-> 13b -1b-> -1b 0.032996 + 5a-> 13a 5b-> 13b 0.028152 + 11a-> 13a 11b-> 13b 0.027918 + 11a-> 25a 11b-> 25b 0.027560 + 10a-> 13a 10b-> 13b 0.026593 + 10a-> 13a 9b-> 13b 0.026446 + 9a-> 13a 10b-> 13b 0.026446 + 11b-> 25b -1b-> -1b 0.024320 + 11a-> 25a -1a-> -1a 0.024320 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034627135 + alpha-alpha-alpha ... -0.000881721 ( 2.5%) + alpha-alpha-beta ... -0.016431846 ( 47.5%) + alpha-beta -beta ... -0.016431846 ( 47.5%) + beta -beta -beta ... -0.000881721 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034627135 + +Final correlation energy ... -0.729017327 +E(CCSD) ... -205.407805250 +E(CCSD(T)) ... -205.442432385 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210905670 sqrt= 1.100411591 +W(HF) = 0.825828159 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.287763 -0.000000 + 1 N : 0.168347 -0.000000 + 2 O : -0.131052 0.000000 + 3 H : 0.250468 -0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.846447 s : 3.846447 + pz : 1.454642 p : 4.378515 + px : 1.234182 + py : 1.689691 + dz2 : 0.013826 d : 0.054492 + dxz : 0.007777 + dyz : 0.008011 + dx2y2 : 0.012562 + dxy : 0.012317 + f0 : 0.000926 f : 0.008308 + f+1 : 0.001338 + f-1 : 0.001251 + f+2 : 0.001006 + f-2 : 0.000720 + f+3 : 0.001380 + f-3 : 0.001687 + 1 N s : 3.879892 s : 3.879892 + pz : 1.000749 p : 2.756023 + px : 0.880722 + py : 0.874552 + dz2 : 0.035269 d : 0.166176 + dxz : 0.042978 + dyz : 0.025219 + dx2y2 : 0.031934 + dxy : 0.030776 + f0 : 0.004293 f : 0.029563 + f+1 : 0.007871 + f-1 : 0.003649 + f+2 : 0.003654 + f-2 : 0.002009 + f+3 : 0.002897 + f-3 : 0.005189 + 2 O s : 3.865528 s : 3.865528 + pz : 1.189444 p : 4.170592 + px : 1.747246 + py : 1.233901 + dz2 : 0.021505 d : 0.084842 + dxz : 0.021753 + dyz : 0.023700 + dx2y2 : 0.008562 + dxy : 0.009322 + f0 : 0.002400 f : 0.010091 + f+1 : 0.002328 + f-1 : 0.001852 + f+2 : 0.001011 + f-2 : 0.001166 + f+3 : 0.000708 + f-3 : 0.000628 + 3 H s : 0.642015 s : 0.642015 + pz : 0.021061 p : 0.089080 + px : 0.024312 + py : 0.043707 + dz2 : 0.004480 d : 0.018436 + dxz : 0.007961 + dyz : 0.002530 + dx2y2 : 0.001426 + dxy : 0.002039 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.598880 0.000000 + 1 N : -0.296381 0.000000 + 2 O : 0.281627 0.000000 + 3 H : -0.584125 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.131769 s : 3.131769 + pz : 1.315608 p : 3.878747 + px : 1.180314 + py : 1.382826 + dz2 : 0.061446 d : 0.302853 + dxz : 0.067863 + dyz : 0.027438 + dx2y2 : 0.092973 + dxy : 0.053133 + f0 : 0.009299 f : 0.087751 + f+1 : 0.017197 + f-1 : 0.006478 + f+2 : 0.016735 + f-2 : 0.003443 + f+3 : 0.017710 + f-3 : 0.016889 + 1 N s : 3.026418 s : 3.026418 + pz : 1.149179 p : 2.881512 + px : 0.913595 + py : 0.818739 + dz2 : 0.237371 d : 0.952302 + dxz : 0.286304 + dyz : 0.138879 + dx2y2 : 0.161092 + dxy : 0.128656 + f0 : 0.082480 f : 0.436149 + f+1 : 0.112544 + f-1 : 0.063229 + f+2 : 0.056513 + f-2 : 0.028874 + f+3 : 0.040778 + f-3 : 0.051732 + 2 O s : 3.318483 s : 3.318483 + pz : 1.362529 p : 3.914889 + px : 1.443666 + py : 1.108694 + dz2 : 0.125610 d : 0.358288 + dxz : 0.095293 + dyz : 0.085764 + dx2y2 : 0.031835 + dxy : 0.019785 + f0 : 0.036617 f : 0.126713 + f+1 : 0.027112 + f-1 : 0.029147 + f+2 : 0.018395 + f-2 : 0.011034 + f+3 : 0.002169 + f-3 : 0.002239 + 3 H s : 0.625669 s : 0.625669 + pz : 0.248423 p : 0.575757 + px : 0.134299 + py : 0.193034 + dz2 : 0.118673 d : 0.382700 + dxz : 0.094300 + dyz : 0.104224 + dx2y2 : 0.037138 + dxy : 0.028365 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2878 8.0000 -0.2878 2.2310 1.7690 0.4620 + 1 N 6.8317 7.0000 0.1683 2.8387 2.3529 0.4857 + 2 O 8.1311 8.0000 -0.1311 2.1644 1.6663 0.4981 + 3 H 0.7495 1.0000 0.2505 0.9862 0.9136 0.0725 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7798 B( 0-O , 3-H ) : 0.8946 B( 1-N , 2-O ) : 1.5629 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 56.924 sec + +Fock Matrix Formation ... 0.203 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 1.814 sec ( 3.2%) +State Vector Update ... 0.089 sec ( 0.2%) +Sigma-vector construction ... 39.529 sec ( 69.4%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (0-ext) ... 0.076 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (2-ext) ... 0.996 sec ( 2.5% of sigma) + (4-ext) ... 21.375 sec ( 54.1% of sigma) + ... 1.438 sec ( 3.6% of sigma) + ... 0.003 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.116 sec ( 0.3% of sigma) + Fock-dressing ... 2.243 sec ( 5.7% of sigma) + (ik|jl)-dressing ... 0.080 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.306 sec ( 26.1% of sigma) + Pair energies ... 0.006 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.846 sec ( 12.0% of ALL) + I/O of integral and amplitudes ... 0.839 sec ( 12.3% of (T)) + External N**7 contributions ... 3.916 sec ( 57.2% of (T)) + Internal N**7 contributions ... 0.315 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.691 sec ( 24.7% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.442432384942 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.007.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.007.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.426477, -0.171381 -0.620685) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.98736 -0.13746 -0.57527 +Nuclear contribution : -0.95974 0.38816 1.28029 + ----------------------------------------- +Total Dipole Moment : 0.02762 0.25070 0.70503 + ----------------------------------------- +Magnitude (a.u.) : 0.74878 +Magnitude (Debye) : 1.90325 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.890655 0.407603 0.364439 +Rotational constants in MHz : 86659.669528 12219.618278 10925.611603 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.385838 0.448339 -0.459126 +x,y,z [Debye]: 0.980723 1.139586 -1.167005 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.426477, -0.171381 -0.620685) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.99613 -0.11776 -0.74725 +Nuclear contribution : -0.95974 0.38816 1.28029 + ----------------------------------------- +Total Dipole Moment : 0.03639 0.27039 0.53304 + ----------------------------------------- +Magnitude (a.u.) : 0.59881 +Magnitude (Debye) : 1.52205 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.890655 0.407603 0.364439 +Rotational constants in MHz : 86659.669528 12219.618278 10925.611603 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.274461 0.319897 -0.425332 +x,y,z [Debye]: 0.697625 0.813114 -1.081107 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 8 * + * * + * Dihedral ( 2, 1, 0, 3) : -122.72727273 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0399452931 RMS(Int)= 0.0003165830 + Iter 1: RMS(Cart)= 0.0000885576 RMS(Int)= 0.0000019762 + Iter 2: RMS(Cart)= 0.0000005528 RMS(Int)= 0.0000000124 + Iter 3: RMS(Cart)= 0.0000000035 RMS(Int)= 0.0000000001 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4721 0.000000 + 2. B(O 2,N 1) 1.1706 0.000000 + 3. B(H 3,O 0) 0.9720 0.000000 + 4. A(N 1,O 0,H 3) 102.0675 0.000000 + 5. A(O 0,N 1,O 2) 110.3968 0.000000 + 6. D(O 2,N 1,O 0,H 3) -122.7273 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.787285 -0.156382 0.191573 + N 0.650956 -0.316864 -0.078255 + O 0.919474 0.117975 -1.131351 + H -0.783144 0.355271 1.018033 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.487753 -0.295519 0.362021 + 1 N 7.0000 0 14.007 1.230129 -0.598786 -0.147880 + 2 O 8.0000 0 15.999 1.737554 0.222940 -2.137944 + 3 H 1.0000 0 1.008 -1.479928 0.671365 1.923803 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.471987271707 0.00000000 0.00000000 + O 2 1 0 1.168442497798 110.46002068 0.00000000 + H 1 2 3 0.969244735755 102.11715110 229.09090893 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.781652816143 0.00000000 0.00000000 + O 2 1 0 2.208036324073 110.46002068 0.00000000 + H 1 2 3 1.831607107322 102.11715110 229.09090893 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2227 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2693 + la=0 lb=0: 548 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 393 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.821237291558 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.8212372916 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.935e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7065480709 0.000000000000 0.00147618 0.00005342 0.0199597 0.7000 + 1 -204.7074648572 -0.000916786376 0.00144691 0.00004863 0.0165388 0.7000 + ***Turning on DIIS*** + 2 -204.7082492747 -0.000784417456 0.00402746 0.00013250 0.0134581 0.0000 + 3 -204.7128279043 -0.004578629570 0.00175732 0.00005645 0.0053455 0.0000 + 4 -204.7099678975 0.002860006793 0.00084849 0.00002736 0.0021369 0.0000 + 5 -204.7117280884 -0.001760190907 0.00059496 0.00002246 0.0011066 0.0000 + 6 -204.7111253308 0.000602757567 0.00075340 0.00002577 0.0007707 0.0000 + 7 -204.7106355316 0.000489799192 0.00033283 0.00001188 0.0003972 0.0000 + 8 -204.7113749775 -0.000739445901 0.00017314 0.00000751 0.0002057 0.0000 + 9 -204.7109789565 0.000396021031 0.00015649 0.00000595 0.0001468 0.0000 + 10 -204.7111859035 -0.000206947043 0.00007639 0.00000255 0.0000648 0.0000 + 11 -204.7112633760 -0.000077472431 0.00002402 0.00000075 0.0000326 0.0000 + 12 -204.7111434506 0.000119925320 0.00000905 0.00000028 0.0000108 0.0000 + 13 -204.7111864504 -0.000042999751 0.00000276 0.00000009 0.0000041 0.0000 + 14 -204.7111725666 0.000013883821 0.00000101 0.00000003 0.0000023 0.0000 + 15 -204.7111757699 -0.000003203343 0.00000066 0.00000002 0.0000015 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 16 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71117826 Eh -5570.47436 eV + +Components: +Nuclear Repulsion : 68.82123729 Eh 1872.72107 eV +Electronic Energy : -273.53241555 Eh -7443.19543 eV +One Electron Energy: -417.36485326 Eh -11357.07504 eV +Two Electron Energy: 143.83243771 Eh 3913.87961 eV + +Virial components: +Potential Energy : -408.94229276 Eh -11127.88552 eV +Kinetic Energy : 204.23111450 Eh 5557.41116 eV +Virial Ratio : 2.00235059 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -2.4908e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.0309e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.5420e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.6321e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.682389 -562.7964 + 1 1.0000 -20.624797 -561.2292 + 2 1.0000 -15.801429 -429.9788 + 3 1.0000 -1.610121 -43.8136 + 4 1.0000 -1.383128 -37.6368 + 5 1.0000 -0.951254 -25.8849 + 6 1.0000 -0.773230 -21.0407 + 7 1.0000 -0.728764 -19.8307 + 8 1.0000 -0.696113 -18.9422 + 9 1.0000 -0.608426 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0.0000 2.418936 65.8226 + 85 0.0000 2.462910 67.0192 + 86 0.0000 2.474253 67.3278 + 87 0.0000 2.480195 67.4895 + 88 0.0000 2.513443 68.3943 + 89 0.0000 2.542886 69.1955 + 90 0.0000 2.562128 69.7190 + 91 0.0000 2.601194 70.7821 + 92 0.0000 2.670781 72.6756 + 93 0.0000 2.699009 73.4438 + 94 0.0000 2.741264 74.5936 + 95 0.0000 2.802342 76.2556 + 96 0.0000 2.844543 77.4040 + 97 0.0000 2.897831 78.8540 + 98 0.0000 2.964439 80.6665 + 99 0.0000 3.039798 82.7171 + 100 0.0000 3.085887 83.9713 + 101 0.0000 3.164805 86.1187 + 102 0.0000 3.249391 88.4204 + 103 0.0000 3.485695 94.8506 + 104 0.0000 3.731537 101.5403 + 105 0.0000 3.851197 104.7964 + 106 0.0000 4.043800 110.0374 + 107 0.0000 4.159205 113.1777 + 108 0.0000 4.198085 114.2357 + 109 0.0000 4.319720 117.5456 + 110 0.0000 4.342052 118.1533 + 111 0.0000 4.390667 119.4761 + 112 0.0000 4.554371 123.9307 + 113 0.0000 4.620233 125.7229 + 114 0.0000 4.714370 128.2845 + 115 0.0000 4.727473 128.6411 + 116 0.0000 4.787166 130.2654 + 117 0.0000 4.881387 132.8293 + 118 0.0000 4.943588 134.5219 + 119 0.0000 4.972091 135.2975 + 120 0.0000 5.069627 137.9516 + 121 0.0000 5.091568 138.5486 + 122 0.0000 5.165042 140.5479 + 123 0.0000 5.196879 141.4143 + 124 0.0000 5.243004 142.6694 + 125 0.0000 5.332433 145.1029 + 126 0.0000 5.383992 146.5059 + 127 0.0000 5.420843 147.5086 + 128 0.0000 5.540855 150.7743 + 129 0.0000 5.711256 155.4112 + 130 0.0000 5.784438 157.4026 + 131 0.0000 5.972233 162.5127 + 132 0.0000 6.155764 167.5069 + 133 0.0000 6.407064 174.3451 + 134 0.0000 6.494067 176.7125 + 135 0.0000 6.506981 177.0640 + 136 0.0000 6.698031 182.2627 + 137 0.0000 6.711383 182.6260 + 138 0.0000 6.761073 183.9782 + 139 0.0000 6.821796 185.6305 + 140 0.0000 6.864301 186.7871 + 141 0.0000 7.067009 192.3031 + 142 0.0000 7.115963 193.6352 + 143 0.0000 7.130130 194.0207 + 144 0.0000 7.193047 195.7328 + 145 0.0000 7.249163 197.2598 + 146 0.0000 7.274626 197.9526 + 147 0.0000 7.352233 200.0644 + 148 0.0000 7.399684 201.3556 + 149 0.0000 7.452915 202.8041 + 150 0.0000 7.472368 203.3335 + 151 0.0000 7.532952 204.9820 + 152 0.0000 7.609689 207.0702 + 153 0.0000 7.615137 207.2184 + 154 0.0000 7.838480 213.2959 + 155 0.0000 7.901301 215.0053 + 156 0.0000 7.995860 217.5784 + 157 0.0000 8.385925 228.1926 + 158 0.0000 14.074104 382.9758 + 159 0.0000 14.824564 403.3969 + 160 0.0000 16.068594 437.2487 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.363494 0.000000 + 1 N : 0.349407 0.000000 + 2 O : -0.248395 0.000000 + 3 H : 0.262482 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.869250 s : 3.869250 + pz : 1.506928 p : 4.466459 + px : 1.238142 + py : 1.721389 + dz2 : 0.007197 d : 0.023200 + dxz : 0.001072 + dyz : 0.001826 + dx2y2 : 0.008876 + dxy : 0.004228 + f0 : 0.000311 f : 0.004585 + f+1 : 0.000878 + f-1 : 0.000659 + f+2 : 0.000432 + f-2 : 0.000060 + f+3 : 0.001155 + f-3 : 0.001091 + 1 N s : 3.824314 s : 3.824314 + pz : 0.997376 p : 2.660354 + px : 0.837202 + py : 0.825776 + dz2 : 0.034374 d : 0.135354 + dxz : 0.030805 + dyz : 0.020221 + dx2y2 : 0.027386 + dxy : 0.022568 + f0 : 0.005405 f : 0.030571 + f+1 : 0.007596 + f-1 : 0.003437 + f+2 : 0.003787 + f-2 : 0.002152 + f+3 : 0.003010 + f-3 : 0.005185 + 2 O s : 3.879120 s : 3.879120 + pz : 1.202713 p : 4.298798 + px : 1.830726 + py : 1.265359 + dz2 : 0.022056 d : 0.062923 + dxz : 0.013591 + dyz : 0.019803 + dx2y2 : 0.003289 + dxy : 0.004184 + f0 : 0.002571 f : 0.007554 + f+1 : 0.001652 + f-1 : 0.001512 + f+2 : 0.000678 + f-2 : 0.000809 + f+3 : 0.000198 + f-3 : 0.000134 + 3 H s : 0.632908 s : 0.632908 + pz : 0.026574 p : 0.083627 + px : 0.020717 + py : 0.036336 + dz2 : 0.006687 d : 0.020983 + dxz : 0.007864 + dyz : 0.002020 + dx2y2 : 0.001618 + dxy : 0.002793 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.582039 0.000000 + 1 N : -0.250017 0.000000 + 2 O : 0.244512 0.000000 + 3 H : -0.576534 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.127457 s : 3.127457 + pz : 1.341553 p : 3.938370 + px : 1.173436 + py : 1.423382 + dz2 : 0.050749 d : 0.271336 + dxz : 0.061263 + dyz : 0.024001 + dx2y2 : 0.086004 + dxy : 0.049319 + f0 : 0.007230 f : 0.080798 + f+1 : 0.016944 + f-1 : 0.005538 + f+2 : 0.016055 + f-2 : 0.002931 + f+3 : 0.015791 + f-3 : 0.016308 + 1 N s : 3.023029 s : 3.023029 + pz : 1.137919 p : 2.840183 + px : 0.895921 + py : 0.806342 + dz2 : 0.222723 d : 0.939963 + dxz : 0.280741 + dyz : 0.145699 + dx2y2 : 0.159666 + dxy : 0.131133 + f0 : 0.078554 f : 0.446843 + f+1 : 0.107390 + f-1 : 0.062735 + f+2 : 0.062922 + f-2 : 0.036908 + f+3 : 0.041525 + f-3 : 0.056810 + 2 O s : 3.317439 s : 3.317439 + pz : 1.353762 p : 3.991577 + px : 1.498722 + py : 1.139093 + dz2 : 0.107362 d : 0.328468 + dxz : 0.089243 + dyz : 0.086316 + dx2y2 : 0.029881 + dxy : 0.015665 + f0 : 0.029684 f : 0.118005 + f+1 : 0.023805 + f-1 : 0.028720 + f+2 : 0.020221 + f-2 : 0.011328 + f+3 : 0.001711 + f-3 : 0.002535 + 3 H s : 0.623110 s : 0.623110 + pz : 0.235593 p : 0.562299 + px : 0.133398 + py : 0.193309 + dz2 : 0.117569 d : 0.391124 + dxz : 0.090829 + dyz : 0.102999 + dx2y2 : 0.043068 + dxy : 0.036660 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3635 8.0000 -0.3635 1.8529 1.8529 -0.0000 + 1 N 6.6506 7.0000 0.3494 2.5682 2.5682 -0.0000 + 2 O 8.2484 8.0000 -0.2484 1.7771 1.7771 -0.0000 + 3 H 0.7375 1.0000 0.2625 0.9681 0.9681 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8417 B( 0-O , 3-H ) : 0.9575 B( 1-N , 2-O ) : 1.7196 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.387 sec +Sum of individual times .... 2.207 sec ( 92.5%) + +Fock matrix formation .... 1.813 sec ( 76.0%) +Diagonalization .... 0.190 sec ( 7.9%) +Density matrix formation .... 0.013 sec ( 0.6%) +Population analysis .... 0.019 sec ( 0.8%) +Initial guess .... 0.010 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.006 sec ( 0.2%) +DIIS solution .... 0.162 sec ( 6.8%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.203 sec +Reference energy ... -204.711176013 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.396 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.400 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.027 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.029 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.017 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.030 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.025 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.351 sec +AO-integral generation ... 0.241 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.055 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.151 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.255 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090155931 +EMP2(bb)= -0.090155931 +EMP2(ab)= -0.516861083 + +Initial guess performed in 0.133 sec +E(0) ... -204.711176013 +E(MP2) ... -0.697172944 +Initial E(tot) ... -205.408348958 + ... 0.188701592 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.408348958 -0.697172944 -0.000000000 0.020586324 2.70 0.000002193 + *** Turning on DIIS *** + 1 -205.380008754 -0.668832741 0.028340203 0.008782092 2.71 0.056155176 + 2 -205.399457531 -0.688281518 -0.019448777 0.004213210 2.74 0.059101511 + 3 -205.403250564 -0.692074550 -0.003793032 0.001692508 2.78 0.072663276 + 4 -205.404795680 -0.693619666 -0.001545116 0.001445690 2.77 0.078911725 + 5 -205.405315760 -0.694139746 -0.000520080 0.000893590 2.85 0.083936024 + 6 -205.405413991 -0.694237978 -0.000098231 0.000574973 2.78 0.086463789 + 7 -205.405456041 -0.694280027 -0.000042050 0.000294018 2.83 0.087705373 + 8 -205.405467473 -0.694291460 -0.000011433 0.000156430 2.84 0.088248492 + 9 -205.405463658 -0.694287644 0.000003816 0.000053176 2.76 0.088436197 + 10 -205.405469120 -0.694293107 -0.000005463 0.000038105 2.72 0.088510560 + 11 -205.405465901 -0.694289888 0.000003219 0.000028422 2.72 0.088505913 + 12 -205.405467755 -0.694291742 -0.000001854 0.000019625 2.72 0.088523002 + 13 -205.405467599 -0.694291586 0.000000156 0.000011829 2.74 0.088518418 + 14 -205.405467941 -0.694291928 -0.000000342 0.000006416 2.81 0.088523889 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.711176013 +E(CORR) ... -0.694291928 +E(TOT) ... -205.405467941 +Singles norm **1/2 ... 0.088523889 ( 0.044261945, 0.044261945) +T1 diagnostic ... 0.020865281 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.050909 + 8a-> 13a 8b-> 13b 0.050806 + 8a-> 13a 9b-> 13b 0.042158 + 9a-> 13a 8b-> 13b 0.042158 + 8a-> 13a -1a-> -1a 0.031160 + 8b-> 13b -1b-> -1b 0.031160 + 10b-> 13b -1b-> -1b 0.029021 + 10a-> 13a -1a-> -1a 0.029021 + 5a-> 13a 5b-> 13b 0.028605 + 11a-> 13a 11b-> 13b 0.028255 + 10a-> 13a 9b-> 13b 0.025658 + 9a-> 13a 10b-> 13b 0.025658 + 11a-> 25a 11b-> 25b 0.025530 + 11a-> 25a -1a-> -1a 0.023226 + 11b-> 25b -1b-> -1b 0.023226 + 11a-> 25a 11b-> 26b 0.022984 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034481388 + alpha-alpha-alpha ... -0.000874415 ( 2.5%) + alpha-alpha-beta ... -0.016366279 ( 47.5%) + alpha-beta -beta ... -0.016366279 ( 47.5%) + beta -beta -beta ... -0.000874415 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034481388 + +Final correlation energy ... -0.728773316 +E(CCSD) ... -205.405467941 +E(CCSD(T)) ... -205.439949330 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210394551 sqrt= 1.100179327 +W(HF) = 0.826176885 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.293137 -0.000000 + 1 N : 0.170204 -0.000000 + 2 O : -0.126671 -0.000000 + 3 H : 0.249605 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.844974 s : 3.844974 + pz : 1.486651 p : 4.385125 + px : 1.230535 + py : 1.667939 + dz2 : 0.013027 d : 0.054704 + dxz : 0.008381 + dyz : 0.008230 + dx2y2 : 0.013272 + dxy : 0.011794 + f0 : 0.000931 f : 0.008334 + f+1 : 0.001309 + f-1 : 0.001303 + f+2 : 0.001005 + f-2 : 0.000749 + f+3 : 0.001418 + f-3 : 0.001619 + 1 N s : 3.878853 s : 3.878853 + pz : 0.984929 p : 2.755246 + px : 0.882303 + py : 0.888013 + dz2 : 0.035677 d : 0.165905 + dxz : 0.042382 + dyz : 0.023488 + dx2y2 : 0.033385 + dxy : 0.030974 + f0 : 0.004199 f : 0.029793 + f+1 : 0.007475 + f-1 : 0.003414 + f+2 : 0.003864 + f-2 : 0.002378 + f+3 : 0.003145 + f-3 : 0.005318 + 2 O s : 3.865797 s : 3.865797 + pz : 1.186928 p : 4.166862 + px : 1.746035 + py : 1.233899 + dz2 : 0.022741 d : 0.084010 + dxz : 0.020475 + dyz : 0.021409 + dx2y2 : 0.009317 + dxy : 0.010069 + f0 : 0.002412 f : 0.010003 + f+1 : 0.002123 + f-1 : 0.001649 + f+2 : 0.001108 + f-2 : 0.001257 + f+3 : 0.000765 + f-3 : 0.000689 + 3 H s : 0.642289 s : 0.642289 + pz : 0.024761 p : 0.090023 + px : 0.024024 + py : 0.041238 + dz2 : 0.005427 d : 0.018083 + dxz : 0.007145 + dyz : 0.001153 + dx2y2 : 0.001766 + dxy : 0.002593 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.591765 0.000000 + 1 N : -0.295786 -0.000000 + 2 O : 0.283572 0.000000 + 3 H : -0.579550 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.132693 s : 3.132693 + pz : 1.325947 p : 3.885805 + px : 1.179142 + py : 1.380717 + dz2 : 0.056833 d : 0.302071 + dxz : 0.067083 + dyz : 0.030814 + dx2y2 : 0.092661 + dxy : 0.054680 + f0 : 0.008072 f : 0.087667 + f+1 : 0.017538 + f-1 : 0.006656 + f+2 : 0.016921 + f-2 : 0.003582 + f+3 : 0.017434 + f-3 : 0.017463 + 1 N s : 3.028095 s : 3.028095 + pz : 1.124096 p : 2.881649 + px : 0.914494 + py : 0.843058 + dz2 : 0.223051 d : 0.949481 + dxz : 0.280443 + dyz : 0.147079 + dx2y2 : 0.166003 + dxy : 0.132904 + f0 : 0.075984 f : 0.436561 + f+1 : 0.105010 + f-1 : 0.062737 + f+2 : 0.060621 + f-2 : 0.035635 + f+3 : 0.042724 + f-3 : 0.053851 + 2 O s : 3.319846 s : 3.319846 + pz : 1.344414 p : 3.912889 + px : 1.444119 + py : 1.124356 + dz2 : 0.113992 d : 0.357346 + dxz : 0.092332 + dyz : 0.093029 + dx2y2 : 0.035778 + dxy : 0.022215 + f0 : 0.032617 f : 0.126347 + f+1 : 0.024837 + f-1 : 0.029627 + f+2 : 0.020846 + f-2 : 0.012860 + f+3 : 0.002521 + f-3 : 0.003039 + 3 H s : 0.623890 s : 0.623890 + pz : 0.241033 p : 0.574560 + px : 0.133834 + py : 0.199692 + dz2 : 0.114021 d : 0.381101 + dxz : 0.087525 + dyz : 0.100958 + dx2y2 : 0.043052 + dxy : 0.035545 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2931 8.0000 -0.2931 2.2064 1.7465 0.4599 + 1 N 6.8298 7.0000 0.1702 2.8420 2.3539 0.4881 + 2 O 8.1267 8.0000 -0.1267 2.1679 1.6686 0.4993 + 3 H 0.7504 1.0000 0.2496 0.9909 0.9179 0.0730 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7641 B( 0-O , 3-H ) : 0.8926 B( 1-N , 2-O ) : 1.5717 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 56.360 sec + +Fock Matrix Formation ... 0.203 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 1.899 sec ( 3.4%) +State Vector Update ... 0.092 sec ( 0.2%) +Sigma-vector construction ... 39.463 sec ( 70.0%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.025 sec ( 0.1% of sigma) + (0-ext) ... 0.072 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (2-ext) ... 0.987 sec ( 2.5% of sigma) + (4-ext) ... 21.677 sec ( 54.9% of sigma) + ... 1.427 sec ( 3.6% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.113 sec ( 0.3% of sigma) + Fock-dressing ... 2.239 sec ( 5.7% of sigma) + (ik|jl)-dressing ... 0.079 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.004 sec ( 25.4% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.696 sec ( 11.9% of ALL) + I/O of integral and amplitudes ... 0.646 sec ( 9.7% of (T)) + External N**7 contributions ... 3.875 sec ( 57.9% of (T)) + Internal N**7 contributions ... 0.306 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.544 sec ( 23.1% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.439949329713 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.002191067 -0.008627376 0.003331874 + 2 N : -0.004261366 -0.009186490 -0.001111335 + 3 O : 0.001608016 0.008515546 0.000595891 + 4 H : 0.000462284 0.009298321 -0.002816430 + +Norm of the cartesian gradient ... 0.019083494 +RMS gradient ... 0.005508930 +MAX gradient ... 0.009298321 + +------- +TIMINGS +------- + +Total numerical gradient time ... 357.348 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: -248.63 cm**-1 ***imaginary mode*** + 7: 589.41 cm**-1 + 8: 802.44 cm**-1 + 9: 1196.23 cm**-1 + 10: 1696.23 cm**-1 + 11: 3713.77 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 0.037441 -0.501400 -0.179799 0.054088 -0.097985 0.000940 + 1 0.043865 -0.034844 0.139811 0.013116 0.009854 -0.032445 + 2 -0.048413 0.289314 -0.132030 0.054464 -0.011303 -0.053703 + 3 -0.029853 0.167772 0.571226 -0.032196 -0.048102 -0.000041 + 4 0.069430 0.117826 -0.157969 -0.026190 -0.285952 0.000754 + 5 0.039144 -0.210229 0.072963 -0.023486 0.662856 -0.001019 + 6 -0.010410 0.350554 -0.278630 0.036674 0.123634 -0.000515 + 7 -0.050576 -0.043137 0.012270 0.009107 0.239729 -0.000831 + 8 -0.017187 -0.138001 0.062883 -0.036951 -0.570228 0.000837 + 9 -0.014206 0.062917 -0.661475 -0.993178 0.261314 -0.006172 + 10 -0.858282 -0.399569 -0.218714 0.011199 0.012144 0.517692 + 11 0.497268 0.519661 0.083621 0.048379 0.019138 0.853239 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 7: 589.41 0.021047 106.36 0.011143 ( 0.092135 -0.011271 -0.050273) + 8: 802.44 0.019025 96.14 0.007399 ( 0.077717 -0.012278 -0.034756) + 9: 1196.23 0.022202 112.20 0.005792 (-0.070265 0.014607 0.025325) + 10: 1696.23 0.028745 145.26 0.005288 (-0.054121 -0.008597 0.047806) + 11: 3713.77 0.013646 68.96 0.001147 (-0.014459 0.014641 0.026892) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 7 +The total number of vibrations considered is 5 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 589.41 E(vib) ... 0.10 +freq. 802.44 E(vib) ... 0.05 +freq. 1196.23 E(vib) ... 0.01 +freq. 1696.23 E(vib) ... 0.00 +freq. 3713.77 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.43994933 Eh +Zero point energy ... 0.01822095 Eh 11.43 kcal/mol +Thermal vibrational correction ... 0.00026278 Eh 0.16 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.41863306 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00309532 Eh 1.94 kcal/mol +Non-thermal (ZPE) correction 0.01822095 Eh 11.43 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02131627 Eh 13.38 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.41863306 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.41768885 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.841799 0.407644 0.365609 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00034275 Eh 0.22 kcal/mol +Rotational entropy ... 0.00991639 Eh 6.22 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02806146 Eh 17.61 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00991639 Eh 6.22 kcal/mol| +| sn= 2 | S(rot)= 0.00926193 Eh 5.81 kcal/mol| +| sn= 3 | S(rot)= 0.00887910 Eh 5.57 kcal/mol| +| sn= 4 | S(rot)= 0.00860748 Eh 5.40 kcal/mol| +| sn= 5 | S(rot)= 0.00839679 Eh 5.27 kcal/mol| +| sn= 6 | S(rot)= 0.00822465 Eh 5.16 kcal/mol| +| sn= 7 | S(rot)= 0.00807910 Eh 5.07 kcal/mol| +| sn= 8 | S(rot)= 0.00795302 Eh 4.99 kcal/mol| +| sn= 9 | S(rot)= 0.00784181 Eh 4.92 kcal/mol| +| sn=10 | S(rot)= 0.00774233 Eh 4.86 kcal/mol| +| sn=11 | S(rot)= 0.00765234 Eh 4.80 kcal/mol| +| sn=12 | S(rot)= 0.00757019 Eh 4.75 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.41768885 Eh +Total entropy correction ... -0.02806146 Eh -17.61 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44575031 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00580098 Eh -3.64 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.439949331 Eh +Current gradient norm .... 0.019083496 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + -0.009597023 0.113835050 0.164505261 0.488990101 0.501298713 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999750048 +Lowest eigenvalues of augmented Hessian: + -0.000086347 0.112353333 0.163655703 0.489008335 0.501196367 +Length of the computed step .... 0.022362741 +The final length of the internal step .... 0.022362741 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0091295508 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0053102258 RMS(Int)= 0.0091338781 + Iter 1: RMS(Cart)= 0.0000120243 RMS(Int)= 0.0000178513 + Iter 2: RMS(Cart)= 0.0000000386 RMS(Int)= 0.0000000729 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0019740074 0.0001000000 NO + MAX gradient 0.0029964897 0.0003000000 NO + RMS step 0.0091295508 0.0020000000 NO + MAX step 0.0205108645 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0109 Max(Angles) 0.13 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4721 -0.002425 0.0109 1.4830 + 2. B(O 2,N 1) 1.1706 0.002996 -0.0036 1.1669 + 3. B(H 3,O 0) 0.9720 0.002502 -0.0027 0.9693 + 4. A(N 1,O 0,H 3) 102.07 -0.000896 0.13 102.20 + 5. A(O 0,N 1,O 2) 110.40 -0.001208 0.06 110.45 + 6. D(O 2,N 1,O 0,H 3) -122.73 0.016863 0.00 -122.73 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.791510 -0.154773 0.194922 + N 0.656302 -0.316952 -0.082048 + O 0.921681 0.116904 -1.132326 + H -0.786472 0.354821 1.019452 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.495736 -0.292479 0.368349 + 1 N 7.0000 0 14.007 1.240232 -0.598952 -0.155049 + 2 O 8.0000 0 15.999 1.741724 0.220917 -2.139785 + 3 H 1.0000 0 1.008 -1.486217 0.670514 1.926485 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.482961096915 0.00000000 0.00000000 + O 2 1 0 1.166935772609 110.45440791 0.00000000 + H 1 2 3 0.969309808586 102.19810976 237.27272733 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.802390340430 0.00000000 0.00000000 + O 2 1 0 2.205189026107 110.45440791 0.00000000 + H 1 2 3 1.831730077152 102.19810976 237.27272733 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.1 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.1 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2225 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2690 + la=0 lb=0: 547 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 392 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.700161610876 Eh + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.942e-04 +Time for diagonalization ... 0.006 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.004 sec +Total time needed ... 0.010 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7108291822 0.000000000000 0.00028253 0.00000822 0.0018354 0.7000 + 1 -204.7108479191 -0.000018736874 0.00023236 0.00000699 0.0014710 0.7000 + ***Turning on DIIS*** + 2 -204.7108634605 -0.000015541419 0.00059566 0.00001836 0.0011953 0.0000 + 3 -204.7104901421 0.000373318383 0.00028114 0.00000880 0.0004244 0.0000 + 4 -204.7109754011 -0.000485259017 0.00008326 0.00000328 0.0001169 0.0000 + 5 -204.7111043439 -0.000128942779 0.00004683 0.00000131 0.0001011 0.0000 + 6 -204.7108482981 0.000256045826 0.00002965 0.00000111 0.0000444 0.0000 + 7 -204.7109609662 -0.000112668128 0.00001586 0.00000069 0.0000185 0.0000 + 8 -204.7108959354 0.000065030824 0.00001372 0.00000056 0.0000126 0.0000 + 9 -204.7109138174 -0.000017882054 0.00000776 0.00000031 0.0000067 0.0000 + 10 -204.7109246909 -0.000010873483 0.00000345 0.00000013 0.0000031 0.0000 + 11 -204.7109067009 0.000017990078 0.00000136 0.00000005 0.0000017 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + +Total Energy : -204.71091608 Eh -5570.46722 eV + Last Energy change ... -9.3751e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.5893e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 5 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.609 sec +Reference energy ... -204.710915082 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 10.840 sec +AO-integral generation ... 0.367 sec +Half transformation ... 0.179 sec +K-integral sorting ... 8.202 sec + +: ------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.069 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.066 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.078 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.112 s ( 0.001 ms/b) + 159120 b 0 skpd 0.048 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.101 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.079 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.067 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.115 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.062 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.924 sec +AO-integral generation ... 0.702 sec +Half transformation ... 0.103 sec +J-integral sorting ... 0.089 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.252 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.402 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090186588 +EMP2(bb)= -0.090186588 +EMP2(ab)= -0.517120482 + +Initial guess performed in 0.198 sec +E(0) ... -204.710915082 +E(MP2) ... -0.697493657 +Initial E(tot) ... -205.408408739 + ... 0.189052829 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.408408739 -0.697493657 -0.000000000 0.020487844 6.42 0.000000667 + *** Turning on DIIS *** + 1 -205.379865093 -0.668950011 0.028543646 0.009065404 6.34 0.056396954 + 2 -205.399379071 -0.688463989 -0.019513977 0.004161901 6.64 0.059272347 + 3 -205.403178743 -0.692263661 -0.003799673 0.001726927 6.21 0.072894901 + 4 -205.404730327 -0.693815245 -0.001551584 0.001479818 5.35 0.079171757 + 5 -205.405255285 -0.694340203 -0.000524958 0.000909867 5.63 0.084258872 + 6 -205.405354851 -0.694439769 -0.000099566 0.000585962 5.49 0.086844714 + 7 -205.405398272 -0.694483190 -0.000043421 0.000295728 6.47 0.088137488 + 8 -205.405410187 -0.694495105 -0.000011915 0.000158587 6.70 0.088697924 + 9 -205.405406245 -0.694491163 0.000003942 0.000054026 8.01 0.088890880 + 10 -205.405411932 -0.694496850 -0.000005687 0.000037986 6.07 0.088968092 + 11 -205.405408600 -0.694493518 0.000003332 0.000028241 6.21 0.088962997 + 12 -205.405410485 -0.694495403 -0.000001885 0.000019469 6.82 0.088981185 + 13 -205.405410322 -0.694495240 0.000000163 0.000011884 6.21 0.088976069 + 14 -205.405410674 -0.694495592 -0.000000352 0.000006527 6.33 0.088981626 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.710915082 +E(CORR) ... -0.694495592 +E(TOT) ... -205.405410674 +Singles norm **1/2 ... 0.088981626 ( 0.044490813, 0.044490813) +T1 diagnostic ... 0.020973170 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.052927 + 9a-> 13a 9b-> 13b 0.049130 + 9a-> 13a 8b-> 13b 0.042420 + 8a-> 13a 9b-> 13b 0.042420 + 8b-> 13b -1b-> -1b 0.030756 + 8a-> 13a -1a-> -1a 0.030756 + 11a-> 25a 11b-> 25b 0.030147 + 10a-> 13a -1a-> -1a 0.029914 + 10b-> 13b -1b-> -1b 0.029914 + 5a-> 13a 5b-> 13b 0.028833 + 11a-> 13a 11b-> 13b 0.027787 + 11b-> 25b -1b-> -1b 0.024504 + 11a-> 25a -1a-> -1a 0.024504 + 10a-> 13a 9b-> 13b 0.024118 + 9a-> 13a 10b-> 13b 0.024118 + 11a-> 26a 11b-> 25b 0.022834 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034582140 + alpha-alpha-alpha ... -0.000875103 ( 2.5%) + alpha-alpha-beta ... -0.016415968 ( 47.5%) + alpha-beta -beta ... -0.016415968 ( 47.5%) + beta -beta -beta ... -0.000875103 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034582140 + +Final correlation energy ... -0.729077733 +E(CCSD) ... -205.405410674 +E(CCSD(T)) ... -205.439992815 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210858345 sqrt= 1.100390088 +W(HF) = 0.825860435 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 126.216 sec + +Fock Matrix Formation ... 0.609 sec ( 0.5%) +Initial Guess ... 0.198 sec ( 0.2%) +DIIS Solver ... 6.055 sec ( 4.8%) +State Vector Update ... 0.261 sec ( 0.2%) +Sigma-vector construction ... 88.579 sec ( 70.2%) + <0|H|D> ... 0.008 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.051 sec ( 0.1% of sigma) + (0-ext) ... 0.159 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.058 sec ( 0.1% of sigma) + (2-ext) ... 2.064 sec ( 2.3% of sigma) + (4-ext) ... 50.442 sec ( 56.9% of sigma) + ... 4.583 sec ( 5.2% of sigma) + ... 0.007 sec ( 0.0% of sigma) + (1-ext) ... 0.025 sec ( 0.0% of sigma) + (1-ext) ... 0.291 sec ( 0.3% of sigma) + Fock-dressing ... 6.051 sec ( 6.8% of sigma) + (ik|jl)-dressing ... 0.204 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 20.176 sec ( 22.8% of sigma) + Pair energies ... 0.035 sec ( 0.0% of sigma) +Total Time for computing (T) ... 16.230 sec ( 12.9% of ALL) + I/O of integral and amplitudes ... 2.266 sec ( 14.0% of (T)) + External N**7 contributions ... 8.771 sec ( 54.0% of (T)) + Internal N**7 contributions ... 0.855 sec ( 5.3% of (T)) + N**6 triples energy contributions ... 3.119 sec ( 19.2% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.439992814685 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.000534199 -0.006939442 0.006395376 + 2 N : -0.001878817 -0.007947780 -0.004936029 + 3 O : 0.001390250 0.007077522 0.003392049 + 4 H : -0.000045633 0.007809700 -0.004851396 + +Norm of the cartesian gradient ... 0.018123555 +RMS gradient ... 0.005231820 +MAX gradient ... 0.007947780 + +------- +TIMINGS +------- + +Total numerical gradient time ... 931.970 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.439992815 Eh +Current gradient norm .... 0.018123555 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999804 +Lowest eigenvalues of augmented Hessian: + -0.000000062 0.110170603 0.162695890 0.490201162 0.502062993 +Length of the computed step .... 0.000625651 +The final length of the internal step .... 0.000625651 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0002554211 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001558388 RMS(Int)= 0.0002554226 + Iter 1: RMS(Cart)= 0.0000000039 RMS(Int)= 0.0000000073 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000434838 0.0000050000 NO + RMS gradient 0.0000598403 0.0001000000 YES + MAX gradient 0.0001050128 0.0003000000 YES + RMS step 0.0002554211 0.0020000000 YES + MAX step 0.0006147136 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0003 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4830 -0.000094 0.0003 1.4833 + 2. B(O 2,N 1) 1.1669 -0.000105 0.0000 1.1670 + 3. B(H 3,O 0) 0.9693 -0.000021 0.0000 0.9693 + 4. A(N 1,O 0,H 3) 102.20 -0.000005 -0.01 102.19 + 5. A(O 0,N 1,O 2) 110.45 -0.000034 0.00 110.45 + 6. D(O 2,N 1,O 0,H 3) -122.73 0.016463 0.00 -122.73 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.791686 -0.154775 0.194982 + N 0.656436 -0.316960 -0.082102 + O 0.921781 0.116897 -1.132407 + H -0.786529 0.354837 1.019527 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.496070 -0.292482 0.368462 + 1 N 7.0000 0 14.007 1.240485 -0.598967 -0.155151 + 2 O 8.0000 0 15.999 1.741913 0.220904 -2.139938 + 3 H 1.0000 0 1.008 -1.486325 0.670545 1.926628 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.483286389363 0.00000000 0.00000000 + O 2 1 0 1.166952578646 110.45499491 0.00000000 + H 1 2 3 0.969333188720 102.19223835 237.27272733 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.803005054068 0.00000000 0.00000000 + O 2 1 0 2.205220784914 110.45499491 0.00000000 + H 1 2 3 1.831774259201 102.19223835 237.27272733 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2225 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2690 + la=0 lb=0: 547 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 392 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.692817751160 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.6928177512 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.943e-04 +Time for diagonalization ... 0.005 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.004 sec +Total time needed ... 0.011 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7108803715 0.000000000000 0.00001031 0.00000022 0.0000540 0.7000 + 1 -204.7108803822 -0.000000010648 0.00000784 0.00000018 0.0000426 0.7000 + ***Turning on DIIS*** + 2 -204.7108803911 -0.000000008944 0.00001922 0.00000048 0.0000331 0.0000 + 3 -204.7108922941 -0.000011903027 0.00000801 0.00000020 0.0000086 0.0000 + 4 -204.7108773654 0.000014928677 0.00000263 0.00000006 0.0000025 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71087518 Eh -5570.46611 eV + +Components: +Nuclear Repulsion : 68.69281775 Eh 1869.22660 eV +Electronic Energy : -273.40369293 Eh -7439.69271 eV +One Electron Energy: -417.10383869 Eh -11349.97247 eV +Two Electron Energy: 143.70014575 Eh 3910.27976 eV + +Virial components: +Potential Energy : -408.94594188 Eh -11127.98481 eV +Kinetic Energy : 204.23506670 Eh 5557.51870 eV +Virial Ratio : 2.00232971 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.1831e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.0483e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.1651e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.2866e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.684818 -562.8625 + 1 1.0000 -20.622250 -561.1599 + 2 1.0000 -15.802656 -430.0121 + 3 1.0000 -1.613407 -43.9030 + 4 1.0000 -1.379980 -37.5512 + 5 1.0000 -0.951486 -25.8913 + 6 1.0000 -0.773017 -21.0349 + 7 1.0000 -0.729505 -19.8508 + 8 1.0000 -0.696071 -18.9411 + 9 1.0000 -0.610374 -16.6091 + 10 1.0000 -0.529261 -14.4019 + 11 1.0000 -0.458950 -12.4887 + 12 0.0000 0.029977 0.8157 + 13 0.0000 0.071637 1.9493 + 14 0.0000 0.092051 2.5048 + 15 0.0000 0.100572 2.7367 + 16 0.0000 0.116693 3.1754 + 17 0.0000 0.153005 4.1635 + 18 0.0000 0.157200 4.2776 + 19 0.0000 0.172882 4.7043 + 20 0.0000 0.185503 5.0478 + 21 0.0000 0.190457 5.1826 + 22 0.0000 0.202288 5.5045 + 23 0.0000 0.236918 6.4469 + 24 0.0000 0.271716 7.3938 + 25 0.0000 0.282127 7.6771 + 26 0.0000 0.308689 8.3998 + 27 0.0000 0.328839 8.9482 + 28 0.0000 0.340342 9.2612 + 29 0.0000 0.359203 9.7744 + 30 0.0000 0.424297 11.5457 + 31 0.0000 0.510986 13.9046 + 32 0.0000 0.520160 14.1543 + 33 0.0000 0.544677 14.8214 + 34 0.0000 0.571722 15.5574 + 35 0.0000 0.608248 16.5513 + 36 0.0000 0.631480 17.1834 + 37 0.0000 0.649810 17.6822 + 38 0.0000 0.698894 19.0179 + 39 0.0000 0.723174 19.6786 + 40 0.0000 0.738900 20.1065 + 41 0.0000 0.741768 20.1845 + 42 0.0000 0.778170 21.1751 + 43 0.0000 0.793050 21.5800 + 44 0.0000 0.803296 21.8588 + 45 0.0000 0.823989 22.4219 + 46 0.0000 0.847870 23.0717 + 47 0.0000 0.863762 23.5042 + 48 0.0000 0.916764 24.9464 + 49 0.0000 0.944272 25.6950 + 50 0.0000 0.958729 26.0883 + 51 0.0000 0.999561 27.1994 + 52 0.0000 1.006040 27.3757 + 53 0.0000 1.023739 27.8574 + 54 0.0000 1.047353 28.4999 + 55 0.0000 1.100904 29.9571 + 56 0.0000 1.142437 31.0873 + 57 0.0000 1.222608 33.2689 + 58 0.0000 1.253456 34.1083 + 59 0.0000 1.298418 35.3318 + 60 0.0000 1.352675 36.8082 + 61 0.0000 1.416915 38.5562 + 62 0.0000 1.435739 39.0684 + 63 0.0000 1.510019 41.0897 + 64 0.0000 1.534311 41.7507 + 65 0.0000 1.559706 42.4418 + 66 0.0000 1.565505 42.5996 + 67 0.0000 1.640470 44.6395 + 68 0.0000 1.660238 45.1774 + 69 0.0000 1.703458 46.3534 + 70 0.0000 1.778076 48.3839 + 71 0.0000 1.796152 48.8758 + 72 0.0000 1.883667 51.2572 + 73 0.0000 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-0.610374 -16.6091 + 10 1.0000 -0.529261 -14.4019 + 11 1.0000 -0.458950 -12.4887 + 12 0.0000 0.029977 0.8157 + 13 0.0000 0.071637 1.9493 + 14 0.0000 0.092051 2.5048 + 15 0.0000 0.100572 2.7367 + 16 0.0000 0.116693 3.1754 + 17 0.0000 0.153005 4.1635 + 18 0.0000 0.157200 4.2776 + 19 0.0000 0.172882 4.7043 + 20 0.0000 0.185503 5.0478 + 21 0.0000 0.190457 5.1826 + 22 0.0000 0.202288 5.5045 + 23 0.0000 0.236918 6.4469 + 24 0.0000 0.271716 7.3938 + 25 0.0000 0.282127 7.6771 + 26 0.0000 0.308689 8.3998 + 27 0.0000 0.328839 8.9482 + 28 0.0000 0.340342 9.2612 + 29 0.0000 0.359203 9.7744 + 30 0.0000 0.424297 11.5457 + 31 0.0000 0.510986 13.9046 + 32 0.0000 0.520160 14.1543 + 33 0.0000 0.544677 14.8214 + 34 0.0000 0.571722 15.5574 + 35 0.0000 0.608248 16.5513 + 36 0.0000 0.631480 17.1834 + 37 0.0000 0.649810 17.6822 + 38 0.0000 0.698894 19.0179 + 39 0.0000 0.723174 19.6786 + 40 0.0000 0.738900 20.1065 + 41 0.0000 0.741768 20.1845 + 42 0.0000 0.778170 21.1751 + 43 0.0000 0.793050 21.5800 + 44 0.0000 0.803296 21.8588 + 45 0.0000 0.823989 22.4219 + 46 0.0000 0.847870 23.0717 + 47 0.0000 0.863762 23.5042 + 48 0.0000 0.916764 24.9464 + 49 0.0000 0.944272 25.6950 + 50 0.0000 0.958729 26.0883 + 51 0.0000 0.999561 27.1994 + 52 0.0000 1.006040 27.3757 + 53 0.0000 1.023739 27.8574 + 54 0.0000 1.047353 28.4999 + 55 0.0000 1.100904 29.9571 + 56 0.0000 1.142437 31.0873 + 57 0.0000 1.222608 33.2689 + 58 0.0000 1.253456 34.1083 + 59 0.0000 1.298418 35.3318 + 60 0.0000 1.352675 36.8082 + 61 0.0000 1.416915 38.5562 + 62 0.0000 1.435739 39.0684 + 63 0.0000 1.510019 41.0897 + 64 0.0000 1.534311 41.7507 + 65 0.0000 1.559706 42.4418 + 66 0.0000 1.565505 42.5996 + 67 0.0000 1.640470 44.6395 + 68 0.0000 1.660238 45.1774 + 69 0.0000 1.703458 46.3534 + 70 0.0000 1.778076 48.3839 + 71 0.0000 1.796152 48.8758 + 72 0.0000 1.883667 51.2572 + 73 0.0000 1.936168 52.6858 + 74 0.0000 1.961926 53.3867 + 75 0.0000 2.033774 55.3418 + 76 0.0000 2.056382 55.9570 + 77 0.0000 2.087670 56.8084 + 78 0.0000 2.155369 58.6506 + 79 0.0000 2.199331 59.8468 + 80 0.0000 2.259228 61.4767 + 81 0.0000 2.293510 62.4096 + 82 0.0000 2.308375 62.8141 + 83 0.0000 2.379004 64.7360 + 84 0.0000 2.418380 65.8075 + 85 0.0000 2.461639 66.9846 + 86 0.0000 2.471806 67.2613 + 87 0.0000 2.479785 67.4784 + 88 0.0000 2.512930 68.3803 + 89 0.0000 2.541094 69.1467 + 90 0.0000 2.561882 69.7123 + 91 0.0000 2.603145 70.8352 + 92 0.0000 2.673155 72.7402 + 93 0.0000 2.696281 73.3695 + 94 0.0000 2.742171 74.6183 + 95 0.0000 2.799320 76.1734 + 96 0.0000 2.840369 77.2904 + 97 0.0000 2.890172 78.6456 + 98 0.0000 2.960488 80.5590 + 99 0.0000 3.034464 82.5720 + 100 0.0000 3.079063 83.7856 + 101 0.0000 3.164085 86.0991 + 102 0.0000 3.251977 88.4908 + 103 0.0000 3.484612 94.8211 + 104 0.0000 3.733574 101.5957 + 105 0.0000 3.847851 104.7054 + 106 0.0000 4.046092 110.0998 + 107 0.0000 4.163794 113.3026 + 108 0.0000 4.200612 114.3045 + 109 0.0000 4.317829 117.4941 + 110 0.0000 4.343813 118.2012 + 111 0.0000 4.392114 119.5155 + 112 0.0000 4.556060 123.9767 + 113 0.0000 4.621612 125.7605 + 114 0.0000 4.709315 128.1470 + 115 0.0000 4.731163 128.7415 + 116 0.0000 4.786821 130.2560 + 117 0.0000 4.883929 132.8985 + 118 0.0000 4.941073 134.4534 + 119 0.0000 4.973576 135.3379 + 120 0.0000 5.067715 137.8995 + 121 0.0000 5.092314 138.5689 + 122 0.0000 5.168024 140.6291 + 123 0.0000 5.199972 141.4984 + 124 0.0000 5.237760 142.5267 + 125 0.0000 5.335221 145.1787 + 126 0.0000 5.385091 146.5358 + 127 0.0000 5.420128 147.4892 + 128 0.0000 5.532851 150.5565 + 129 0.0000 5.713414 155.4699 + 130 0.0000 5.781881 157.3330 + 131 0.0000 5.961310 162.2155 + 132 0.0000 6.155707 167.5053 + 133 0.0000 6.403286 174.2423 + 134 0.0000 6.491866 176.6527 + 135 0.0000 6.504208 176.9885 + 136 0.0000 6.699707 182.3083 + 137 0.0000 6.712013 182.6432 + 138 0.0000 6.763454 184.0429 + 139 0.0000 6.819275 185.5619 + 140 0.0000 6.859919 186.6679 + 141 0.0000 7.064278 192.2288 + 142 0.0000 7.115615 193.6257 + 143 0.0000 7.129355 193.9996 + 144 0.0000 7.198499 195.8811 + 145 0.0000 7.251450 197.3220 + 146 0.0000 7.276190 197.9952 + 147 0.0000 7.358108 200.2243 + 148 0.0000 7.402200 201.4241 + 149 0.0000 7.449369 202.7076 + 150 0.0000 7.468257 203.2216 + 151 0.0000 7.537861 205.1156 + 152 0.0000 7.606979 206.9964 + 153 0.0000 7.609592 207.0675 + 154 0.0000 7.828861 213.0342 + 155 0.0000 7.907747 215.1807 + 156 0.0000 7.977688 217.0839 + 157 0.0000 8.386093 228.1972 + 158 0.0000 14.079517 383.1231 + 159 0.0000 14.830088 403.5472 + 160 0.0000 16.150577 439.4795 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.368027 0.000000 + 1 N : 0.353093 0.000000 + 2 O : -0.243903 0.000000 + 3 H : 0.258836 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.870283 s : 3.870283 + pz : 1.505261 p : 4.470496 + px : 1.242163 + py : 1.723072 + dz2 : 0.007035 d : 0.022759 + dxz : 0.001066 + dyz : 0.001776 + dx2y2 : 0.008805 + dxy : 0.004078 + f0 : 0.000297 f : 0.004488 + f+1 : 0.000862 + f-1 : 0.000648 + f+2 : 0.000417 + f-2 : 0.000060 + f+3 : 0.001145 + f-3 : 0.001058 + 1 N s : 3.824593 s : 3.824593 + pz : 0.996380 p : 2.657127 + px : 0.835584 + py : 0.825162 + dz2 : 0.034123 d : 0.134817 + dxz : 0.031066 + dyz : 0.020149 + dx2y2 : 0.027380 + dxy : 0.022099 + f0 : 0.005341 f : 0.030370 + f+1 : 0.007618 + f-1 : 0.003430 + f+2 : 0.003706 + f-2 : 0.002170 + f+3 : 0.003007 + f-3 : 0.005098 + 2 O s : 3.877973 s : 3.877973 + pz : 1.202725 p : 4.294613 + px : 1.825986 + py : 1.265903 + dz2 : 0.022233 d : 0.063720 + dxz : 0.013928 + dyz : 0.019980 + dx2y2 : 0.003342 + dxy : 0.004236 + f0 : 0.002581 f : 0.007597 + f+1 : 0.001675 + f-1 : 0.001518 + f+2 : 0.000677 + f-2 : 0.000813 + f+3 : 0.000197 + f-3 : 0.000136 + 3 H s : 0.635647 s : 0.635647 + pz : 0.026567 p : 0.084438 + px : 0.021144 + py : 0.036727 + dz2 : 0.006726 d : 0.021079 + dxz : 0.007872 + dyz : 0.002074 + dx2y2 : 0.001628 + dxy : 0.002778 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.582766 0.000000 + 1 N : -0.243324 0.000000 + 2 O : 0.246227 0.000000 + 3 H : -0.585669 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.129887 s : 3.129887 + pz : 1.343628 p : 3.942512 + px : 1.172308 + py : 1.426576 + dz2 : 0.050021 d : 0.266198 + dxz : 0.059597 + dyz : 0.023755 + dx2y2 : 0.084984 + dxy : 0.047843 + f0 : 0.006935 f : 0.078637 + f+1 : 0.016604 + f-1 : 0.005498 + f+2 : 0.015460 + f-2 : 0.002868 + f+3 : 0.015530 + f-3 : 0.015742 + 1 N s : 3.026854 s : 3.026854 + pz : 1.140582 p : 2.838818 + px : 0.890229 + py : 0.808007 + dz2 : 0.221934 d : 0.934490 + dxz : 0.279803 + dyz : 0.145799 + dx2y2 : 0.158570 + dxy : 0.128384 + f0 : 0.077848 f : 0.443161 + f+1 : 0.107406 + f-1 : 0.062685 + f+2 : 0.061817 + f-2 : 0.036936 + f+3 : 0.040976 + f-3 : 0.055493 + 2 O s : 3.316217 s : 3.316217 + pz : 1.355800 p : 3.989352 + px : 1.493964 + py : 1.139588 + dz2 : 0.107931 d : 0.329944 + dxz : 0.089598 + dyz : 0.086932 + dx2y2 : 0.029911 + dxy : 0.015572 + f0 : 0.029824 f : 0.118261 + f+1 : 0.023842 + f-1 : 0.028955 + f+2 : 0.020168 + f-2 : 0.011279 + f+3 : 0.001685 + f-3 : 0.002509 + 3 H s : 0.625859 s : 0.625859 + pz : 0.237401 p : 0.567502 + px : 0.134810 + py : 0.195292 + dz2 : 0.118199 d : 0.392307 + dxz : 0.091206 + dyz : 0.103474 + dx2y2 : 0.042963 + dxy : 0.036464 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3680 8.0000 -0.3680 1.8552 1.8552 -0.0000 + 1 N 6.6469 7.0000 0.3531 2.5711 2.5711 0.0000 + 2 O 8.2439 8.0000 -0.2439 1.7845 1.7845 -0.0000 + 3 H 0.7412 1.0000 0.2588 0.9712 0.9712 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8386 B( 0-O , 3-H ) : 0.9605 B( 1-N , 2-O ) : 1.7251 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.963 sec +Sum of individual times .... 2.588 sec ( 87.3%) + +Fock matrix formation .... 2.230 sec ( 75.2%) +Diagonalization .... 0.151 sec ( 5.1%) +Density matrix formation .... 0.014 sec ( 0.5%) +Population analysis .... 0.046 sec ( 1.5%) +Initial guess .... 0.022 sec ( 0.7%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.013 sec ( 0.4%) +DIIS solution .... 0.125 sec ( 4.2%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.679 sec +Reference energy ... -204.710880420 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 12.272 sec +AO-integral generation ... 0.416 sec +Half transformation ... 0.188 sec +K-integral sorting ... 8.893 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.065 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.066 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.084 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.127 s ( 0.001 ms/b) +: 159120 b 0 skpd 0.049 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.099 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.083 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.061 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.107 s ( 0.001 ms/b) + 27846 b 0 skpd 0.066 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.939 sec +AO-integral generation ... 0.690 sec +Half transformation ... 0.122 sec +J-integral sorting ... 0.084 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.269 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.513 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090190761 +EMP2(bb)= -0.090190761 +EMP2(ab)= -0.517148032 + +Initial guess performed in 0.206 sec +E(0) ... -204.710880420 +E(MP2) ... -0.697529553 +Initial E(tot) ... -205.408409973 + ... 0.189086937 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.408409973 -0.697529553 -0.000000000 0.020489479 6.72 0.000001610 + *** Turning on DIIS *** + 1 -205.379849370 -0.668968950 0.028560604 0.009072606 6.55 0.056412338 + 2 -205.399369253 -0.688488833 -0.019519883 0.004161799 7.06 0.059284905 + 3 -205.403169942 -0.692289522 -0.003800688 0.001727900 6.77 0.072911869 + 4 -205.404722205 -0.693841785 -0.001552263 0.001480816 6.66 0.079190932 + 5 -205.405247540 -0.694367120 -0.000525335 0.000910471 6.21 0.084281126 + 6 -205.405347171 -0.694466751 -0.000099632 0.000586436 6.22 0.086869005 + 7 -205.405390643 -0.694510223 -0.000043471 0.000295948 7.77 0.088163515 + 8 -205.405402580 -0.694522160 -0.000011937 0.000158737 7.67 0.088724771 + 9 -205.405398634 -0.694518214 0.000003946 0.000054090 6.67 0.088918021 + 10 -205.405404331 -0.694523911 -0.000005698 0.000038000 5.78 0.088995378 + 11 -205.405400994 -0.694520574 0.000003337 0.000028252 6.47 0.088990265 + 12 -205.405402881 -0.694522461 -0.000001887 0.000019478 8.46 0.089008494 + 13 -205.405402718 -0.694522298 0.000000163 0.000011895 7.46 0.089003361 + 14 -205.405403071 -0.694522651 -0.000000352 0.000006535 5.95 0.089008925 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.710880420 +E(CORR) ... -0.694522651 +E(TOT) ... -205.405403071 +Singles norm **1/2 ... 0.089008925 ( 0.044504462, 0.044504462) +T1 diagnostic ... 0.020979605 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.052971 + 9a-> 13a 9b-> 13b 0.049121 + 9a-> 13a 8b-> 13b 0.042439 + 8a-> 13a 9b-> 13b 0.042439 + 8b-> 13b -1b-> -1b 0.030755 + 8a-> 13a -1a-> -1a 0.030755 + 11a-> 25a 11b-> 25b 0.030250 + 10a-> 13a -1a-> -1a 0.029939 + 10b-> 13b -1b-> -1b 0.029939 + 5a-> 13a 5b-> 13b 0.028846 + 11a-> 13a 11b-> 13b 0.027777 + 11a-> 25a -1a-> -1a 0.024535 + 11b-> 25b -1b-> -1b 0.024535 + 9a-> 13a 10b-> 13b 0.024098 + 10a-> 13a 9b-> 13b 0.024098 + 11a-> 25a 11b-> 26b 0.022802 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034589766 + alpha-alpha-alpha ... -0.000875190 ( 2.5%) + alpha-alpha-beta ... -0.016419693 ( 47.5%) + alpha-beta -beta ... -0.016419693 ( 47.5%) + beta -beta -beta ... -0.000875190 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034589766 + +Final correlation energy ... -0.729112417 +E(CCSD) ... -205.405403071 +E(CCSD(T)) ... -205.439992837 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210899716 sqrt= 1.100408886 +W(HF) = 0.825832219 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.298230 -0.000000 + 1 N : 0.173520 0.000000 + 2 O : -0.121658 -0.000000 + 3 H : 0.246367 -0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.846544 s : 3.846544 + pz : 1.485333 p : 4.389093 + px : 1.234062 + py : 1.669698 + dz2 : 0.012896 d : 0.054343 + dxz : 0.008338 + dyz : 0.008183 + dx2y2 : 0.013275 + dxy : 0.011650 + f0 : 0.000917 f : 0.008251 + f+1 : 0.001297 + f-1 : 0.001293 + f+2 : 0.000990 + f-2 : 0.000748 + f+3 : 0.001410 + f-3 : 0.001595 + 1 N s : 3.878615 s : 3.878615 + pz : 0.983705 p : 2.753150 + px : 0.883275 + py : 0.886171 + dz2 : 0.035401 d : 0.165149 + dxz : 0.042499 + dyz : 0.023395 + dx2y2 : 0.033300 + dxy : 0.030555 + f0 : 0.004142 f : 0.029565 + f+1 : 0.007473 + f-1 : 0.003404 + f+2 : 0.003780 + f-2 : 0.002384 + f+3 : 0.003146 + f-3 : 0.005236 + 2 O s : 3.864832 s : 3.864832 + pz : 1.187184 p : 4.162115 + px : 1.739781 + py : 1.235150 + dz2 : 0.022863 d : 0.084688 + dxz : 0.020802 + dyz : 0.021554 + dx2y2 : 0.009358 + dxy : 0.010110 + f0 : 0.002414 f : 0.010022 + f+1 : 0.002142 + f-1 : 0.001654 + f+2 : 0.001105 + f-2 : 0.001258 + f+3 : 0.000761 + f-3 : 0.000689 + 3 H s : 0.644695 s : 0.644695 + pz : 0.024738 p : 0.090855 + px : 0.024411 + py : 0.041705 + dz2 : 0.005436 d : 0.018082 + dxz : 0.007125 + dyz : 0.001186 + dx2y2 : 0.001764 + dxy : 0.002571 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.592438 -0.000000 + 1 N : -0.289530 0.000000 + 2 O : 0.285359 -0.000000 + 3 H : -0.588267 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.135004 s : 3.135004 + pz : 1.328128 p : 3.889954 + px : 1.178075 + py : 1.383752 + dz2 : 0.056135 d : 0.297091 + dxz : 0.065458 + dyz : 0.030577 + dx2y2 : 0.091726 + dxy : 0.053195 + f0 : 0.007791 f : 0.085513 + f+1 : 0.017206 + f-1 : 0.006604 + f+2 : 0.016362 + f-2 : 0.003519 + f+3 : 0.017179 + f-3 : 0.016852 + 1 N s : 3.031788 s : 3.031788 + pz : 1.126583 p : 2.881038 + px : 0.910769 + py : 0.843686 + dz2 : 0.222274 d : 0.943730 + dxz : 0.279135 + dyz : 0.147283 + dx2y2 : 0.164647 + dxy : 0.130390 + f0 : 0.075396 f : 0.432974 + f+1 : 0.104883 + f-1 : 0.062690 + f+2 : 0.059565 + f-2 : 0.035625 + f+3 : 0.042194 + f-3 : 0.052620 + 2 O s : 3.318633 s : 3.318633 + pz : 1.346628 p : 3.910617 + px : 1.438542 + py : 1.125447 + dz2 : 0.114497 d : 0.358723 + dxz : 0.092715 + dyz : 0.093608 + dx2y2 : 0.035766 + dxy : 0.022137 + f0 : 0.032740 f : 0.126668 + f+1 : 0.024939 + f-1 : 0.029851 + f+2 : 0.020787 + f-2 : 0.012844 + f+3 : 0.002493 + f-3 : 0.003014 + 3 H s : 0.626432 s : 0.626432 + pz : 0.242893 p : 0.579765 + px : 0.135060 + py : 0.201812 + dz2 : 0.114588 d : 0.382070 + dxz : 0.087802 + dyz : 0.101397 + dx2y2 : 0.042944 + dxy : 0.035339 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2982 8.0000 -0.2982 2.2096 1.7470 0.4626 + 1 N 6.8265 7.0000 0.1735 2.8445 2.3558 0.4887 + 2 O 8.1217 8.0000 -0.1217 2.1754 1.6771 0.4983 + 3 H 0.7536 1.0000 0.2464 0.9936 0.9204 0.0731 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7594 B( 0-O , 3-H ) : 0.8953 B( 1-N , 2-O ) : 1.5780 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 136.556 sec + +Fock Matrix Formation ... 0.679 sec ( 0.5%) +Initial Guess ... 0.206 sec ( 0.2%) +DIIS Solver ... 6.645 sec ( 4.9%) +State Vector Update ... 0.318 sec ( 0.2%) +Sigma-vector construction ... 95.447 sec ( 69.9%) + <0|H|D> ... 0.010 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.052 sec ( 0.1% of sigma) + (0-ext) ... 0.163 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.061 sec ( 0.1% of sigma) + (2-ext) ... 2.294 sec ( 2.4% of sigma) + (4-ext) ... 55.087 sec ( 57.7% of sigma) + ... 4.999 sec ( 5.2% of sigma) + ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.025 sec ( 0.0% of sigma) + (1-ext) ... 0.262 sec ( 0.3% of sigma) + Fock-dressing ... 6.314 sec ( 6.6% of sigma) + (ik|jl)-dressing ... 0.207 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 21.335 sec ( 22.4% of sigma) + Pair energies ... 0.042 sec ( 0.0% of sigma) +Total Time for computing (T) ... 17.232 sec ( 12.6% of ALL) + I/O of integral and amplitudes ... 1.666 sec ( 9.7% of (T)) + External N**7 contributions ... 9.297 sec ( 53.9% of (T)) + Internal N**7 contributions ... 0.924 sec ( 5.4% of (T)) + N**6 triples energy contributions ... 3.321 sec ( 19.3% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.439992836585 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.008.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.008.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.421383, -0.188437 -0.607768) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 1.01798 -0.14080 -0.60007 +Nuclear contribution : -0.94939 0.42764 1.25520 + ----------------------------------------- +Total Dipole Moment : 0.06859 0.28684 0.65513 + ----------------------------------------- +Magnitude (a.u.) : 0.71846 +Magnitude (Debye) : 1.82618 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.842475 0.404552 0.363071 +Rotational constants in MHz : 85215.253676 12128.177029 10884.581476 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.312692 -0.385230 0.519619 +x,y,z [Debye]: 0.794799 -0.979177 1.320767 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.421383, -0.188437 -0.607768) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 1.03785 -0.11624 -0.77189 +Nuclear contribution : -0.94939 0.42764 1.25520 + ----------------------------------------- +Total Dipole Moment : 0.08846 0.31140 0.48331 + ----------------------------------------- +Magnitude (a.u.) : 0.58171 +Magnitude (Debye) : 1.47859 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.842475 0.404552 0.363071 +Rotational constants in MHz : 85215.253676 12128.177029 10884.581476 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.192264 -0.264711 0.480988 +x,y,z [Debye]: 0.488696 -0.672841 1.222573 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 9 * + * * + * Dihedral ( 2, 1, 0, 3) : -114.54545455 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0399560581 RMS(Int)= 0.0003534442 + Iter 1: RMS(Cart)= 0.0000988955 RMS(Int)= 0.0000024001 + Iter 2: RMS(Cart)= 0.0000006716 RMS(Int)= 0.0000000163 + Iter 3: RMS(Cart)= 0.0000000046 RMS(Int)= 0.0000000001 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4835 0.000000 + 2. B(O 2,N 1) 1.1690 0.000000 + 3. B(H 3,O 0) 0.9721 0.000000 + 4. A(N 1,O 0,H 3) 102.1342 0.000000 + 5. A(O 0,N 1,O 2) 110.3861 0.000000 + 6. D(O 2,N 1,O 0,H 3) -114.5455 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.792386 -0.184408 0.208610 + N 0.651212 -0.350355 -0.089920 + O 0.915253 0.148188 -1.113833 + H -0.774078 0.386575 0.995143 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.497392 -0.348480 0.394215 + 1 N 7.0000 0 14.007 1.230612 -0.662075 -0.169924 + 2 O 8.0000 0 15.999 1.729578 0.280035 -2.104839 + 3 H 1.0000 0 1.008 -1.462796 0.730520 1.880548 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.483286389363 0.00000000 0.00000000 + O 2 1 0 1.166952578646 110.45499491 0.00000000 + H 1 2 3 0.969333188720 102.19223835 237.27272733 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.803005054068 0.00000000 0.00000000 + O 2 1 0 2.205220784914 110.45499491 0.00000000 + H 1 2 3 1.831774259201 102.19223835 237.27272733 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2228 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2695 + la=0 lb=0: 548 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 394 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.650941679968 Eh + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.6509416800 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.926e-04 +Time for diagonalization ... 0.006 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.005 sec +Total time needed ... 0.013 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7041889662 0.000000000000 0.00137026 0.00005296 0.0199729 0.7000 + 1 -204.7051070809 -0.000918114742 0.00134376 0.00004833 0.0165531 0.7000 + ***Turning on DIIS*** + 2 -204.7058934696 -0.000786388717 0.00376224 0.00013206 0.0134737 0.0000 + 3 -204.7104971405 -0.004603670915 0.00171232 0.00005726 0.0053168 0.0000 + 4 -204.7076156611 0.002881479446 0.00082978 0.00002836 0.0021205 0.0000 + 5 -204.7094322040 -0.001816542920 0.00067883 0.00002365 0.0011320 0.0000 + 6 -204.7087315131 0.000700690856 0.00084244 0.00002713 0.0007775 0.0000 + 7 -204.7083184061 0.000413107043 0.00033157 0.00001199 0.0004101 0.0000 + 8 -204.7090656991 -0.000747292990 0.00018303 0.00000761 0.0002043 0.0000 + 9 -204.7086448751 0.000420823950 0.00015339 0.00000619 0.0001472 0.0000 + 10 -204.7088596728 -0.000214797688 0.00007404 0.00000260 0.0000644 0.0000 + 11 -204.7089340161 -0.000074343247 0.00002327 0.00000076 0.0000334 0.0000 + 12 -204.7088155917 0.000118424361 0.00000904 0.00000029 0.0000114 0.0000 + 13 -204.7088583070 -0.000042715265 0.00000277 0.00000009 0.0000041 0.0000 + 14 -204.7088450442 0.000013262786 0.00000113 0.00000003 0.0000025 0.0000 + 15 -204.7088481531 -0.000003108892 0.00000077 0.00000002 0.0000017 0.0000 + 16 -204.7088508628 -0.000002709728 0.00000053 0.00000002 0.0000011 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 17 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70884758 Eh -5570.41094 eV + +Components: +Nuclear Repulsion : 68.65094168 Eh 1868.08709 eV +Electronic Energy : -273.35978926 Eh -7438.49803 eV +One Electron Energy: -417.02452972 Eh -11347.81437 eV +Two Electron Energy: 143.66474046 Eh 3909.31633 eV + +Virial components: +Potential Energy : -408.93652640 Eh -11127.72861 eV +Kinetic Energy : 204.22767882 Eh 5557.31767 eV +Virial Ratio : 2.00235604 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.2819e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.9288e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.6607e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 4.8154e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.685931 -562.8928 + 1 1.0000 -20.621512 -561.1399 + 2 1.0000 -15.802536 -430.0089 + 3 1.0000 -1.612287 -43.8726 + 4 1.0000 -1.378659 -37.5152 + 5 1.0000 -0.952188 -25.9103 + 6 1.0000 -0.771004 -20.9801 + 7 1.0000 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0.0000 0.029995 0.8162 + 13 0.0000 0.069884 1.9016 + 14 0.0000 0.092142 2.5073 + 15 0.0000 0.101204 2.7539 + 16 0.0000 0.114979 3.1287 + 17 0.0000 0.153767 4.1842 + 18 0.0000 0.157158 4.2765 + 19 0.0000 0.173081 4.7098 + 20 0.0000 0.184612 5.0235 + 21 0.0000 0.189829 5.1655 + 22 0.0000 0.201838 5.4923 + 23 0.0000 0.237430 6.4608 + 24 0.0000 0.272303 7.4098 + 25 0.0000 0.285538 7.7699 + 26 0.0000 0.307799 8.3756 + 27 0.0000 0.329313 8.9611 + 28 0.0000 0.336323 9.1518 + 29 0.0000 0.357078 9.7166 + 30 0.0000 0.423326 11.5193 + 31 0.0000 0.508239 13.8299 + 32 0.0000 0.522998 14.2315 + 33 0.0000 0.544998 14.8301 + 34 0.0000 0.572644 15.5824 + 35 0.0000 0.606285 16.4979 + 36 0.0000 0.629292 17.1239 + 37 0.0000 0.649609 17.6768 + 38 0.0000 0.698612 19.0102 + 39 0.0000 0.721743 19.6396 + 40 0.0000 0.741319 20.1723 + 41 0.0000 0.745985 20.2993 + 42 0.0000 0.774026 21.0623 + 43 0.0000 0.792811 21.5735 + 44 0.0000 0.805616 21.9219 + 45 0.0000 0.821446 22.3527 + 46 0.0000 0.851531 23.1713 + 47 0.0000 0.867560 23.6075 + 48 0.0000 0.909107 24.7381 + 49 0.0000 0.939348 25.5610 + 50 0.0000 0.957506 26.0551 + 51 0.0000 0.994692 27.0669 + 52 0.0000 0.999887 27.2083 + 53 0.0000 1.023805 27.8591 + 54 0.0000 1.047767 28.5112 + 55 0.0000 1.110900 30.2291 + 56 0.0000 1.139732 31.0137 + 57 0.0000 1.233202 33.5571 + 58 0.0000 1.249294 33.9950 + 59 0.0000 1.289622 35.0924 + 60 0.0000 1.337667 36.3998 + 61 0.0000 1.418173 38.5905 + 62 0.0000 1.429914 38.9099 + 63 0.0000 1.508833 41.0574 + 64 0.0000 1.529423 41.6177 + 65 0.0000 1.563065 42.5332 + 66 0.0000 1.577535 42.9269 + 67 0.0000 1.641811 44.6759 + 68 0.0000 1.654792 45.0292 + 69 0.0000 1.702901 46.3383 + 70 0.0000 1.778393 48.3925 + 71 0.0000 1.796212 48.8774 + 72 0.0000 1.883997 51.2662 + 73 0.0000 1.935900 52.6785 + 74 0.0000 1.967732 53.5447 + 75 0.0000 2.040856 55.5345 + 76 0.0000 2.058928 56.0263 + 77 0.0000 2.081844 56.6499 + 78 0.0000 2.149472 58.4901 + 79 0.0000 2.209927 60.1352 + 80 0.0000 2.248870 61.1949 + 81 0.0000 2.300584 62.6021 + 82 0.0000 2.305415 62.7335 + 83 0.0000 2.378402 64.7196 + 84 0.0000 2.412114 65.6370 + 85 0.0000 2.457064 66.8601 + 86 0.0000 2.469631 67.2021 + 87 0.0000 2.477517 67.4167 + 88 0.0000 2.512233 68.3613 + 89 0.0000 2.548805 69.3565 + 90 0.0000 2.558917 69.6317 + 91 0.0000 2.599678 70.7408 + 92 0.0000 2.671672 72.6999 + 93 0.0000 2.707953 73.6871 + 94 0.0000 2.753079 74.9151 + 95 0.0000 2.802156 76.2505 + 96 0.0000 2.851297 77.5877 + 97 0.0000 2.892127 78.6988 + 98 0.0000 2.959669 80.5367 + 99 0.0000 3.018199 82.1294 + 100 0.0000 3.068099 83.4872 + 101 0.0000 3.164271 86.1042 + 102 0.0000 3.239672 88.1560 + 103 0.0000 3.487524 94.9004 + 104 0.0000 3.730635 101.5158 + 105 0.0000 3.833478 104.3142 + 106 0.0000 4.048587 110.1676 + 107 0.0000 4.164758 113.3288 + 108 0.0000 4.191220 114.0489 + 109 0.0000 4.314277 117.3974 + 110 0.0000 4.340070 118.0993 + 111 0.0000 4.392318 119.5210 + 112 0.0000 4.543568 123.6368 + 113 0.0000 4.617888 125.6591 + 114 0.0000 4.695595 127.7736 + 115 0.0000 4.720726 128.4575 + 116 0.0000 4.794542 130.4661 + 117 0.0000 4.885785 132.9490 + 118 0.0000 4.938766 134.3907 + 119 0.0000 4.961241 135.0022 + 120 0.0000 5.064726 137.8182 + 121 0.0000 5.092857 138.5837 + 122 0.0000 5.166788 140.5955 + 123 0.0000 5.197084 141.4198 + 124 0.0000 5.229953 142.3142 + 125 0.0000 5.335379 145.1830 + 126 0.0000 5.376760 146.3091 + 127 0.0000 5.451083 148.3315 + 128 0.0000 5.533058 150.5622 + 129 0.0000 5.719771 155.6429 + 130 0.0000 5.773659 157.1093 + 131 0.0000 5.956494 162.0844 + 132 0.0000 6.168384 167.8503 + 133 0.0000 6.408769 174.3915 + 134 0.0000 6.492232 176.6626 + 135 0.0000 6.504534 176.9974 + 136 0.0000 6.699557 182.3042 + 137 0.0000 6.717135 182.7825 + 138 0.0000 6.767575 184.1551 + 139 0.0000 6.813897 185.4156 + 140 0.0000 6.847241 186.3229 + 141 0.0000 7.064597 192.2374 + 142 0.0000 7.110702 193.4920 + 143 0.0000 7.123526 193.8410 + 144 0.0000 7.196140 195.8169 + 145 0.0000 7.254429 197.4031 + 146 0.0000 7.277611 198.0339 + 147 0.0000 7.349875 200.0003 + 148 0.0000 7.396981 201.2821 + 149 0.0000 7.452961 202.8054 + 150 0.0000 7.462771 203.0723 + 151 0.0000 7.536335 205.0741 + 152 0.0000 7.600597 206.8228 + 153 0.0000 7.607485 207.0102 + 154 0.0000 7.801009 212.2763 + 155 0.0000 7.900424 214.9815 + 156 0.0000 7.975292 217.0187 + 157 0.0000 8.391608 228.3473 + 158 0.0000 14.075644 383.0177 + 159 0.0000 14.804042 402.8385 + 160 0.0000 16.056354 436.9156 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.369000 0.000000 + 1 N : 0.350848 0.000000 + 2 O : -0.240350 0.000000 + 3 H : 0.258502 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.869357 s : 3.869357 + pz : 1.540229 p : 4.471686 + px : 1.240361 + py : 1.691096 + dz2 : 0.005934 d : 0.023437 + dxz : 0.001813 + dyz : 0.002159 + dx2y2 : 0.009806 + dxy : 0.003726 + f0 : 0.000358 f : 0.004520 + f+1 : 0.000837 + f-1 : 0.000645 + f+2 : 0.000430 + f-2 : 0.000079 + f+3 : 0.001168 + f-3 : 0.001002 + 1 N s : 3.822749 s : 3.822749 + pz : 0.972509 p : 2.660618 + px : 0.836832 + py : 0.851278 + dz2 : 0.035153 d : 0.135187 + dxz : 0.030713 + dyz : 0.017992 + dx2y2 : 0.028995 + dxy : 0.022333 + f0 : 0.005291 f : 0.030598 + f+1 : 0.007115 + f-1 : 0.003116 + f+2 : 0.003925 + f-2 : 0.002629 + f+3 : 0.003285 + f-3 : 0.005238 + 2 O s : 3.878055 s : 3.878055 + pz : 1.200037 p : 4.291886 + px : 1.823000 + py : 1.268850 + dz2 : 0.023642 d : 0.062878 + dxz : 0.012530 + dyz : 0.017264 + dx2y2 : 0.004202 + dxy : 0.005240 + f0 : 0.002562 f : 0.007531 + f+1 : 0.001440 + f-1 : 0.001316 + f+2 : 0.000803 + f-2 : 0.000936 + f+3 : 0.000265 + f-3 : 0.000210 + 3 H s : 0.636274 s : 0.636274 + pz : 0.029198 p : 0.084619 + px : 0.020885 + py : 0.034535 + dz2 : 0.007365 d : 0.020605 + dxz : 0.006894 + dyz : 0.000862 + dx2y2 : 0.002064 + dxy : 0.003419 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.577872 0.000000 + 1 N : -0.244012 0.000000 + 2 O : 0.246403 0.000000 + 3 H : -0.580263 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.131315 s : 3.131315 + pz : 1.355456 p : 3.946563 + px : 1.172725 + py : 1.418383 + dz2 : 0.045833 d : 0.265693 + dxz : 0.058936 + dyz : 0.026390 + dx2y2 : 0.084815 + dxy : 0.049719 + f0 : 0.006155 f : 0.078556 + f+1 : 0.016915 + f-1 : 0.005287 + f+2 : 0.015491 + f-2 : 0.003015 + f+3 : 0.015208 + f-3 : 0.016486 + 1 N s : 3.028439 s : 3.028439 + pz : 1.107446 p : 2.840492 + px : 0.890472 + py : 0.842575 + dz2 : 0.208482 d : 0.931626 + dxz : 0.272433 + dyz : 0.152801 + dx2y2 : 0.164514 + dxy : 0.133397 + f0 : 0.071341 f : 0.443455 + f+1 : 0.099065 + f-1 : 0.061765 + f+2 : 0.065980 + f-2 : 0.044503 + f+3 : 0.043307 + f-3 : 0.057493 + 2 O s : 3.317171 s : 3.317171 + pz : 1.335018 p : 3.988860 + px : 1.493444 + py : 1.160399 + dz2 : 0.095496 d : 0.329556 + dxz : 0.086119 + dyz : 0.094837 + dx2y2 : 0.034449 + dxy : 0.018655 + f0 : 0.025523 f : 0.118010 + f+1 : 0.021458 + f-1 : 0.029485 + f+2 : 0.022650 + f-2 : 0.013280 + f+3 : 0.002036 + f-3 : 0.003577 + 3 H s : 0.624256 s : 0.624256 + pz : 0.228965 p : 0.565441 + px : 0.134599 + py : 0.201877 + dz2 : 0.113050 d : 0.390566 + dxz : 0.083795 + dyz : 0.099951 + dx2y2 : 0.049319 + dxy : 0.044452 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3690 8.0000 -0.3690 1.8385 1.8385 0.0000 + 1 N 6.6492 7.0000 0.3508 2.5793 2.5793 0.0000 + 2 O 8.2404 8.0000 -0.2404 1.7904 1.7904 0.0000 + 3 H 0.7415 1.0000 0.2585 0.9750 0.9750 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8283 B( 0-O , 3-H ) : 0.9567 B( 1-N , 2-O ) : 1.7348 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 9 sec + +Total time .... 9.506 sec +Sum of individual times .... 9.003 sec ( 94.7%) + +Fock matrix formation .... 6.977 sec ( 73.4%) +Diagonalization .... 1.003 sec ( 10.5%) +Density matrix formation .... 0.038 sec ( 0.4%) +Population analysis .... 0.051 sec ( 0.5%) +Initial guess .... 0.024 sec ( 0.2%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.013 sec ( 0.1%) +DIIS solution .... 0.910 sec ( 9.6%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.881 sec +Reference energy ... -204.708848592 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 11.369 sec +AO-integral generation ... 0.490 sec +Half transformation ... 0.249 sec +K-integral sorting ... 8.928 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.075 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.071 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.079 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.108 s ( 0.001 ms/b) +: 159120 b 0 skpd 0.045 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.092 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.081 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.062 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.106 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.063 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.893 sec +AO-integral generation ... 0.691 sec +Half transformation ... 0.096 sec +J-integral sorting ... 0.079 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.303 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.535 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090090153 +EMP2(bb)= -0.090090153 +EMP2(ab)= -0.517085812 + +Initial guess performed in 0.220 sec +E(0) ... -204.708848592 +E(MP2) ... -0.697266118 +Initial E(tot) ... -205.406114710 + ... 0.189025173 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.406114710 -0.697266118 -0.000000000 0.019711798 6.48 0.000001500 + *** Turning on DIIS *** + 1 -205.377838372 -0.668989779 0.028276339 0.009590025 5.42 0.055794596 + 2 -205.397309297 -0.688460704 -0.019470925 0.003962431 6.78 0.058666248 + 3 -205.401118019 -0.692269427 -0.003808723 0.001770946 6.22 0.071943853 + 4 -205.402656968 -0.693808375 -0.001538948 0.001206977 6.85 0.077959794 + 5 -205.403160647 -0.694312054 -0.000503679 0.000770452 8.93 0.082650957 + 6 -205.403249887 -0.694401295 -0.000089241 0.000511276 7.77 0.084929239 + 7 -205.403287367 -0.694438775 -0.000037480 0.000284565 6.70 0.086022225 + 8 -205.403297159 -0.694448567 -0.000009792 0.000158834 6.30 0.086514129 + 9 -205.403293667 -0.694445075 0.000003492 0.000066797 7.73 0.086699769 + 10 -205.403298949 -0.694450357 -0.000005282 0.000043991 7.55 0.086780161 + 11 -205.403295630 -0.694447038 0.000003319 0.000031095 7.25 0.086781390 + 12 -205.403297869 -0.694449277 -0.000002238 0.000020232 6.65 0.086799681 + 13 -205.403297756 -0.694449163 0.000000113 0.000012082 7.03 0.086796523 + 14 -205.403298099 -0.694449507 -0.000000343 0.000006314 7.20 0.086802510 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.708848592 +E(CORR) ... -0.694449507 +E(TOT) ... -205.403298099 +Singles norm **1/2 ... 0.086802510 ( 0.043401255, 0.043401255) +T1 diagnostic ... 0.020459548 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.056827 + 8a-> 13a 8b-> 13b 0.051029 + 8a-> 13a 9b-> 13b 0.044691 + 9a-> 13a 8b-> 13b 0.044691 + 8a-> 13a -1a-> -1a 0.029263 + 8b-> 13b -1b-> -1b 0.029263 + 5a-> 13a 5b-> 13b 0.029248 + 11a-> 13a 11b-> 13b 0.028088 + 11a-> 25a 11b-> 25b 0.025416 + 10a-> 13a -1a-> -1a 0.024158 + 10b-> 13b -1b-> -1b 0.024158 + 11b-> 25b -1b-> -1b 0.022357 + 11a-> 25a -1a-> -1a 0.022357 + 9a-> 13a 10b-> 13b 0.021232 + 10a-> 13a 9b-> 13b 0.021232 + 9a-> 13a 9b-> 22b 0.021080 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034458070 + alpha-alpha-alpha ... -0.000868212 ( 2.5%) + alpha-alpha-beta ... -0.016360822 ( 47.5%) + alpha-beta -beta ... -0.016360822 ( 47.5%) + beta -beta -beta ... -0.000868212 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034458070 + +Final correlation energy ... -0.728907576 +E(CCSD) ... -205.403298099 +E(CCSD(T)) ... -205.437756168 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210319849 sqrt= 1.100145376 +W(HF) = 0.826227878 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.303618 -0.000000 + 1 N : 0.174964 0.000000 + 2 O : -0.117079 -0.000000 + 3 H : 0.245733 -0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.845050 s : 3.845050 + pz : 1.519607 p : 4.395561 + px : 1.231042 + py : 1.644913 + dz2 : 0.012046 d : 0.054747 + dxz : 0.008913 + dyz : 0.008466 + dx2y2 : 0.014064 + dxy : 0.011259 + f0 : 0.000952 f : 0.008259 + f+1 : 0.001275 + f-1 : 0.001292 + f+2 : 0.001003 + f-2 : 0.000769 + f+3 : 0.001438 + f-3 : 0.001529 + 1 N s : 3.877499 s : 3.877499 + pz : 0.966220 p : 2.752317 + px : 0.883954 + py : 0.902143 + dz2 : 0.035895 d : 0.165459 + dxz : 0.042185 + dyz : 0.021806 + dx2y2 : 0.034963 + dxy : 0.030609 + f0 : 0.004058 f : 0.029761 + f+1 : 0.007032 + f-1 : 0.003188 + f+2 : 0.003932 + f-2 : 0.002768 + f+3 : 0.003417 + f-3 : 0.005365 + 2 O s : 3.864925 s : 3.864925 + pz : 1.183307 p : 4.158340 + px : 1.737522 + py : 1.237512 + dz2 : 0.023926 d : 0.083867 + dxz : 0.019439 + dyz : 0.019362 + dx2y2 : 0.010118 + dxy : 0.011022 + f0 : 0.002381 f : 0.009947 + f+1 : 0.001927 + f-1 : 0.001503 + f+2 : 0.001193 + f-2 : 0.001359 + f+3 : 0.000828 + f-3 : 0.000757 + 3 H s : 0.644936 s : 0.644936 + pz : 0.028525 p : 0.091603 + px : 0.024130 + py : 0.038948 + dz2 : 0.006175 d : 0.017728 + dxz : 0.006269 + dyz : 0.000089 + dx2y2 : 0.002068 + dxy : 0.003126 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.585642 -0.000000 + 1 N : -0.288785 0.000000 + 2 O : 0.287105 0.000000 + 3 H : -0.583962 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.136046 s : 3.136046 + pz : 1.338988 p : 3.896519 + px : 1.177188 + py : 1.380343 + dz2 : 0.051796 d : 0.296388 + dxz : 0.064861 + dyz : 0.033366 + dx2y2 : 0.091458 + dxy : 0.054908 + f0 : 0.007031 f : 0.085406 + f+1 : 0.017470 + f-1 : 0.006338 + f+2 : 0.016508 + f-2 : 0.003717 + f+3 : 0.016873 + f-3 : 0.017468 + 1 N s : 3.033434 s : 3.033434 + pz : 1.098156 p : 2.880976 + px : 0.910888 + py : 0.871932 + dz2 : 0.207697 d : 0.940829 + dxz : 0.272497 + dyz : 0.155294 + dx2y2 : 0.170398 + dxy : 0.134944 + f0 : 0.069106 f : 0.433546 + f+1 : 0.096832 + f-1 : 0.061847 + f+2 : 0.063616 + f-2 : 0.042692 + f+3 : 0.044543 + f-3 : 0.054911 + 2 O s : 3.319750 s : 3.319750 + pz : 1.325469 p : 3.908946 + px : 1.438429 + py : 1.145048 + dz2 : 0.102441 d : 0.357883 + dxz : 0.089353 + dyz : 0.100783 + dx2y2 : 0.040334 + dxy : 0.024971 + f0 : 0.028786 f : 0.126316 + f+1 : 0.022483 + f-1 : 0.030045 + f+2 : 0.023252 + f-2 : 0.014759 + f+3 : 0.002933 + f-3 : 0.004059 + 3 H s : 0.624736 s : 0.624736 + pz : 0.235094 p : 0.578627 + px : 0.134760 + py : 0.208773 + dz2 : 0.109311 d : 0.380599 + dxz : 0.080626 + dyz : 0.098554 + dx2y2 : 0.049090 + dxy : 0.043018 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3036 8.0000 -0.3036 2.1869 1.7261 0.4607 + 1 N 6.8250 7.0000 0.1750 2.8485 2.3575 0.4910 + 2 O 8.1171 8.0000 -0.1171 2.1787 1.6794 0.4993 + 3 H 0.7543 1.0000 0.2457 0.9979 0.9244 0.0735 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7456 B( 0-O , 3-H ) : 0.8932 B( 1-N , 2-O ) : 1.5864 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 137.659 sec + +Fock Matrix Formation ... 0.881 sec ( 0.6%) +Initial Guess ... 0.220 sec ( 0.2%) +DIIS Solver ... 7.267 sec ( 5.3%) +State Vector Update ... 0.380 sec ( 0.3%) +Sigma-vector construction ... 97.210 sec ( 70.6%) + <0|H|D> ... 0.009 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.059 sec ( 0.1% of sigma) + (0-ext) ... 0.186 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.067 sec ( 0.1% of sigma) + (2-ext) ... 2.394 sec ( 2.5% of sigma) + (4-ext) ... 55.690 sec ( 57.3% of sigma) + ... 5.861 sec ( 6.0% of sigma) + ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.026 sec ( 0.0% of sigma) + (1-ext) ... 0.267 sec ( 0.3% of sigma) + Fock-dressing ... 6.396 sec ( 6.6% of sigma) + (ik|jl)-dressing ... 0.228 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 21.249 sec ( 21.9% of sigma) + Pair energies ... 0.038 sec ( 0.0% of sigma) +Total Time for computing (T) ... 16.527 sec ( 12.0% of ALL) + I/O of integral and amplitudes ... 1.615 sec ( 9.8% of (T)) + External N**7 contributions ... 8.850 sec ( 53.5% of (T)) + Internal N**7 contributions ... 0.842 sec ( 5.1% of (T)) + N**6 triples energy contributions ... 3.139 sec ( 19.0% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.437756168433 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.002035250 -0.007406592 0.003116816 + 2 N : -0.003740088 -0.008020483 -0.001076122 + 3 O : 0.001368401 0.007436293 0.000689826 + 4 H : 0.000336437 0.007990781 -0.002730520 + +Norm of the cartesian gradient ... 0.016651041 +RMS gradient ... 0.004806742 +MAX gradient ... 0.008020483 + +------- +TIMINGS +------- + +Total numerical gradient time ... 903.720 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: -374.93 cm**-1 ***imaginary mode*** + 7: 575.53 cm**-1 + 8: 795.20 cm**-1 + 9: 1167.10 cm**-1 + 10: 1698.67 cm**-1 + 11: 3714.05 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 0.025415 0.538887 -0.184373 0.054172 -0.093197 0.000032 + 1 0.042127 0.046171 0.165790 0.017474 0.011490 -0.036297 + 2 -0.051451 -0.305292 -0.157172 0.046613 -0.003987 -0.051153 + 3 -0.018269 -0.212138 0.630722 -0.023744 -0.051360 -0.000036 + 4 0.067125 -0.116642 -0.202469 -0.027773 -0.335565 0.000619 + 5 0.042159 0.216343 0.074411 -0.026373 0.652597 -0.000872 + 6 -0.009935 -0.354384 -0.331544 0.029148 0.127042 -0.000515 + 7 -0.049337 0.035544 0.019573 0.007349 0.281178 -0.000775 + 8 -0.020855 0.147697 0.088402 -0.028274 -0.568414 0.000739 + 9 0.008169 0.019389 -0.575767 -0.992524 0.176492 0.008177 + 10 -0.818321 0.323847 -0.128610 -0.008064 0.017721 0.579798 + 11 0.561811 -0.504911 0.057516 0.075396 0.016795 0.812300 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 7: 575.53 0.023133 116.90 0.012543 (-0.097321 0.006600 0.055027) + 8: 795.20 0.019135 96.70 0.007509 ( 0.078756 -0.010066 -0.034719) + 9: 1167.10 0.019640 99.25 0.005251 (-0.066391 0.014949 0.024902) + 10: 1698.67 0.030244 152.84 0.005556 (-0.055861 -0.009912 0.048346) + 11: 3714.05 0.013071 66.06 0.001098 (-0.014068 0.015527 0.025676) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 7 +The total number of vibrations considered is 5 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 575.53 E(vib) ... 0.11 +freq. 795.20 E(vib) ... 0.05 +freq. 1167.10 E(vib) ... 0.01 +freq. 1698.67 E(vib) ... 0.00 +freq. 3714.05 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.43775617 Eh +Zero point energy ... 0.01811268 Eh 11.37 kcal/mol +Thermal vibrational correction ... 0.00027501 Eh 0.17 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.41653594 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00310755 Eh 1.95 kcal/mol +Non-thermal (ZPE) correction 0.01811268 Eh 11.37 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02122023 Eh 13.32 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.41653594 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.41559173 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.793779 0.404836 0.364207 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00036021 Eh 0.23 kcal/mol +Rotational entropy ... 0.00992951 Eh 6.23 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02809204 Eh 17.63 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00992951 Eh 6.23 kcal/mol| +| sn= 2 | S(rot)= 0.00927506 Eh 5.82 kcal/mol| +| sn= 3 | S(rot)= 0.00889222 Eh 5.58 kcal/mol| +| sn= 4 | S(rot)= 0.00862060 Eh 5.41 kcal/mol| +| sn= 5 | S(rot)= 0.00840991 Eh 5.28 kcal/mol| +| sn= 6 | S(rot)= 0.00823777 Eh 5.17 kcal/mol| +| sn= 7 | S(rot)= 0.00809222 Eh 5.08 kcal/mol| +| sn= 8 | S(rot)= 0.00796614 Eh 5.00 kcal/mol| +| sn= 9 | S(rot)= 0.00785493 Eh 4.93 kcal/mol| +| sn=10 | S(rot)= 0.00775545 Eh 4.87 kcal/mol| +| sn=11 | S(rot)= 0.00766546 Eh 4.81 kcal/mol| +| sn=12 | S(rot)= 0.00758331 Eh 4.76 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.41559173 Eh +Total entropy correction ... -0.02809204 Eh -17.63 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44368377 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00592760 Eh -3.72 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.437756168 Eh +Current gradient norm .... 0.016651041 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + -0.018007727 0.107582887 0.161338045 0.484420913 0.498529775 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999780877 +Lowest eigenvalues of augmented Hessian: + -0.000077782 0.106601447 0.160723822 0.484378629 0.498459815 +Length of the computed step .... 0.020937771 +The final length of the internal step .... 0.020937771 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0085478093 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0052639979 RMS(Int)= 0.0085524263 + Iter 1: RMS(Cart)= 0.0000100624 RMS(Int)= 0.0000153913 + Iter 2: RMS(Cart)= 0.0000000323 RMS(Int)= 0.0000000591 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0019305237 0.0001000000 NO + MAX gradient 0.0028764914 0.0003000000 NO + RMS step 0.0085478093 0.0020000000 NO + MAX step 0.0189465570 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0100 Max(Angles) 0.17 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4835 -0.002165 0.0100 1.4935 + 2. B(O 2,N 1) 1.1690 0.002876 -0.0034 1.1656 + 3. B(H 3,O 0) 0.9721 0.002491 -0.0027 0.9694 + 4. A(N 1,O 0,H 3) 102.13 -0.000951 0.17 102.30 + 5. A(O 0,N 1,O 2) 110.39 -0.001514 0.10 110.49 + 6. D(O 2,N 1,O 0,H 3) -114.55 0.014477 0.00 -114.55 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.796182 -0.182723 0.212040 + N 0.656014 -0.350235 -0.093812 + O 0.917847 0.146927 -1.115067 + H -0.777678 0.386031 0.996839 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.504566 -0.345297 0.400698 + 1 N 7.0000 0 14.007 1.239687 -0.661847 -0.177280 + 2 O 8.0000 0 15.999 1.734480 0.277652 -2.107172 + 3 H 1.0000 0 1.008 -1.469599 0.729493 1.883753 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.493479164962 0.00000000 0.00000000 + O 2 1 0 1.165627600076 110.48775831 0.00000000 + H 1 2 3 0.969398273214 102.30055775 245.45454517 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.822266608496 0.00000000 0.00000000 + O 2 1 0 2.202716938284 110.48775831 0.00000000 + H 1 2 3 1.831897251070 102.30055775 245.45454517 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2227 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2694 + la=0 lb=0: 548 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 393 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.538691995576 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.933e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7085476119 0.000000000000 0.00025290 0.00000757 0.0016392 0.7000 + 1 -204.7085634675 -0.000015855579 0.00020805 0.00000646 0.0013207 0.7000 + ***Turning on DIIS*** + 2 -204.7085766466 -0.000013179095 0.00053989 0.00001704 0.0010770 0.0000 + 3 -204.7081872416 0.000389405022 0.00027525 0.00000839 0.0003913 0.0000 + 4 -204.7086858913 -0.000498649763 0.00007861 0.00000330 0.0001190 0.0000 + 5 -204.7088366509 -0.000150759561 0.00004866 0.00000138 0.0001038 0.0000 + 6 -204.7085483475 0.000288303384 0.00003269 0.00000121 0.0000453 0.0000 + 7 -204.7086725167 -0.000124169189 0.00001798 0.00000076 0.0000200 0.0000 + 8 -204.7086020957 0.000070420992 0.00001483 0.00000059 0.0000131 0.0000 + 9 -204.7086147226 -0.000012626890 0.00000752 0.00000031 0.0000068 0.0000 + 10 -204.7086327710 -0.000018048374 0.00000356 0.00000014 0.0000034 0.0000 + 11 -204.7086126204 0.000020150563 0.00000138 0.00000005 0.0000018 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + +Total Energy : -204.70862171 Eh -5570.40479 eV + Last Energy change ... -9.0942e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.9753e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 2 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.240 sec +Reference energy ... -204.708621049 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.716 sec +AO-integral generation ... 0.156 sec +Half transformation ... 0.088 sec +K-integral sorting ... 5.653 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: + 251940 b 0 skpd 0.029 s ( 0.000 ms/b) +: : 377910 b 0 skpd 0.031 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.034 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.041 s ( 0.000 ms/b) + 159120 b 0 skpd 0.022 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.038 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.051 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.027 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.044 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.029 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.426 sec +AO-integral generation ... 0.305 sec +Half transformation ... 0.044 sec +J-integral sorting ... 0.056 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.174 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.266 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090119814 +EMP2(bb)= -0.090119814 +EMP2(ab)= -0.517320246 + +Initial guess performed in 0.136 sec +E(0) ... -204.708621049 +E(MP2) ... -0.697559873 +Initial E(tot) ... -205.406180922 + ... 0.189345567 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.406180922 -0.697559873 -0.000000000 0.019670709 4.31 0.000000722 + *** Turning on DIIS *** + 1 -205.377708485 -0.669087436 0.028472437 0.009331396 3.65 0.056019939 + 2 -205.397239182 -0.688618133 -0.019530697 0.003926824 3.11 0.058822466 + 3 -205.401052565 -0.692431516 -0.003813383 0.001720902 3.38 0.072148506 + 4 -205.402597221 -0.693976172 -0.001544656 0.001226487 3.58 0.078185487 + 5 -205.403104519 -0.694483471 -0.000507299 0.000778954 3.68 0.082920695 + 6 -205.403194550 -0.694573502 -0.000090031 0.000517354 3.57 0.085240370 + 7 -205.403233018 -0.694611969 -0.000038468 0.000284833 3.81 0.086371047 + 8 -205.403243128 -0.694622080 -0.000010110 0.000159936 3.65 0.086875850 + 9 -205.403239521 -0.694618472 0.000003608 0.000066958 3.47 0.087064428 + 10 -205.403244975 -0.694623927 -0.000005455 0.000043898 4.32 0.087147262 + 11 -205.403241561 -0.694620513 0.000003414 0.000030971 4.33 0.087147785 + 12 -205.403243833 -0.694622785 -0.000002272 0.000020022 3.82 0.087167195 + 13 -205.403243719 -0.694622670 0.000000114 0.000012110 4.22 0.087163384 + 14 -205.403244061 -0.694623012 -0.000000342 0.000006375 4.44 0.087169374 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.708621049 +E(CORR) ... -0.694623012 +E(TOT) ... -205.403244061 +Singles norm **1/2 ... 0.087169374 ( 0.043584687, 0.043584687) +T1 diagnostic ... 0.020546019 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.054575 + 8a-> 13a 8b-> 13b 0.053190 + 9a-> 13a 8b-> 13b 0.044804 + 8a-> 13a 9b-> 13b 0.044804 + 5a-> 13a 5b-> 13b 0.029437 + 8b-> 13b -1b-> -1b 0.028971 + 8a-> 13a -1a-> -1a 0.028971 + 11a-> 13a 11b-> 13b 0.027647 + 11a-> 25a 11b-> 25b 0.025718 + 10a-> 13a -1a-> -1a 0.024701 + 10b-> 13b -1b-> -1b 0.024701 + 11b-> 25b -1b-> -1b 0.021816 + 11a-> 25a -1a-> -1a 0.021816 + 9a-> 13a 9b-> 22b 0.020405 + 9a-> 22a 9b-> 13b 0.020405 + 9a-> 13a 10b-> 13b 0.019910 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034551207 + alpha-alpha-alpha ... -0.000868757 ( 2.5%) + alpha-alpha-beta ... -0.016406846 ( 47.5%) + alpha-beta -beta ... -0.016406846 ( 47.5%) + beta -beta -beta ... -0.000868757 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034551207 + +Final correlation energy ... -0.729174219 +E(CCSD) ... -205.403244061 +E(CCSD(T)) ... -205.437795268 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210705600 sqrt= 1.100320681 +W(HF) = 0.825964627 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 74.533 sec + +Fock Matrix Formation ... 0.240 sec ( 0.3%) +Initial Guess ... 0.136 sec ( 0.2%) +DIIS Solver ... 3.186 sec ( 4.3%) +State Vector Update ... 0.176 sec ( 0.2%) +Sigma-vector construction ... 53.977 sec ( 72.4%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.026 sec ( 0.0% of sigma) + (0-ext) ... 0.076 sec ( 0.1% of sigma) + (2-ext Fock) ... 0.028 sec ( 0.1% of sigma) + (2-ext) ... 1.025 sec ( 1.9% of sigma) + (4-ext) ... 31.479 sec ( 58.3% of sigma) + ... 2.170 sec ( 4.0% of sigma) + ... 0.003 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.147 sec ( 0.3% of sigma) + Fock-dressing ... 2.901 sec ( 5.4% of sigma) + (ik|jl)-dressing ... 0.085 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 12.989 sec ( 24.1% of sigma) + Pair energies ... 0.011 sec ( 0.0% of sigma) +Total Time for computing (T) ... 8.309 sec ( 11.1% of ALL) + I/O of integral and amplitudes ... 0.845 sec ( 10.2% of (T)) + External N**7 contributions ... 3.953 sec ( 47.6% of (T)) + Internal N**7 contributions ... 0.317 sec ( 3.8% of (T)) + N**6 triples energy contributions ... 1.745 sec ( 21.0% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.437795267858 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.000704212 -0.005665555 0.006136194 + 2 N : -0.001794953 -0.006585863 -0.004796522 + 3 O : 0.001319843 0.005863254 0.003309287 + 4 H : -0.000229101 0.006388164 -0.004648959 + +Norm of the cartesian gradient ... 0.015792227 +RMS gradient ... 0.004558823 +MAX gradient ... 0.006585863 + +------- +TIMINGS +------- + +Total numerical gradient time ... 429.536 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.437795268 Eh +Current gradient norm .... 0.015792227 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999879 +Lowest eigenvalues of augmented Hessian: + -0.000000044 0.105137710 0.159558078 0.483914475 0.500242928 +Length of the computed step .... 0.000491661 +The final length of the internal step .... 0.000491661 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0002007197 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001399652 RMS(Int)= 0.0002007208 + Iter 1: RMS(Cart)= 0.0000000028 RMS(Int)= 0.0000000040 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000390996 0.0000050000 NO + RMS gradient 0.0000556430 0.0001000000 YES + MAX gradient 0.0001017609 0.0003000000 YES + RMS step 0.0002007197 0.0020000000 YES + MAX step 0.0004868862 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0003 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4935 -0.000077 0.0003 1.4937 + 2. B(O 2,N 1) 1.1656 -0.000102 0.0000 1.1657 + 3. B(H 3,O 0) 0.9694 -0.000020 0.0000 0.9694 + 4. A(N 1,O 0,H 3) 102.30 -0.000015 -0.00 102.30 + 5. A(O 0,N 1,O 2) 110.49 -0.000041 0.00 110.49 + 6. D(O 2,N 1,O 0,H 3) -114.55 0.014150 0.00 -114.55 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.796310 -0.182718 0.212103 + N 0.656124 -0.350247 -0.093870 + O 0.917945 0.146919 -1.115152 + H -0.777759 0.386047 0.996919 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.504807 -0.345287 0.400816 + 1 N 7.0000 0 14.007 1.239895 -0.661872 -0.177388 + 2 O 8.0000 0 15.999 1.734665 0.277637 -2.107332 + 3 H 1.0000 0 1.008 -1.469752 0.729522 1.883904 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.493736814059 0.00000000 0.00000000 + O 2 1 0 1.165651379463 110.48944470 0.00000000 + H 1 2 3 0.969419279610 102.29972609 245.45454517 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.822753494728 0.00000000 0.00000000 + O 2 1 0 2.202761874813 110.48944470 0.00000000 + H 1 2 3 1.831936947406 102.29972609 245.45454517 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2227 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2694 + la=0 lb=0: 548 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 393 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.532437531723 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.5324375317 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.933e-04 +Time for diagonalization ... 0.004 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.003 sec +Total time needed ... 0.008 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7085919270 0.000000000000 0.00000843 0.00000017 0.0000425 0.7000 + 1 -204.7085919336 -0.000000006616 0.00000656 0.00000014 0.0000334 0.7000 + ***Turning on DIIS*** + 2 -204.7085919392 -0.000000005558 0.00001512 0.00000038 0.0000259 0.0000 + 3 -204.7086035070 -0.000011567814 0.00000671 0.00000016 0.0000065 0.0000 + 4 -204.7085894836 0.000014023397 0.00000193 0.00000005 0.0000020 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70858706 Eh -5570.40385 eV + +Components: +Nuclear Repulsion : 68.53243753 Eh 1864.86243 eV +Electronic Energy : -273.24102459 Eh -7435.26628 eV +One Electron Energy: -416.78274358 Eh -11341.23503 eV +Two Electron Energy: 143.54171899 Eh 3905.96875 eV + +Virial components: +Potential Energy : -408.94073458 Eh -11127.84312 eV +Kinetic Energy : 204.23214752 Eh 5557.43927 eV +Virial Ratio : 2.00233283 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.4255e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 9.3720e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.1280e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.9306e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.688156 -562.9533 + 1 1.0000 -20.619174 -561.0763 + 2 1.0000 -15.803678 -430.0399 + 3 1.0000 -1.615500 -43.9600 + 4 1.0000 -1.375815 -37.4378 + 5 1.0000 -0.952465 -25.9179 + 6 1.0000 -0.771007 -20.9802 + 7 1.0000 -0.730156 -19.8686 + 8 1.0000 -0.697753 -18.9868 + 9 1.0000 -0.608684 -16.5631 + 10 1.0000 -0.528891 -14.3919 + 11 1.0000 -0.458375 -12.4730 + 12 0.0000 0.030309 0.8247 + 13 0.0000 0.069867 1.9012 + 14 0.0000 0.091775 2.4973 + 15 0.0000 0.101125 2.7517 + 16 0.0000 0.115256 3.1363 + 17 0.0000 0.154083 4.1928 + 18 0.0000 0.157185 4.2772 + 19 0.0000 0.173047 4.7088 + 20 0.0000 0.184390 5.0175 + 21 0.0000 0.189939 5.1685 + 22 0.0000 0.201624 5.4865 + 23 0.0000 0.236886 6.4460 + 24 0.0000 0.271375 7.3845 + 25 0.0000 0.283305 7.7091 + 26 0.0000 0.306774 8.3478 + 27 0.0000 0.328959 8.9514 + 28 0.0000 0.336172 9.1477 + 29 0.0000 0.356863 9.7107 + 30 0.0000 0.424716 11.5571 + 31 0.0000 0.508092 13.8259 + 32 0.0000 0.522800 14.2261 + 33 0.0000 0.544152 14.8071 + 34 0.0000 0.572391 15.5756 + 35 0.0000 0.605908 16.4876 + 36 0.0000 0.630630 17.1603 + 37 0.0000 0.650761 17.7081 + 38 0.0000 0.697954 18.9923 + 39 0.0000 0.722138 19.6504 + 40 0.0000 0.740431 20.1482 + 41 0.0000 0.744950 20.2711 + 42 0.0000 0.774196 21.0669 + 43 0.0000 0.792846 21.5744 + 44 0.0000 0.806097 21.9350 + 45 0.0000 0.821128 22.3440 + 46 0.0000 0.851374 23.1671 + 47 0.0000 0.867492 23.6056 + 48 0.0000 0.909357 24.7449 + 49 0.0000 0.940067 25.5805 + 50 0.0000 0.957674 26.0596 + 51 0.0000 0.995249 27.0821 + 52 0.0000 1.000634 27.2286 + 53 0.0000 1.024474 27.8774 + 54 0.0000 1.048244 28.5242 + 55 0.0000 1.110056 30.2061 + 56 0.0000 1.138513 30.9805 + 57 0.0000 1.232021 33.5250 + 58 0.0000 1.248983 33.9866 + 59 0.0000 1.289415 35.0868 + 60 0.0000 1.337037 36.3826 + 61 0.0000 1.419859 38.6363 + 62 0.0000 1.432380 38.9770 + 63 0.0000 1.510412 41.1004 + 64 0.0000 1.528132 41.5826 + 65 0.0000 1.561968 42.5033 + 66 0.0000 1.577564 42.9277 + 67 0.0000 1.640704 44.6458 + 68 0.0000 1.654103 45.0104 + 69 0.0000 1.701982 46.3133 + 70 0.0000 1.776968 48.3538 + 71 0.0000 1.794868 48.8408 + 72 0.0000 1.882750 51.2322 + 73 0.0000 1.935303 52.6623 + 74 0.0000 1.966981 53.5243 + 75 0.0000 2.036863 55.4259 + 76 0.0000 2.057401 55.9847 + 77 0.0000 2.079685 56.5911 + 78 0.0000 2.148434 58.4619 + 79 0.0000 2.209468 60.1227 + 80 0.0000 2.246902 61.1413 + 81 0.0000 2.299923 62.5841 + 82 0.0000 2.305068 62.7241 + 83 0.0000 2.379095 64.7385 + 84 0.0000 2.411898 65.6311 + 85 0.0000 2.456134 66.8348 + 86 0.0000 2.466147 67.1073 + 87 0.0000 2.477656 67.4205 + 88 0.0000 2.511702 68.3469 + 89 0.0000 2.547832 69.3300 + 90 0.0000 2.557523 69.5937 + 91 0.0000 2.601336 70.7859 + 92 0.0000 2.674241 72.7698 + 93 0.0000 2.704184 73.5846 + 94 0.0000 2.754411 74.9513 + 95 0.0000 2.799524 76.1789 + 96 0.0000 2.847575 77.4865 + 97 0.0000 2.887298 78.5674 + 98 0.0000 2.955236 80.4161 + 99 0.0000 3.013465 82.0005 + 100 0.0000 3.061923 83.3192 + 101 0.0000 3.163006 86.0698 + 102 0.0000 3.242818 88.2416 + 103 0.0000 3.486797 94.8806 + 104 0.0000 3.733227 101.5863 + 105 0.0000 3.830507 104.2334 + 106 0.0000 4.050783 110.2274 + 107 0.0000 4.169135 113.4479 + 108 0.0000 4.194513 114.1385 + 109 0.0000 4.315194 117.4224 + 110 0.0000 4.339294 118.0782 + 111 0.0000 4.393195 119.5449 + 112 0.0000 4.545946 123.7015 + 113 0.0000 4.619136 125.6931 + 114 0.0000 4.689869 127.6178 + 115 0.0000 4.724160 128.5509 + 116 0.0000 4.795722 130.4982 + 117 0.0000 4.888401 133.0201 + 118 0.0000 4.936465 134.3280 + 119 0.0000 4.963502 135.0638 + 120 0.0000 5.062720 137.7636 + 121 0.0000 5.093513 138.6015 + 122 0.0000 5.170464 140.6955 + 123 0.0000 5.199665 141.4901 + 124 0.0000 5.224806 142.1742 + 125 0.0000 5.339129 145.2851 + 126 0.0000 5.377408 146.3267 + 127 0.0000 5.449126 148.2783 + 128 0.0000 5.526278 150.3777 + 129 0.0000 5.721354 155.6860 + 130 0.0000 5.769884 157.0065 + 131 0.0000 5.945325 161.7805 + 132 0.0000 6.168357 167.8495 + 133 0.0000 6.406059 174.3177 + 134 0.0000 6.490245 176.6085 + 135 0.0000 6.501757 176.9218 + 136 0.0000 6.700747 182.3366 + 137 0.0000 6.718024 182.8067 + 138 0.0000 6.770863 184.2445 + 139 0.0000 6.811568 185.3522 + 140 0.0000 6.843196 186.2128 + 141 0.0000 7.062151 192.1709 + 142 0.0000 7.110534 193.4875 + 143 0.0000 7.122649 193.8171 + 144 0.0000 7.201825 195.9716 + 145 0.0000 7.256432 197.4576 + 146 0.0000 7.279582 198.0875 + 147 0.0000 7.355681 200.1583 + 148 0.0000 7.398521 201.3240 + 149 0.0000 7.448547 202.6853 + 150 0.0000 7.461832 203.0468 + 151 0.0000 7.539340 205.1559 + 152 0.0000 7.598204 206.7576 + 153 0.0000 7.602284 206.8687 + 154 0.0000 7.793841 212.0812 + 155 0.0000 7.905661 215.1240 + 156 0.0000 7.960483 216.6158 + 157 0.0000 8.391207 228.3364 + 158 0.0000 14.079022 383.1097 + 159 0.0000 14.817531 403.2055 + 160 0.0000 16.135820 439.0780 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.688156 -562.9533 + 1 1.0000 -20.619174 -561.0763 + 2 1.0000 -15.803678 -430.0399 + 3 1.0000 -1.615500 -43.9600 + 4 1.0000 -1.375815 -37.4378 + 5 1.0000 -0.952465 -25.9179 + 6 1.0000 -0.771007 -20.9802 + 7 1.0000 -0.730156 -19.8686 + 8 1.0000 -0.697753 -18.9868 + 9 1.0000 -0.608684 -16.5631 + 10 1.0000 -0.528891 -14.3919 + 11 1.0000 -0.458375 -12.4730 + 12 0.0000 0.030309 0.8247 + 13 0.0000 0.069867 1.9012 + 14 0.0000 0.091775 2.4973 + 15 0.0000 0.101125 2.7517 + 16 0.0000 0.115256 3.1363 + 17 0.0000 0.154083 4.1928 + 18 0.0000 0.157185 4.2772 + 19 0.0000 0.173047 4.7088 + 20 0.0000 0.184390 5.0175 + 21 0.0000 0.189939 5.1685 + 22 0.0000 0.201624 5.4865 + 23 0.0000 0.236886 6.4460 + 24 0.0000 0.271375 7.3845 + 25 0.0000 0.283305 7.7091 + 26 0.0000 0.306774 8.3478 + 27 0.0000 0.328959 8.9514 + 28 0.0000 0.336172 9.1477 + 29 0.0000 0.356863 9.7107 + 30 0.0000 0.424716 11.5571 + 31 0.0000 0.508092 13.8259 + 32 0.0000 0.522800 14.2261 + 33 0.0000 0.544152 14.8071 + 34 0.0000 0.572391 15.5756 + 35 0.0000 0.605908 16.4876 + 36 0.0000 0.630630 17.1603 + 37 0.0000 0.650761 17.7081 + 38 0.0000 0.697954 18.9923 + 39 0.0000 0.722138 19.6504 + 40 0.0000 0.740431 20.1482 + 41 0.0000 0.744950 20.2711 + 42 0.0000 0.774196 21.0669 + 43 0.0000 0.792846 21.5744 + 44 0.0000 0.806097 21.9350 + 45 0.0000 0.821128 22.3440 + 46 0.0000 0.851374 23.1671 + 47 0.0000 0.867492 23.6056 + 48 0.0000 0.909357 24.7449 + 49 0.0000 0.940067 25.5805 + 50 0.0000 0.957674 26.0596 + 51 0.0000 0.995249 27.0821 + 52 0.0000 1.000634 27.2286 + 53 0.0000 1.024474 27.8774 + 54 0.0000 1.048244 28.5242 + 55 0.0000 1.110056 30.2061 + 56 0.0000 1.138513 30.9805 + 57 0.0000 1.232021 33.5250 + 58 0.0000 1.248983 33.9866 + 59 0.0000 1.289415 35.0868 + 60 0.0000 1.337037 36.3826 + 61 0.0000 1.419859 38.6363 + 62 0.0000 1.432380 38.9770 + 63 0.0000 1.510412 41.1004 + 64 0.0000 1.528132 41.5826 + 65 0.0000 1.561968 42.5033 + 66 0.0000 1.577564 42.9277 + 67 0.0000 1.640704 44.6458 + 68 0.0000 1.654103 45.0104 + 69 0.0000 1.701982 46.3133 + 70 0.0000 1.776968 48.3538 + 71 0.0000 1.794868 48.8408 + 72 0.0000 1.882750 51.2322 + 73 0.0000 1.935303 52.6623 + 74 0.0000 1.966981 53.5243 + 75 0.0000 2.036863 55.4259 + 76 0.0000 2.057401 55.9847 + 77 0.0000 2.079685 56.5911 + 78 0.0000 2.148434 58.4619 + 79 0.0000 2.209468 60.1227 + 80 0.0000 2.246902 61.1413 + 81 0.0000 2.299923 62.5841 + 82 0.0000 2.305068 62.7241 + 83 0.0000 2.379095 64.7385 + 84 0.0000 2.411898 65.6311 + 85 0.0000 2.456134 66.8348 + 86 0.0000 2.466147 67.1073 + 87 0.0000 2.477656 67.4205 + 88 0.0000 2.511702 68.3469 + 89 0.0000 2.547832 69.3300 + 90 0.0000 2.557523 69.5937 + 91 0.0000 2.601336 70.7859 + 92 0.0000 2.674241 72.7698 + 93 0.0000 2.704184 73.5846 + 94 0.0000 2.754411 74.9513 + 95 0.0000 2.799524 76.1789 + 96 0.0000 2.847575 77.4865 + 97 0.0000 2.887298 78.5674 + 98 0.0000 2.955236 80.4161 + 99 0.0000 3.013465 82.0005 + 100 0.0000 3.061923 83.3192 + 101 0.0000 3.163006 86.0698 + 102 0.0000 3.242818 88.2416 + 103 0.0000 3.486797 94.8806 + 104 0.0000 3.733227 101.5863 + 105 0.0000 3.830507 104.2334 + 106 0.0000 4.050783 110.2274 + 107 0.0000 4.169135 113.4479 + 108 0.0000 4.194513 114.1385 + 109 0.0000 4.315194 117.4224 + 110 0.0000 4.339294 118.0782 + 111 0.0000 4.393195 119.5449 + 112 0.0000 4.545946 123.7015 + 113 0.0000 4.619136 125.6931 + 114 0.0000 4.689869 127.6178 + 115 0.0000 4.724160 128.5509 + 116 0.0000 4.795722 130.4982 + 117 0.0000 4.888401 133.0201 + 118 0.0000 4.936465 134.3280 + 119 0.0000 4.963502 135.0638 + 120 0.0000 5.062720 137.7636 + 121 0.0000 5.093513 138.6015 + 122 0.0000 5.170464 140.6955 + 123 0.0000 5.199665 141.4901 + 124 0.0000 5.224806 142.1742 + 125 0.0000 5.339129 145.2851 + 126 0.0000 5.377408 146.3267 + 127 0.0000 5.449126 148.2783 + 128 0.0000 5.526278 150.3777 + 129 0.0000 5.721354 155.6860 + 130 0.0000 5.769884 157.0065 + 131 0.0000 5.945325 161.7805 + 132 0.0000 6.168357 167.8495 + 133 0.0000 6.406059 174.3177 + 134 0.0000 6.490245 176.6085 + 135 0.0000 6.501757 176.9218 + 136 0.0000 6.700747 182.3366 + 137 0.0000 6.718024 182.8067 + 138 0.0000 6.770863 184.2445 + 139 0.0000 6.811568 185.3522 + 140 0.0000 6.843196 186.2128 + 141 0.0000 7.062151 192.1709 + 142 0.0000 7.110534 193.4875 + 143 0.0000 7.122649 193.8171 + 144 0.0000 7.201825 195.9716 + 145 0.0000 7.256432 197.4576 + 146 0.0000 7.279582 198.0875 + 147 0.0000 7.355681 200.1583 + 148 0.0000 7.398521 201.3240 + 149 0.0000 7.448547 202.6853 + 150 0.0000 7.461832 203.0468 + 151 0.0000 7.539340 205.1559 + 152 0.0000 7.598204 206.7576 + 153 0.0000 7.602284 206.8687 + 154 0.0000 7.793841 212.0812 + 155 0.0000 7.905661 215.1240 + 156 0.0000 7.960483 216.6158 + 157 0.0000 8.391207 228.3364 + 158 0.0000 14.079022 383.1097 + 159 0.0000 14.817531 403.2055 + 160 0.0000 16.135820 439.0780 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.372997 0.000000 + 1 N : 0.354359 0.000000 + 2 O : -0.236322 0.000000 + 3 H : 0.254961 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.870198 s : 3.870198 + pz : 1.538580 p : 4.475336 + px : 1.244403 + py : 1.692353 + dz2 : 0.005800 d : 0.023033 + dxz : 0.001804 + dyz : 0.002101 + dx2y2 : 0.009719 + dxy : 0.003609 + f0 : 0.000347 f : 0.004430 + f+1 : 0.000822 + f-1 : 0.000636 + f+2 : 0.000417 + f-2 : 0.000078 + f+3 : 0.001158 + f-3 : 0.000972 + 1 N s : 3.823046 s : 3.823046 + pz : 0.971822 p : 2.657499 + px : 0.834978 + py : 0.850700 + dz2 : 0.034911 d : 0.134690 + dxz : 0.030933 + dyz : 0.017943 + dx2y2 : 0.028954 + dxy : 0.021949 + f0 : 0.005228 f : 0.030406 + f+1 : 0.007128 + f-1 : 0.003119 + f+2 : 0.003850 + f-2 : 0.002644 + f+3 : 0.003277 + f-3 : 0.005161 + 2 O s : 3.876893 s : 3.876893 + pz : 1.200192 p : 4.288218 + px : 1.818034 + py : 1.269991 + dz2 : 0.023807 d : 0.063642 + dxz : 0.012840 + dyz : 0.017419 + dx2y2 : 0.004264 + dxy : 0.005311 + f0 : 0.002572 f : 0.007570 + f+1 : 0.001458 + f-1 : 0.001319 + f+2 : 0.000802 + f-2 : 0.000941 + f+3 : 0.000264 + f-3 : 0.000213 + 3 H s : 0.638881 s : 0.638881 + pz : 0.029226 p : 0.085440 + px : 0.021342 + py : 0.034872 + dz2 : 0.007412 d : 0.020719 + dxz : 0.006906 + dyz : 0.000911 + dx2y2 : 0.002080 + dxy : 0.003409 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.578791 0.000000 + 1 N : -0.237842 0.000000 + 2 O : 0.247983 0.000000 + 3 H : -0.588932 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.133360 s : 3.133360 + pz : 1.357127 p : 3.950261 + px : 1.171924 + py : 1.421209 + dz2 : 0.045173 d : 0.261002 + dxz : 0.057520 + dyz : 0.026150 + dx2y2 : 0.083855 + dxy : 0.048303 + f0 : 0.005923 f : 0.076586 + f+1 : 0.016572 + f-1 : 0.005251 + f+2 : 0.014980 + f-2 : 0.002957 + f+3 : 0.014963 + f-3 : 0.015942 + 1 N s : 3.031868 s : 3.031868 + pz : 1.109851 p : 2.839164 + px : 0.885181 + py : 0.844132 + dz2 : 0.207730 d : 0.926839 + dxz : 0.271734 + dyz : 0.152883 + dx2y2 : 0.163600 + dxy : 0.130892 + f0 : 0.070738 f : 0.439971 + f+1 : 0.098973 + f-1 : 0.061708 + f+2 : 0.065036 + f-2 : 0.044509 + f+3 : 0.042765 + f-3 : 0.056242 + 2 O s : 3.316064 s : 3.316064 + pz : 1.336917 p : 3.986897 + px : 1.488634 + py : 1.161345 + dz2 : 0.095971 d : 0.330829 + dxz : 0.086373 + dyz : 0.095410 + dx2y2 : 0.034520 + dxy : 0.018555 + f0 : 0.025643 f : 0.118227 + f+1 : 0.021474 + f-1 : 0.029689 + f+2 : 0.022634 + f-2 : 0.013225 + f+3 : 0.002016 + f-3 : 0.003546 + 3 H s : 0.626884 s : 0.626884 + pz : 0.230739 p : 0.570421 + px : 0.135942 + py : 0.203739 + dz2 : 0.113678 d : 0.391627 + dxz : 0.084096 + dyz : 0.100351 + dx2y2 : 0.049273 + dxy : 0.044230 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3730 8.0000 -0.3730 1.8411 1.8411 0.0000 + 1 N 6.6456 7.0000 0.3544 2.5818 2.5818 -0.0000 + 2 O 8.2363 8.0000 -0.2363 1.7974 1.7974 0.0000 + 3 H 0.7450 1.0000 0.2550 0.9780 0.9780 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8256 B( 0-O , 3-H ) : 0.9597 B( 1-N , 2-O ) : 1.7397 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.046 sec +Sum of individual times .... 0.830 sec ( 79.4%) + +Fock matrix formation .... 0.666 sec ( 63.7%) +Diagonalization .... 0.069 sec ( 6.6%) +Density matrix formation .... 0.007 sec ( 0.7%) +Population analysis .... 0.025 sec ( 2.4%) +Initial guess .... 0.010 sec ( 1.0%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.006 sec ( 0.6%) +DIIS solution .... 0.053 sec ( 5.1%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.248 sec +Reference energy ... -204.708591956 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.752 sec +AO-integral generation ... 0.150 sec +Half transformation ... 0.084 sec +K-integral sorting ... 5.553 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.026 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.028 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.034 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.041 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.036 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.032 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.024 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.041 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.024 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.368 sec +AO-integral generation ... 0.264 sec +Half transformation ... 0.042 sec +J-integral sorting ... 0.048 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.150 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.254 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090123356 +EMP2(bb)= -0.090123356 +EMP2(ab)= -0.517343446 + +Initial guess performed in 0.134 sec +E(0) ... -204.708591956 +E(MP2) ... -0.697590157 +Initial E(tot) ... -205.406182113 + ... 0.189374438 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.406182113 -0.697590157 -0.000000000 0.019673104 2.94 0.000001919 + *** Turning on DIIS *** + 1 -205.377695239 -0.669103284 0.028486873 0.009331059 3.02 0.056032852 + 2 -205.397230939 -0.688638984 -0.019535700 0.003926970 3.14 0.058832992 + 3 -205.401045171 -0.692453215 -0.003814232 0.001720943 3.28 0.072162622 + 4 -205.402590408 -0.693998453 -0.001545237 0.001227054 3.09 0.078201389 + 5 -205.403098012 -0.694506057 -0.000507604 0.000779312 3.07 0.082938899 + 6 -205.403188089 -0.694596133 -0.000090077 0.000517644 3.32 0.085259996 + 7 -205.403226591 -0.694634636 -0.000038502 0.000284986 3.22 0.086391865 + 8 -205.403236717 -0.694644762 -0.000010126 0.000160039 3.16 0.086897287 + 9 -205.403233106 -0.694641150 0.000003611 0.000067017 3.07 0.087086104 + 10 -205.403238569 -0.694646614 -0.000005463 0.000043931 3.11 0.087169081 + 11 -205.403235150 -0.694643195 0.000003419 0.000030993 3.82 0.087169599 + 12 -205.403237425 -0.694645470 -0.000002275 0.000020034 4.55 0.087189052 + 13 -205.403237311 -0.694645355 0.000000115 0.000012120 4.79 0.087185227 + 14 -205.403237653 -0.694645698 -0.000000342 0.000006381 3.83 0.087191227 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.708591956 +E(CORR) ... -0.694645698 +E(TOT) ... -205.403237653 +Singles norm **1/2 ... 0.087191227 ( 0.043595613, 0.043595613) +T1 diagnostic ... 0.020551169 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.054563 + 8a-> 13a 8b-> 13b 0.053228 + 9a-> 13a 8b-> 13b 0.044819 + 8a-> 13a 9b-> 13b 0.044819 + 5a-> 13a 5b-> 13b 0.029448 + 8b-> 13b -1b-> -1b 0.028972 + 8a-> 13a -1a-> -1a 0.028972 + 11a-> 13a 11b-> 13b 0.027639 + 11a-> 25a 11b-> 25b 0.025675 + 10a-> 13a -1a-> -1a 0.024715 + 10b-> 13b -1b-> -1b 0.024715 + 11a-> 25a -1a-> -1a 0.021788 + 11b-> 25b -1b-> -1b 0.021788 + 9a-> 13a 9b-> 22b 0.020397 + 9a-> 22a 9b-> 13b 0.020397 + 10a-> 13a 9b-> 13b 0.019897 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034557629 + alpha-alpha-alpha ... -0.000868829 ( 2.5%) + alpha-alpha-beta ... -0.016409986 ( 47.5%) + alpha-beta -beta ... -0.016409986 ( 47.5%) + beta -beta -beta ... -0.000868829 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034557629 + +Final correlation energy ... -0.729203327 +E(CCSD) ... -205.403237653 +E(CCSD(T)) ... -205.437795282 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210739916 sqrt= 1.100336274 +W(HF) = 0.825941218 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.308071 0.000000 + 1 N : 0.177989 -0.000000 + 2 O : -0.112526 0.000000 + 3 H : 0.242609 -0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.846416 s : 3.846416 + pz : 1.518286 p : 4.399047 + px : 1.234502 + py : 1.646260 + dz2 : 0.011941 d : 0.054426 + dxz : 0.008876 + dyz : 0.008414 + dx2y2 : 0.014050 + dxy : 0.011145 + f0 : 0.000940 f : 0.008182 + f+1 : 0.001265 + f-1 : 0.001283 + f+2 : 0.000989 + f-2 : 0.000767 + f+3 : 0.001430 + f-3 : 0.001508 + 1 N s : 3.877324 s : 3.877324 + pz : 0.965262 p : 2.750409 + px : 0.884573 + py : 0.900574 + dz2 : 0.035655 d : 0.164740 + dxz : 0.042257 + dyz : 0.021727 + dx2y2 : 0.034851 + dxy : 0.030251 + f0 : 0.004001 f : 0.029538 + f+1 : 0.007024 + f-1 : 0.003187 + f+2 : 0.003853 + f-2 : 0.002769 + f+3 : 0.003412 + f-3 : 0.005292 + 2 O s : 3.863943 s : 3.863943 + pz : 1.183728 p : 4.154099 + px : 1.731218 + py : 1.239153 + dz2 : 0.024043 d : 0.084520 + dxz : 0.019732 + dyz : 0.019496 + dx2y2 : 0.010173 + dxy : 0.011076 + f0 : 0.002383 f : 0.009965 + f+1 : 0.001942 + f-1 : 0.001506 + f+2 : 0.001190 + f-2 : 0.001361 + f+3 : 0.000824 + f-3 : 0.000758 + 3 H s : 0.647218 s : 0.647218 + pz : 0.028538 p : 0.092426 + px : 0.024542 + py : 0.039347 + dz2 : 0.006194 d : 0.017747 + dxz : 0.006255 + dyz : 0.000120 + dx2y2 : 0.002071 + dxy : 0.003107 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.586514 0.000000 + 1 N : -0.283030 0.000000 + 2 O : 0.288747 -0.000000 + 3 H : -0.592232 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.137985 s : 3.137985 + pz : 1.340785 p : 3.900198 + px : 1.176350 + py : 1.383064 + dz2 : 0.051167 d : 0.291855 + dxz : 0.063483 + dyz : 0.033134 + dx2y2 : 0.090569 + dxy : 0.053502 + f0 : 0.006810 f : 0.083447 + f+1 : 0.017135 + f-1 : 0.006293 + f+2 : 0.016029 + f-2 : 0.003659 + f+3 : 0.016630 + f-3 : 0.016892 + 1 N s : 3.036732 s : 3.036732 + pz : 1.100351 p : 2.880444 + px : 0.907458 + py : 0.872634 + dz2 : 0.206992 d : 0.935724 + dxz : 0.271449 + dyz : 0.155433 + dx2y2 : 0.169225 + dxy : 0.132627 + f0 : 0.068611 f : 0.430130 + f+1 : 0.096622 + f-1 : 0.061782 + f+2 : 0.062706 + f-2 : 0.042660 + f+3 : 0.044014 + f-3 : 0.053735 + 2 O s : 3.318654 s : 3.318654 + pz : 1.327559 p : 3.906917 + px : 1.432920 + py : 1.146439 + dz2 : 0.102860 d : 0.359081 + dxz : 0.089643 + dyz : 0.101325 + dx2y2 : 0.040361 + dxy : 0.024892 + f0 : 0.028889 f : 0.126601 + f+1 : 0.022556 + f-1 : 0.030239 + f+2 : 0.023227 + f-2 : 0.014749 + f+3 : 0.002911 + f-3 : 0.004030 + 3 H s : 0.627176 s : 0.627176 + pz : 0.236915 p : 0.583595 + px : 0.135925 + py : 0.210755 + dz2 : 0.109878 d : 0.381461 + dxz : 0.080841 + dyz : 0.098926 + dx2y2 : 0.049032 + dxy : 0.042783 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3081 8.0000 -0.3081 2.1902 1.7270 0.4632 + 1 N 6.8220 7.0000 0.1780 2.8504 2.3590 0.4914 + 2 O 8.1125 8.0000 -0.1125 2.1859 1.6875 0.4984 + 3 H 0.7574 1.0000 0.2426 1.0005 0.9268 0.0736 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7412 B( 0-O , 3-H ) : 0.8959 B( 1-N , 2-O ) : 1.5922 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 67.851 sec + +Fock Matrix Formation ... 0.248 sec ( 0.4%) +Initial Guess ... 0.134 sec ( 0.2%) +DIIS Solver ... 3.042 sec ( 4.5%) +State Vector Update ... 0.122 sec ( 0.2%) +Sigma-vector construction ... 48.240 sec ( 71.1%) + <0|H|D> ... 0.006 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.029 sec ( 0.1% of sigma) + (0-ext) ... 0.085 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.031 sec ( 0.1% of sigma) + (2-ext) ... 1.140 sec ( 2.4% of sigma) + (4-ext) ... 27.807 sec ( 57.6% of sigma) + ... 1.742 sec ( 3.6% of sigma) + ... 0.003 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.128 sec ( 0.3% of sigma) + Fock-dressing ... 2.410 sec ( 5.0% of sigma) + (ik|jl)-dressing ... 0.094 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 11.883 sec ( 24.6% of sigma) + Pair energies ... 0.008 sec ( 0.0% of sigma) +Total Time for computing (T) ... 7.696 sec ( 11.3% of ALL) + I/O of integral and amplitudes ... 0.929 sec ( 12.1% of (T)) + External N**7 contributions ... 4.425 sec ( 57.5% of (T)) + Internal N**7 contributions ... 0.379 sec ( 4.9% of (T)) + N**6 triples energy contributions ... 1.863 sec ( 24.2% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.437795282449 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.009.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.009.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.416123, -0.204578 -0.593203) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 1.04408 -0.14314 -0.62269 +Nuclear contribution : -0.93858 0.46509 1.22693 + ----------------------------------------- +Total Dipole Moment : 0.10550 0.32195 0.60424 + ----------------------------------------- +Magnitude (a.u.) : 0.69274 +Magnitude (Debye) : 1.76081 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.798691 0.401776 0.361738 +Rotational constants in MHz : 83902.636223 12044.953401 10844.617653 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.241547 -0.310647 0.570125 +x,y,z [Debye]: 0.613965 -0.789602 1.449142 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.416123, -0.204578 -0.593203) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 1.07484 -0.11308 -0.79428 +Nuclear contribution : -0.93858 0.46509 1.22693 + ----------------------------------------- +Total Dipole Moment : 0.13627 0.35200 0.43265 + ----------------------------------------- +Magnitude (a.u.) : 0.57416 +Magnitude (Debye) : 1.45939 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.798691 0.401776 0.361738 +Rotational constants in MHz : 83902.636223 12044.953401 10844.617653 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.111967 -0.198161 0.527118 +x,y,z [Debye]: 0.284597 -0.503686 1.339828 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 10 * + * * + * Dihedral ( 2, 1, 0, 3) : -106.36363636 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0398970170 RMS(Int)= 0.0003995163 + Iter 1: RMS(Cart)= 0.0001116215 RMS(Int)= 0.0000029861 + Iter 2: RMS(Cart)= 0.0000008343 RMS(Int)= 0.0000000224 + Iter 3: RMS(Cart)= 0.0000000063 RMS(Int)= 0.0000000002 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4940 0.000000 + 2. B(O 2,N 1) 1.1677 0.000000 + 3. B(H 3,O 0) 0.9722 0.000000 + 4. A(N 1,O 0,H 3) 102.2321 0.000000 + 5. A(O 0,N 1,O 2) 110.4139 0.000000 + 6. D(O 2,N 1,O 0,H 3) -106.3636 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.796278 -0.210895 0.227644 + N 0.650457 -0.382404 -0.103200 + O 0.910714 0.177272 -1.094454 + H -0.764892 0.416026 0.970010 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.504748 -0.398534 0.430186 + 1 N 7.0000 0 14.007 1.229185 -0.722638 -0.195021 + 2 O 8.0000 0 15.999 1.721001 0.334996 -2.068219 + 3 H 1.0000 0 1.008 -1.445436 0.786176 1.833054 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.493736814059 0.00000000 0.00000000 + O 2 1 0 1.165651379463 110.48944470 0.00000000 + H 1 2 3 0.969419279610 102.29972609 245.45454517 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.822753494728 0.00000000 0.00000000 + O 2 1 0 2.202761874813 110.48944470 0.00000000 + H 1 2 3 1.831936947406 102.29972609 245.45454517 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2228 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2695 + la=0 lb=0: 548 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 394 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.494318097081 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.4943180971 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.915e-04 +Time for diagonalization ... 0.004 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.007 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7021902114 0.000000000000 0.00143640 0.00005253 0.0199441 0.7000 + 1 -204.7031069620 -0.000916750635 0.00135976 0.00004803 0.0165325 0.7000 + ***Turning on DIIS*** + 2 -204.7038930148 -0.000786052822 0.00381536 0.00013156 0.0134607 0.0000 + 3 -204.7084944571 -0.004601442268 0.00179255 0.00005791 0.0052692 0.0000 + 4 -204.7056092625 0.002885194600 0.00086302 0.00002923 0.0020907 0.0000 + 5 -204.7074989613 -0.001889698833 0.00075783 0.00002472 0.0011588 0.0000 + 6 -204.7066559588 0.000843002517 0.00091740 0.00002846 0.0007663 0.0000 + 7 -204.7063596839 0.000296274932 0.00035051 0.00001210 0.0004060 0.0000 + 8 -204.7071158850 -0.000756201098 0.00019046 0.00000765 0.0002000 0.0000 + 9 -204.7066505084 0.000465376549 0.00014754 0.00000636 0.0001450 0.0000 + 10 -204.7068712441 -0.000220735662 0.00006914 0.00000259 0.0000628 0.0000 + 11 -204.7069511676 -0.000079923509 0.00002302 0.00000080 0.0000339 0.0000 + 12 -204.7068350634 0.000116104206 0.00000893 0.00000030 0.0000115 0.0000 + 13 -204.7068748015 -0.000039738126 0.00000266 0.00000009 0.0000039 0.0000 + 14 -204.7068630474 0.000011754064 0.00000124 0.00000004 0.0000027 0.0000 + 15 -204.7068659562 -0.000002908716 0.00000086 0.00000002 0.0000018 0.0000 + 16 -204.7068686045 -0.000002648357 0.00000059 0.00000002 0.0000012 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 17 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70686567 Eh -5570.35701 eV + +Components: +Nuclear Repulsion : 68.49431810 Eh 1863.82515 eV +Electronic Energy : -273.20118377 Eh -7434.18216 eV +One Electron Energy: -416.70963944 Eh -11339.24577 eV +Two Electron Energy: 143.50845567 Eh 3905.06361 eV + +Virial components: +Potential Energy : -408.93071294 Eh -11127.57041 eV +Kinetic Energy : 204.22384726 Eh 5557.21341 eV +Virial Ratio : 2.00236514 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.9309e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.4217e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.7564e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 4.7496e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.689017 -562.9768 + 1 1.0000 -20.618822 -561.0667 + 2 1.0000 -15.803747 -430.0418 + 3 1.0000 -1.614388 -43.9297 + 4 1.0000 -1.374656 -37.4063 + 5 1.0000 -0.953206 -25.9381 + 6 1.0000 -0.769044 -20.9267 + 7 1.0000 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0.0000 0.030341 0.8256 + 13 0.0000 0.068204 1.8559 + 14 0.0000 0.091894 2.5006 + 15 0.0000 0.101760 2.7690 + 16 0.0000 0.113956 3.1009 + 17 0.0000 0.154666 4.2087 + 18 0.0000 0.157066 4.2740 + 19 0.0000 0.173408 4.7187 + 20 0.0000 0.183244 4.9863 + 21 0.0000 0.189589 5.1590 + 22 0.0000 0.201263 5.4766 + 23 0.0000 0.237073 6.4511 + 24 0.0000 0.271063 7.3760 + 25 0.0000 0.287931 7.8350 + 26 0.0000 0.304549 8.2872 + 27 0.0000 0.329706 8.9718 + 28 0.0000 0.333757 9.0820 + 29 0.0000 0.354942 9.6585 + 30 0.0000 0.423787 11.5318 + 31 0.0000 0.506132 13.7726 + 32 0.0000 0.525346 14.2954 + 33 0.0000 0.544619 14.8198 + 34 0.0000 0.572654 15.5827 + 35 0.0000 0.603447 16.4206 + 36 0.0000 0.628926 17.1139 + 37 0.0000 0.649527 17.6745 + 38 0.0000 0.699646 19.0383 + 39 0.0000 0.720408 19.6033 + 40 0.0000 0.740765 20.1572 + 41 0.0000 0.750519 20.4227 + 42 0.0000 0.769398 20.9364 + 43 0.0000 0.792504 21.5651 + 44 0.0000 0.809161 22.0184 + 45 0.0000 0.817350 22.2412 + 46 0.0000 0.855753 23.2862 + 47 0.0000 0.870174 23.6786 + 48 0.0000 0.900566 24.5056 + 49 0.0000 0.937861 25.5205 + 50 0.0000 0.957811 26.0634 + 51 0.0000 0.989992 26.9391 + 52 0.0000 0.997238 27.1362 + 53 0.0000 1.025286 27.8995 + 54 0.0000 1.047854 28.5136 + 55 0.0000 1.116323 30.3767 + 56 0.0000 1.140169 31.0256 + 57 0.0000 1.235879 33.6300 + 58 0.0000 1.247856 33.9559 + 59 0.0000 1.279384 34.8138 + 60 0.0000 1.325036 36.0561 + 61 0.0000 1.416449 38.5435 + 62 0.0000 1.433167 38.9985 + 63 0.0000 1.512267 41.1509 + 64 0.0000 1.524827 41.4927 + 65 0.0000 1.565660 42.6038 + 66 0.0000 1.583900 43.1001 + 67 0.0000 1.637887 44.5692 + 68 0.0000 1.650295 44.9068 + 69 0.0000 1.705056 46.3969 + 70 0.0000 1.776910 48.3522 + 71 0.0000 1.794241 48.8238 + 72 0.0000 1.883178 51.2439 + 73 0.0000 1.930621 52.5349 + 74 0.0000 1.976919 53.7947 + 75 0.0000 2.032571 55.3091 + 76 0.0000 2.066296 56.2268 + 77 0.0000 2.074506 56.4502 + 78 0.0000 2.144609 58.3578 + 79 0.0000 2.217083 60.3299 + 80 0.0000 2.241430 60.9924 + 81 0.0000 2.299658 62.5769 + 82 0.0000 2.308939 62.8294 + 83 0.0000 2.373127 64.5761 + 84 0.0000 2.410264 65.5866 + 85 0.0000 2.454098 66.7794 + 86 0.0000 2.464561 67.0641 + 87 0.0000 2.476691 67.3942 + 88 0.0000 2.509174 68.2781 + 89 0.0000 2.552801 69.4652 + 90 0.0000 2.564400 69.7809 + 91 0.0000 2.598319 70.7039 + 92 0.0000 2.673416 72.7473 + 93 0.0000 2.716393 73.9168 + 94 0.0000 2.757512 75.0357 + 95 0.0000 2.807564 76.3977 + 96 0.0000 2.844243 77.3958 + 97 0.0000 2.885614 78.5216 + 98 0.0000 2.957653 80.4818 + 99 0.0000 2.999741 81.6271 + 100 0.0000 3.057909 83.2099 + 101 0.0000 3.164725 86.1165 + 102 0.0000 3.230642 87.9102 + 103 0.0000 3.487133 94.8897 + 104 0.0000 3.729616 101.4880 + 105 0.0000 3.819488 103.9335 + 106 0.0000 4.051717 110.2528 + 107 0.0000 4.170327 113.4804 + 108 0.0000 4.184557 113.8676 + 109 0.0000 4.303870 117.1143 + 110 0.0000 4.345692 118.2523 + 111 0.0000 4.392328 119.5213 + 112 0.0000 4.532077 123.3241 + 113 0.0000 4.609996 125.4444 + 114 0.0000 4.678658 127.3127 + 115 0.0000 4.718347 128.3927 + 116 0.0000 4.805383 130.7611 + 117 0.0000 4.893205 133.1509 + 118 0.0000 4.935416 134.2995 + 119 0.0000 4.951868 134.7472 + 120 0.0000 5.058335 137.6443 + 121 0.0000 5.095225 138.6481 + 122 0.0000 5.174433 140.8035 + 123 0.0000 5.197522 141.4318 + 124 0.0000 5.217898 141.9862 + 125 0.0000 5.334670 145.1637 + 126 0.0000 5.372055 146.1810 + 127 0.0000 5.475263 148.9895 + 128 0.0000 5.531560 150.5214 + 129 0.0000 5.726835 155.8351 + 130 0.0000 5.756176 156.6335 + 131 0.0000 5.943068 161.7191 + 132 0.0000 6.177081 168.0869 + 133 0.0000 6.411417 174.4635 + 134 0.0000 6.488759 176.5681 + 135 0.0000 6.503585 176.9716 + 136 0.0000 6.700839 182.3391 + 137 0.0000 6.723702 182.9612 + 138 0.0000 6.768499 184.1802 + 139 0.0000 6.811381 185.3471 + 140 0.0000 6.834383 185.9730 + 141 0.0000 7.062450 192.1790 + 142 0.0000 7.104273 193.3171 + 143 0.0000 7.121176 193.7771 + 144 0.0000 7.195789 195.8074 + 145 0.0000 7.256394 197.4565 + 146 0.0000 7.279459 198.0842 + 147 0.0000 7.345770 199.8886 + 148 0.0000 7.392649 201.1642 + 149 0.0000 7.449948 202.7234 + 150 0.0000 7.461060 203.0258 + 151 0.0000 7.543689 205.2742 + 152 0.0000 7.596294 206.7057 + 153 0.0000 7.605047 206.9438 + 154 0.0000 7.765879 211.3203 + 155 0.0000 7.898240 214.9220 + 156 0.0000 7.948963 216.3023 + 157 0.0000 8.395690 228.4583 + 158 0.0000 14.069820 382.8593 + 159 0.0000 14.796693 402.6385 + 160 0.0000 16.043619 436.5691 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.373902 0.000000 + 1 N : 0.351751 0.000000 + 2 O : -0.232923 0.000000 + 3 H : 0.255073 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.868904 s : 3.868904 + pz : 1.574539 p : 4.476671 + px : 1.243813 + py : 1.658320 + dz2 : 0.004754 d : 0.023893 + dxz : 0.002499 + dyz : 0.002474 + dx2y2 : 0.010716 + dxy : 0.003448 + f0 : 0.000429 f : 0.004434 + f+1 : 0.000803 + f-1 : 0.000584 + f+2 : 0.000443 + f-2 : 0.000087 + f+3 : 0.001164 + f-3 : 0.000925 + 1 N s : 3.821746 s : 3.821746 + pz : 0.946237 p : 2.660299 + px : 0.835225 + py : 0.878838 + dz2 : 0.035795 d : 0.135591 + dxz : 0.030872 + dyz : 0.016161 + dx2y2 : 0.030710 + dxy : 0.022053 + f0 : 0.005100 f : 0.030612 + f+1 : 0.006598 + f-1 : 0.002923 + f+2 : 0.004001 + f-2 : 0.003100 + f+3 : 0.003579 + f-3 : 0.005311 + 2 O s : 3.876958 s : 3.876958 + pz : 1.196559 p : 4.285636 + px : 1.813533 + py : 1.275544 + dz2 : 0.024833 d : 0.062813 + dxz : 0.011442 + dyz : 0.014997 + dx2y2 : 0.005095 + dxy : 0.006447 + f0 : 0.002469 f : 0.007516 + f+1 : 0.001224 + f-1 : 0.001214 + f+2 : 0.000908 + f-2 : 0.001058 + f+3 : 0.000348 + f-3 : 0.000293 + 3 H s : 0.639182 s : 0.639182 + pz : 0.031694 p : 0.085465 + px : 0.021097 + py : 0.032675 + dz2 : 0.007736 d : 0.020280 + dxz : 0.005923 + dyz : 0.000121 + dx2y2 : 0.002454 + dxy : 0.004046 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.574290 0.000000 + 1 N : -0.238214 0.000000 + 2 O : 0.247843 0.000000 + 3 H : -0.583918 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.134898 s : 3.134898 + pz : 1.369073 p : 3.953704 + px : 1.172994 + py : 1.411637 + dz2 : 0.041459 d : 0.260615 + dxz : 0.057132 + dyz : 0.028104 + dx2y2 : 0.083702 + dxy : 0.050217 + f0 : 0.005589 f : 0.076494 + f+1 : 0.016759 + f-1 : 0.004680 + f+2 : 0.014962 + f-2 : 0.003174 + f+3 : 0.014618 + f-3 : 0.016713 + 1 N s : 3.033423 s : 3.033423 + pz : 1.073699 p : 2.840255 + px : 0.884523 + py : 0.882033 + dz2 : 0.194564 d : 0.924124 + dxz : 0.263734 + dyz : 0.159178 + dx2y2 : 0.170377 + dxy : 0.136272 + f0 : 0.064599 f : 0.440411 + f+1 : 0.090436 + f-1 : 0.060434 + f+2 : 0.068957 + f-2 : 0.052003 + f+3 : 0.045553 + f-3 : 0.058428 + 2 O s : 3.316737 s : 3.316737 + pz : 1.313999 p : 3.986972 + px : 1.487187 + py : 1.185786 + dz2 : 0.083760 d : 0.330479 + dxz : 0.082518 + dyz : 0.102429 + dx2y2 : 0.039768 + dxy : 0.022003 + f0 : 0.021761 f : 0.117970 + f+1 : 0.018995 + f-1 : 0.029595 + f+2 : 0.025057 + f-2 : 0.015208 + f+3 : 0.002473 + f-3 : 0.004881 + 3 H s : 0.625338 s : 0.625338 + pz : 0.222019 p : 0.568445 + px : 0.135922 + py : 0.210504 + dz2 : 0.107619 d : 0.390135 + dxz : 0.076462 + dyz : 0.097804 + dx2y2 : 0.055714 + dxy : 0.052536 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3739 8.0000 -0.3739 1.8278 1.8278 0.0000 + 1 N 6.6482 7.0000 0.3518 2.5893 2.5893 0.0000 + 2 O 8.2329 8.0000 -0.2329 1.8022 1.8022 0.0000 + 3 H 0.7449 1.0000 0.2551 0.9812 0.9812 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8180 B( 0-O , 3-H ) : 0.9561 B( 1-N , 2-O ) : 1.7474 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 3 sec + +Total time .... 3.019 sec +Sum of individual times .... 2.815 sec ( 93.2%) + +Fock matrix formation .... 2.373 sec ( 78.6%) +Diagonalization .... 0.216 sec ( 7.2%) +Density matrix formation .... 0.017 sec ( 0.6%) +Population analysis .... 0.024 sec ( 0.8%) +Initial guess .... 0.010 sec ( 0.3%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.2%) +DIIS solution .... 0.175 sec ( 5.8%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.288 sec +Reference energy ... -204.706866536 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.660 sec +AO-integral generation ... 0.155 sec +Half transformation ... 0.086 sec +K-integral sorting ... 5.592 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.033 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.031 s ( 0.000 ms/b) + 277134 b 0 skpd 0.035 s ( 0.000 ms/b) +: : 151164 b 0 skpd 0.042 s ( 0.000 ms/b) + 159120 b 0 skpd 0.023 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.043 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.039 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.050 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.030 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.426 sec +AO-integral generation ... 0.309 sec +Half transformation ... 0.047 sec +J-integral sorting ... 0.054 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.160 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.258 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090052807 +EMP2(bb)= -0.090052807 +EMP2(ab)= -0.517355833 + +Initial guess performed in 0.137 sec +E(0) ... -204.706866536 +E(MP2) ... -0.697461447 +Initial E(tot) ... -205.404327982 + ... 0.189395811 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.404327982 -0.697461447 -0.000000000 0.019097562 3.04 0.000001555 + *** Turning on DIIS *** + 1 -205.376035112 -0.669168576 0.028292871 0.010408875 3.24 0.055541344 + 2 -205.395543379 -0.688676844 -0.019508267 0.003785078 3.44 0.058327412 + 3 -205.399365061 -0.692498525 -0.003821681 0.001968467 3.39 0.071354743 + 4 -205.400900167 -0.694033631 -0.001535106 0.000952341 4.39 0.077158852 + 5 -205.401389342 -0.694522807 -0.000489176 0.000573314 4.65 0.081538641 + 6 -205.401469884 -0.694603349 -0.000080542 0.000393783 4.51 0.083564943 + 7 -205.401502357 -0.694635821 -0.000032472 0.000237487 3.30 0.084486394 + 8 -205.401510153 -0.694643618 -0.000007796 0.000142277 3.19 0.084897128 + 9 -205.401506890 -0.694640355 0.000003263 0.000084239 3.16 0.085063047 + 10 -205.401511769 -0.694645233 -0.000004878 0.000050009 3.86 0.085144805 + 11 -205.401508366 -0.694641831 0.000003402 0.000031072 3.64 0.085156701 + 12 -205.401510964 -0.694644428 -0.000002598 0.000018294 3.70 0.085174693 + 13 -205.401510877 -0.694644341 0.000000087 0.000010495 3.33 0.085174327 + 14 -205.401511312 -0.694644776 -0.000000435 0.000005465 3.76 0.085180361 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.706866536 +E(CORR) ... -0.694644776 +E(TOT) ... -205.401511312 +Singles norm **1/2 ... 0.085180361 ( 0.042590181, 0.042590181) +T1 diagnostic ... 0.020077204 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.060682 + 8a-> 13a 8b-> 13b 0.052010 + 8a-> 13a 9b-> 13b 0.046444 + 9a-> 13a 8b-> 13b 0.046444 + 5a-> 13a 5b-> 13b 0.029772 + 8a-> 13a -1a-> -1a 0.027939 + 8b-> 13b -1b-> -1b 0.027939 + 11a-> 13a 11b-> 13b 0.027921 + 11a-> 25a 11b-> 25b 0.023766 + 9a-> 22a 9b-> 13b 0.022900 + 9a-> 13a 9b-> 22b 0.022900 + 11b-> 25b -1b-> -1b 0.020864 + 11a-> 25a -1a-> -1a 0.020864 + 11a-> 25a 11b-> 24b 0.019227 + 11a-> 24a 11b-> 25b 0.019227 + 11a-> 24a 11b-> 24b 0.017853 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034463373 + alpha-alpha-alpha ... -0.000863177 ( 2.5%) + alpha-alpha-beta ... -0.016368509 ( 47.5%) + alpha-beta -beta ... -0.016368509 ( 47.5%) + beta -beta -beta ... -0.000863177 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034463373 + +Final correlation energy ... -0.729108149 +E(CCSD) ... -205.401511312 +E(CCSD(T)) ... -205.435974685 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210254482 sqrt= 1.100115667 +W(HF) = 0.826272503 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.312834 0.000000 + 1 N : 0.178685 0.000000 + 2 O : -0.108264 -0.000000 + 3 H : 0.242412 -0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.845005 s : 3.845005 + pz : 1.553307 p : 4.404634 + px : 1.232682 + py : 1.618646 + dz2 : 0.011126 d : 0.055027 + dxz : 0.009409 + dyz : 0.008714 + dx2y2 : 0.014856 + dxy : 0.010922 + f0 : 0.000998 f : 0.008167 + f+1 : 0.001250 + f-1 : 0.001232 + f+2 : 0.001013 + f-2 : 0.000777 + f+3 : 0.001445 + f-3 : 0.001451 + 1 N s : 3.876450 s : 3.876450 + pz : 0.946782 p : 2.749669 + px : 0.883977 + py : 0.918909 + dz2 : 0.036150 d : 0.165487 + dxz : 0.042155 + dyz : 0.020416 + dx2y2 : 0.036627 + dxy : 0.030138 + f0 : 0.003922 f : 0.029709 + f+1 : 0.006555 + f-1 : 0.003007 + f+2 : 0.003946 + f-2 : 0.003155 + f+3 : 0.003701 + f-3 : 0.005424 + 2 O s : 3.864012 s : 3.864012 + pz : 1.178731 p : 4.150621 + px : 1.727599 + py : 1.244290 + dz2 : 0.024817 d : 0.083729 + dxz : 0.018357 + dyz : 0.017539 + dx2y2 : 0.010913 + dxy : 0.012102 + f0 : 0.002295 f : 0.009903 + f+1 : 0.001728 + f-1 : 0.001421 + f+2 : 0.001268 + f-2 : 0.001457 + f+3 : 0.000903 + f-3 : 0.000831 + 3 H s : 0.647263 s : 0.647263 + pz : 0.032202 p : 0.092914 + px : 0.024306 + py : 0.036406 + dz2 : 0.006650 d : 0.017411 + dxz : 0.005392 + dyz : -0.000592 + dx2y2 : 0.002300 + dxy : 0.003661 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.580394 0.000000 + 1 N : -0.282193 0.000000 + 2 O : 0.290008 -0.000000 + 3 H : -0.588209 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.139217 s : 3.139217 + pz : 1.351575 p : 3.905741 + px : 1.176098 + py : 1.378068 + dz2 : 0.047327 d : 0.291313 + dxz : 0.063144 + dyz : 0.035192 + dx2y2 : 0.090329 + dxy : 0.055320 + f0 : 0.006521 f : 0.083336 + f+1 : 0.017280 + f-1 : 0.005641 + f+2 : 0.016116 + f-2 : 0.003929 + f+3 : 0.016294 + f-3 : 0.017555 + 1 N s : 3.038341 s : 3.038341 + pz : 1.069291 p : 2.880201 + px : 0.906489 + py : 0.904420 + dz2 : 0.192924 d : 0.932837 + dxz : 0.264104 + dyz : 0.162714 + dx2y2 : 0.175767 + dxy : 0.137327 + f0 : 0.062786 f : 0.430814 + f+1 : 0.088324 + f-1 : 0.060591 + f+2 : 0.066489 + f-2 : 0.049683 + f+3 : 0.046782 + f-3 : 0.056160 + 2 O s : 3.319460 s : 3.319460 + pz : 1.304001 p : 3.905869 + px : 1.431985 + py : 1.169883 + dz2 : 0.091000 d : 0.358399 + dxz : 0.085915 + dyz : 0.107825 + dx2y2 : 0.045574 + dxy : 0.028085 + f0 : 0.025189 f : 0.126264 + f+1 : 0.019996 + f-1 : 0.030066 + f+2 : 0.025570 + f-2 : 0.016642 + f+3 : 0.003458 + f-3 : 0.005342 + 3 H s : 0.625599 s : 0.625599 + pz : 0.228825 p : 0.582419 + px : 0.135811 + py : 0.217783 + dz2 : 0.103909 d : 0.380192 + dxz : 0.073461 + dyz : 0.096801 + dx2y2 : 0.055233 + dxy : 0.050787 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3128 8.0000 -0.3128 2.1716 1.7098 0.4618 + 1 N 6.8213 7.0000 0.1787 2.8544 2.3609 0.4935 + 2 O 8.1083 8.0000 -0.1083 2.1884 1.6892 0.4992 + 3 H 0.7576 1.0000 0.2424 1.0041 0.9301 0.0740 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7304 B( 0-O , 3-H ) : 0.8937 B( 1-N , 2-O ) : 1.5988 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 71.288 sec + +Fock Matrix Formation ... 0.288 sec ( 0.4%) +Initial Guess ... 0.137 sec ( 0.2%) +DIIS Solver ... 2.898 sec ( 4.1%) +State Vector Update ... 0.132 sec ( 0.2%) +Sigma-vector construction ... 51.569 sec ( 72.3%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (0-ext) ... 0.081 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.031 sec ( 0.1% of sigma) + (2-ext) ... 1.121 sec ( 2.2% of sigma) + (4-ext) ... 30.364 sec ( 58.9% of sigma) + ... 2.244 sec ( 4.4% of sigma) + ... 0.003 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.136 sec ( 0.3% of sigma) + Fock-dressing ... 2.678 sec ( 5.2% of sigma) + (ik|jl)-dressing ... 0.089 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 11.859 sec ( 23.0% of sigma) + Pair energies ... 0.011 sec ( 0.0% of sigma) +Total Time for computing (T) ... 7.891 sec ( 11.1% of ALL) + I/O of integral and amplitudes ... 0.813 sec ( 10.3% of (T)) + External N**7 contributions ... 4.089 sec ( 51.8% of (T)) + Internal N**7 contributions ... 0.328 sec ( 4.2% of (T)) + N**6 triples energy contributions ... 1.753 sec ( 22.2% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.435974684995 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.001559380 -0.005773192 0.002209805 + 2 N : -0.002771720 -0.006441766 -0.000548632 + 3 O : 0.000951909 0.005933804 0.000418014 + 4 H : 0.000260431 0.006281155 -0.002079186 + +Norm of the cartesian gradient ... 0.013048336 +RMS gradient ... 0.003766730 +MAX gradient ... 0.006441766 + +------- +TIMINGS +------- + +Total numerical gradient time ... 412.772 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: -454.46 cm**-1 ***imaginary mode*** + 7: 561.79 cm**-1 + 8: 788.37 cm**-1 + 9: 1142.77 cm**-1 + 10: 1701.60 cm**-1 + 11: 3713.99 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 -0.012588 -0.572250 0.194513 0.053636 -0.087634 -0.000831 + 1 -0.040359 -0.056877 -0.194589 0.022992 0.013573 -0.039954 + 2 0.054357 0.323740 0.183349 0.037287 0.002289 -0.048309 + 3 0.005058 0.253571 -0.699305 -0.012203 -0.054093 -0.000038 + 4 -0.064119 0.112115 0.253860 -0.030332 -0.382238 0.000454 + 5 -0.044953 -0.225111 -0.072371 -0.028053 0.634182 -0.000744 + 6 0.010396 0.357077 0.392318 0.019439 0.128988 -0.000510 + 7 0.047779 -0.026533 -0.028322 0.005115 0.319898 -0.000684 + 8 0.024193 -0.156065 -0.120456 -0.019427 -0.558705 0.000663 + 9 -0.035499 -0.108346 0.403216 -0.990279 0.095293 0.021813 + 10 0.773215 -0.234045 0.010466 -0.024625 0.018667 0.638716 + 11 -0.622095 0.466760 0.007425 0.106343 0.018963 0.766572 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 7: 561.79 0.024967 126.17 0.013869 ( 0.101292 -0.001670 -0.060050) + 8: 788.37 0.020250 102.33 0.008016 (-0.081321 0.008434 0.036486) + 9: 1142.77 0.016736 84.58 0.004570 (-0.061265 0.015058 0.024292) + 10: 1701.60 0.031617 159.78 0.005798 (-0.057299 -0.011166 0.048894) + 11: 3713.99 0.012426 62.79 0.001044 (-0.013608 0.016176 0.024437) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 7 +The total number of vibrations considered is 5 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 561.79 E(vib) ... 0.11 +freq. 788.37 E(vib) ... 0.05 +freq. 1142.77 E(vib) ... 0.01 +freq. 1701.60 E(vib) ... 0.00 +freq. 3713.99 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.43597468 Eh +Zero point energy ... 0.01801694 Eh 11.31 kcal/mol +Thermal vibrational correction ... 0.00028727 Eh 0.18 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.41483794 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00311981 Eh 1.96 kcal/mol +Non-thermal (ZPE) correction 0.01801694 Eh 11.31 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02113675 Eh 13.26 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.41483794 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.41389373 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.751286 0.402356 0.362746 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00037792 Eh 0.24 kcal/mol +Rotational entropy ... 0.00994155 Eh 6.24 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02812178 Eh 17.65 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00994155 Eh 6.24 kcal/mol| +| sn= 2 | S(rot)= 0.00928709 Eh 5.83 kcal/mol| +| sn= 3 | S(rot)= 0.00890426 Eh 5.59 kcal/mol| +| sn= 4 | S(rot)= 0.00863263 Eh 5.42 kcal/mol| +| sn= 5 | S(rot)= 0.00842195 Eh 5.28 kcal/mol| +| sn= 6 | S(rot)= 0.00824980 Eh 5.18 kcal/mol| +| sn= 7 | S(rot)= 0.00810425 Eh 5.09 kcal/mol| +| sn= 8 | S(rot)= 0.00797818 Eh 5.01 kcal/mol| +| sn= 9 | S(rot)= 0.00786697 Eh 4.94 kcal/mol| +| sn=10 | S(rot)= 0.00776749 Eh 4.87 kcal/mol| +| sn=11 | S(rot)= 0.00767750 Eh 4.82 kcal/mol| +| sn=12 | S(rot)= 0.00759534 Eh 4.77 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.41389373 Eh +Total entropy correction ... -0.02812178 Eh -17.65 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44201551 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00604083 Eh -3.79 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.435974685 Eh +Current gradient norm .... 0.013048336 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + -0.024711064 0.101707410 0.159703725 0.477914285 0.497745177 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999846508 +Lowest eigenvalues of augmented Hessian: + -0.000062177 0.101296028 0.159344815 0.477773658 0.497721519 +Length of the computed step .... 0.017522993 +The final length of the internal step .... 0.017522993 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0071537319 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0048297239 RMS(Int)= 0.0071579543 + Iter 1: RMS(Cart)= 0.0000062894 RMS(Int)= 0.0000109523 + Iter 2: RMS(Cart)= 0.0000000261 RMS(Int)= 0.0000000372 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0018554711 0.0001000000 NO + MAX gradient 0.0027016639 0.0003000000 NO + RMS step 0.0071537319 0.0020000000 NO + MAX step 0.0150505979 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0080 Max(Angles) 0.21 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4940 -0.001675 0.0080 1.5019 + 2. B(O 2,N 1) 1.1677 0.002702 -0.0030 1.1647 + 3. B(H 3,O 0) 0.9722 0.002471 -0.0027 0.9695 + 4. A(N 1,O 0,H 3) 102.23 -0.000968 0.21 102.45 + 5. A(O 0,N 1,O 2) 110.41 -0.001873 0.17 110.58 + 6. D(O 2,N 1,O 0,H 3) -106.36 0.010992 0.00 -106.36 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.799107 -0.209228 0.230955 + N 0.654091 -0.381965 -0.106914 + O 0.913584 0.175851 -1.095865 + H -0.768566 0.415342 0.971823 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.510094 -0.395383 0.436442 + 1 N 7.0000 0 14.007 1.236052 -0.721809 -0.202037 + 2 O 8.0000 0 15.999 1.726423 0.332310 -2.070885 + 3 H 1.0000 0 1.008 -1.452379 0.784883 1.836480 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.501924477094 0.00000000 0.00000000 + O 2 1 0 1.164697264893 110.57910728 0.00000000 + H 1 2 3 0.969487363522 102.44613785 253.63636358 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.838225935541 0.00000000 0.00000000 + O 2 1 0 2.200958859575 110.57910728 0.00000000 + H 1 2 3 1.832065607354 102.44613785 253.63636358 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2693 + la=0 lb=0: 548 shell pairs + la=1 lb=0: 534 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 394 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.408015475556 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.920e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7067019855 0.000000000000 0.00019271 0.00000642 0.0012624 0.7000 + 1 -204.7067129752 -0.000010989694 0.00016142 0.00000549 0.0010348 0.7000 + ***Turning on DIIS*** + 2 -204.7067221293 -0.000009154180 0.00047928 0.00001497 0.0008487 0.0000 + 3 -204.7063603527 0.000361776609 0.00023321 0.00000690 0.0002945 0.0000 + 4 -204.7068562002 -0.000495847515 0.00007086 0.00000293 0.0000914 0.0000 + 5 -204.7069619585 -0.000105758215 0.00004347 0.00000129 0.0000772 0.0000 + 6 -204.7066568769 0.000305081568 0.00003006 0.00000111 0.0000394 0.0000 + 7 -204.7068020161 -0.000145139200 0.00001587 0.00000072 0.0000188 0.0000 + 8 -204.7067520456 0.000049970541 0.00001405 0.00000053 0.0000123 0.0000 + 9 -204.7067213602 0.000030685398 0.00000646 0.00000028 0.0000072 0.0000 + 10 -204.7067638651 -0.000042504948 0.00000439 0.00000017 0.0000031 0.0000 + 11 -204.7067484660 0.000015399112 0.00000119 0.00000005 0.0000010 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + +Total Energy : -204.70675270 Eh -5570.35393 eV + Last Energy change ... -4.2328e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.1482e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.205 sec +Reference energy ... -204.706753653 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.408 sec +AO-integral generation ... 0.143 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.410 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.024 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.028 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.032 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.023 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.361 sec +AO-integral generation ... 0.246 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.055 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.154 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.253 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090070094 +EMP2(bb)= -0.090070094 +EMP2(ab)= -0.517493212 + +Initial guess performed in 0.134 sec +E(0) ... -204.706753653 +E(MP2) ... -0.697633400 +Initial E(tot) ... -205.404387053 + ... 0.189596829 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.404387053 -0.697633400 -0.000000000 0.019096478 2.78 0.000000722 + *** Turning on DIIS *** + 1 -205.375953328 -0.669199674 0.028433726 0.010125199 2.72 0.055712467 + 2 -205.395501347 -0.688747694 -0.019548020 0.003763630 2.89 0.058441750 + 3 -205.399323886 -0.692570232 -0.003822538 0.001910573 2.80 0.071499824 + 4 -205.400862640 -0.694108987 -0.001538755 0.000913023 2.80 0.077316769 + 5 -205.401353883 -0.694600229 -0.000491243 0.000576111 2.82 0.081722671 + 6 -205.401434798 -0.694681145 -0.000080915 0.000395741 2.78 0.083775209 + 7 -205.401467900 -0.694714246 -0.000033101 0.000236580 2.85 0.084720601 + 8 -205.401475863 -0.694722209 -0.000007963 0.000142051 2.85 0.085139600 + 9 -205.401472522 -0.694718869 0.000003340 0.000084355 2.78 0.085306448 + 10 -205.401477485 -0.694723832 -0.000004963 0.000049921 2.74 0.085389356 + 11 -205.401474011 -0.694720358 0.000003474 0.000030992 2.73 0.085400584 + 12 -205.401476670 -0.694723017 -0.000002659 0.000018021 2.75 0.085419380 + 13 -205.401476563 -0.694722910 0.000000107 0.000010475 2.99 0.085418412 + 14 -205.401477000 -0.694723347 -0.000000437 0.000005430 2.81 0.085424459 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.706753653 +E(CORR) ... -0.694723347 +E(TOT) ... -205.401477000 +Singles norm **1/2 ... 0.085424459 ( 0.042712229, 0.042712229) +T1 diagnostic ... 0.020134738 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.058348 + 8a-> 13a 8b-> 13b 0.053931 + 9a-> 13a 8b-> 13b 0.046407 + 8a-> 13a 9b-> 13b 0.046407 + 5a-> 13a 5b-> 13b 0.029898 + 8b-> 13b -1b-> -1b 0.027749 + 8a-> 13a -1a-> -1a 0.027749 + 11a-> 13a 11b-> 13b 0.027578 + 11a-> 25a 11b-> 25b 0.022932 + 11a-> 24a 11b-> 24b 0.022475 + 9a-> 22a 9b-> 13b 0.022151 + 9a-> 13a 9b-> 22b 0.022151 + 11a-> 25a 11b-> 24b 0.021332 + 11a-> 24a 11b-> 25b 0.021332 + 11b-> 25b -1b-> -1b 0.019951 + 11a-> 25a -1a-> -1a 0.019951 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034528870 + alpha-alpha-alpha ... -0.000863448 ( 2.5%) + alpha-alpha-beta ... -0.016400987 ( 47.5%) + alpha-beta -beta ... -0.016400987 ( 47.5%) + beta -beta -beta ... -0.000863448 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034528870 + +Final correlation energy ... -0.729252216 +E(CCSD) ... -205.401477000 +E(CCSD(T)) ... -205.436005870 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210479030 sqrt= 1.100217719 +W(HF) = 0.826119227 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 57.339 sec + +Fock Matrix Formation ... 0.205 sec ( 0.4%) +Initial Guess ... 0.134 sec ( 0.2%) +DIIS Solver ... 1.949 sec ( 3.4%) +State Vector Update ... 0.092 sec ( 0.2%) +Sigma-vector construction ... 40.059 sec ( 69.9%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (0-ext) ... 0.073 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (2-ext) ... 0.998 sec ( 2.5% of sigma) + (4-ext) ... 22.232 sec ( 55.5% of sigma) + ... 1.417 sec ( 3.5% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.114 sec ( 0.3% of sigma) + Fock-dressing ... 2.210 sec ( 5.5% of sigma) + (ik|jl)-dressing ... 0.079 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.140 sec ( 25.3% of sigma) + Pair energies ... 0.006 sec ( 0.0% of sigma) +Total Time for computing (T) ... 7.027 sec ( 12.3% of ALL) + I/O of integral and amplitudes ... 0.777 sec ( 11.1% of (T)) + External N**7 contributions ... 3.910 sec ( 55.6% of (T)) + Internal N**7 contributions ... 0.320 sec ( 4.5% of (T)) + N**6 triples energy contributions ... 1.707 sec ( 24.3% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.436005869802 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.000744202 -0.004060144 0.005133183 + 2 N : -0.001516117 -0.004807535 -0.004058544 + 3 O : 0.001110678 0.004275428 0.002806592 + 4 H : -0.000338764 0.004592250 -0.003881231 + +Norm of the cartesian gradient ... 0.012203618 +RMS gradient ... 0.003522881 +MAX gradient ... 0.005133183 + +------- +TIMINGS +------- + +Total numerical gradient time ... 371.261 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.436005870 Eh +Current gradient norm .... 0.012203618 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999956 +Lowest eigenvalues of augmented Hessian: + -0.000000023 0.100752679 0.157987710 0.475864213 0.499785569 +Length of the computed step .... 0.000297418 +The final length of the internal step .... 0.000297418 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0001214203 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001126780 RMS(Int)= 0.0001214210 + Iter 1: RMS(Cart)= 0.0000000022 RMS(Int)= 0.0000000031 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000311850 0.0000050000 NO + RMS gradient 0.0000465616 0.0001000000 YES + MAX gradient 0.0000876475 0.0003000000 YES + RMS step 0.0001214203 0.0020000000 YES + MAX step 0.0002717291 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.5019 -0.000050 0.0001 1.5021 + 2. B(O 2,N 1) 1.1647 -0.000088 0.0000 1.1647 + 3. B(H 3,O 0) 0.9695 -0.000018 0.0000 0.9695 + 4. A(N 1,O 0,H 3) 102.45 -0.000024 0.00 102.45 + 5. A(O 0,N 1,O 2) 110.58 -0.000044 0.00 110.58 + 6. D(O 2,N 1,O 0,H 3) -106.36 0.010777 0.00 -106.36 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.799163 -0.209216 0.231008 + N 0.654156 -0.381980 -0.106966 + O 0.913670 0.175841 -1.095944 + H -0.768663 0.415355 0.971901 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.510198 -0.395360 0.436543 + 1 N 7.0000 0 14.007 1.236176 -0.721838 -0.202136 + 2 O 8.0000 0 15.999 1.726586 0.332292 -2.071034 + 3 H 1.0000 0 1.008 -1.452562 0.784906 1.836627 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.502068269921 0.00000000 0.00000000 + O 2 1 0 1.164727483571 110.58204511 0.00000000 + H 1 2 3 0.969505191682 102.45113132 253.63636358 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.838497664603 0.00000000 0.00000000 + O 2 1 0 2.201015964601 110.58204511 0.00000000 + H 1 2 3 1.832099297694 102.45113132 253.63636358 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2693 + la=0 lb=0: 548 shell pairs + la=1 lb=0: 534 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 394 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.403747669692 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.4037476697 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.920e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.003 sec +Total time needed ... 0.006 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7067346425 0.000000000000 0.00000537 0.00000011 0.0000250 0.7000 + 1 -204.7067346454 -0.000000002953 0.00000441 0.00000009 0.0000194 0.7000 + ***Turning on DIIS*** + 2 -204.7067346480 -0.000000002517 0.00001066 0.00000024 0.0000149 0.0000 + 3 -204.7067443111 -0.000009663123 0.00000439 0.00000010 0.0000034 0.0000 + 4 -204.7067330407 0.000011270425 0.00000114 0.00000004 0.0000012 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70673062 Eh -5570.35333 eV + +Components: +Nuclear Repulsion : 68.40374767 Eh 1861.36060 eV +Electronic Energy : -273.11047829 Eh -7431.71394 eV +One Electron Energy: -416.52309519 Eh -11334.16964 eV +Two Electron Energy: 143.41261690 Eh 3902.45570 eV + +Virial components: +Potential Energy : -408.93630612 Eh -11127.72261 eV +Kinetic Energy : 204.22957550 Eh 5557.36928 eV +Virial Ratio : 2.00233637 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.4182e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.0352e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.5779e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.3039e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.690813 -563.0256 + 1 1.0000 -20.616880 -561.0138 + 2 1.0000 -15.804629 -430.0658 + 3 1.0000 -1.617265 -44.0080 + 4 1.0000 -1.372542 -37.3488 + 5 1.0000 -0.953476 -25.9454 + 6 1.0000 -0.769355 -20.9352 + 7 1.0000 -0.731069 -19.8934 + 8 1.0000 -0.698947 -19.0193 + 9 1.0000 -0.607408 -16.5284 + 10 1.0000 -0.528565 -14.3830 + 11 1.0000 -0.457984 -12.4624 + 12 0.0000 0.030590 0.8324 + 13 0.0000 0.068328 1.8593 + 14 0.0000 0.091590 2.4923 + 15 0.0000 0.101713 2.7677 + 16 0.0000 0.114200 3.1075 + 17 0.0000 0.154807 4.2125 + 18 0.0000 0.157218 4.2781 + 19 0.0000 0.173338 4.7168 + 20 0.0000 0.182982 4.9792 + 21 0.0000 0.189735 5.1629 + 22 0.0000 0.201107 5.4724 + 23 0.0000 0.236599 6.4382 + 24 0.0000 0.269819 7.3422 + 25 0.0000 0.286454 7.7948 + 26 0.0000 0.304151 8.2764 + 27 0.0000 0.329393 8.9632 + 28 0.0000 0.333560 9.0766 + 29 0.0000 0.354846 9.6559 + 30 0.0000 0.425079 11.5670 + 31 0.0000 0.506088 13.7714 + 32 0.0000 0.525178 14.2908 + 33 0.0000 0.543908 14.8005 + 34 0.0000 0.572505 15.5787 + 35 0.0000 0.603274 16.4159 + 36 0.0000 0.630159 17.1475 + 37 0.0000 0.650590 17.7035 + 38 0.0000 0.699127 19.0242 + 39 0.0000 0.720694 19.6111 + 40 0.0000 0.740075 20.1385 + 41 0.0000 0.749503 20.3950 + 42 0.0000 0.769491 20.9389 + 43 0.0000 0.792393 21.5621 + 44 0.0000 0.809444 22.0261 + 45 0.0000 0.817018 22.2322 + 46 0.0000 0.855686 23.2844 + 47 0.0000 0.870175 23.6787 + 48 0.0000 0.900726 24.5100 + 49 0.0000 0.938519 25.5384 + 50 0.0000 0.957846 26.0643 + 51 0.0000 0.990718 26.9588 + 52 0.0000 0.997805 27.1517 + 53 0.0000 1.025864 27.9152 + 54 0.0000 1.048417 28.5289 + 55 0.0000 1.115596 30.3569 + 56 0.0000 1.138962 30.9927 + 57 0.0000 1.235258 33.6131 + 58 0.0000 1.247440 33.9446 + 59 0.0000 1.279526 34.8177 + 60 0.0000 1.324045 36.0291 + 61 0.0000 1.417896 38.5829 + 62 0.0000 1.435593 39.0645 + 63 0.0000 1.513867 41.1944 + 64 0.0000 1.523829 41.4655 + 65 0.0000 1.564848 42.5817 + 66 0.0000 1.583490 43.0889 + 67 0.0000 1.637203 44.5506 + 68 0.0000 1.649982 44.8983 + 69 0.0000 1.704632 46.3854 + 70 0.0000 1.775623 48.3172 + 71 0.0000 1.793369 48.8001 + 72 0.0000 1.882469 51.2246 + 73 0.0000 1.930531 52.5324 + 74 0.0000 1.975919 53.7675 + 75 0.0000 2.030372 55.2492 + 76 0.0000 2.062755 56.1304 + 77 0.0000 2.074331 56.4454 + 78 0.0000 2.143184 58.3190 + 79 0.0000 2.216688 60.3192 + 80 0.0000 2.239655 60.9441 + 81 0.0000 2.300051 62.5876 + 82 0.0000 2.307973 62.8031 + 83 0.0000 2.373557 64.5878 + 84 0.0000 2.410246 65.5861 + 85 0.0000 2.453294 66.7575 + 86 0.0000 2.461411 66.9784 + 87 0.0000 2.477020 67.4031 + 88 0.0000 2.508492 68.2595 + 89 0.0000 2.552543 69.4582 + 90 0.0000 2.562212 69.7213 + 91 0.0000 2.599224 70.7285 + 92 0.0000 2.675575 72.8061 + 93 0.0000 2.713088 73.8269 + 94 0.0000 2.757974 75.0483 + 95 0.0000 2.806399 76.3660 + 96 0.0000 2.843318 77.3706 + 97 0.0000 2.883098 78.4531 + 98 0.0000 2.952770 80.3490 + 99 0.0000 2.996116 81.5285 + 100 0.0000 3.053457 83.0888 + 101 0.0000 3.163093 86.0721 + 102 0.0000 3.234220 88.0076 + 103 0.0000 3.487023 94.8867 + 104 0.0000 3.732568 101.5683 + 105 0.0000 3.817283 103.8735 + 106 0.0000 4.053518 110.3018 + 107 0.0000 4.174662 113.5983 + 108 0.0000 4.188250 113.9681 + 109 0.0000 4.305733 117.1650 + 110 0.0000 4.344543 118.2210 + 111 0.0000 4.392954 119.5384 + 112 0.0000 4.534175 123.3812 + 113 0.0000 4.611841 125.4946 + 114 0.0000 4.674399 127.1969 + 115 0.0000 4.721300 128.4731 + 116 0.0000 4.807666 130.8232 + 117 0.0000 4.895365 133.2097 + 118 0.0000 4.933613 134.2504 + 119 0.0000 4.954704 134.8243 + 120 0.0000 5.056820 137.6031 + 121 0.0000 5.096173 138.6739 + 122 0.0000 5.179014 140.9281 + 123 0.0000 5.198775 141.4659 + 124 0.0000 5.213696 141.8719 + 125 0.0000 5.340341 145.3181 + 126 0.0000 5.371483 146.1655 + 127 0.0000 5.471752 148.8939 + 128 0.0000 5.527683 150.4159 + 129 0.0000 5.728147 155.8708 + 130 0.0000 5.752286 156.5276 + 131 0.0000 5.933677 161.4636 + 132 0.0000 6.176656 168.0754 + 133 0.0000 6.410223 174.4310 + 134 0.0000 6.487135 176.5239 + 135 0.0000 6.501117 176.9044 + 136 0.0000 6.701608 182.3600 + 137 0.0000 6.724210 182.9751 + 138 0.0000 6.772424 184.2870 + 139 0.0000 6.809211 185.2881 + 140 0.0000 6.831251 185.8878 + 141 0.0000 7.061633 192.1568 + 142 0.0000 7.104134 193.3133 + 143 0.0000 7.120553 193.7601 + 144 0.0000 7.201679 195.9677 + 145 0.0000 7.258011 197.5005 + 146 0.0000 7.281864 198.1496 + 147 0.0000 7.351468 200.0436 + 148 0.0000 7.393538 201.1884 + 149 0.0000 7.446590 202.6320 + 150 0.0000 7.461010 203.0244 + 151 0.0000 7.545509 205.3237 + 152 0.0000 7.594575 206.6589 + 153 0.0000 7.600497 206.8200 + 154 0.0000 7.762086 211.2171 + 155 0.0000 7.902953 215.0503 + 156 0.0000 7.939258 216.0382 + 157 0.0000 8.395320 228.4483 + 158 0.0000 14.073230 382.9520 + 159 0.0000 14.819677 403.2639 + 160 0.0000 16.116256 438.5456 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.690813 -563.0256 + 1 1.0000 -20.616880 -561.0138 + 2 1.0000 -15.804629 -430.0658 + 3 1.0000 -1.617265 -44.0080 + 4 1.0000 -1.372542 -37.3488 + 5 1.0000 -0.953476 -25.9454 + 6 1.0000 -0.769355 -20.9352 + 7 1.0000 -0.731069 -19.8934 + 8 1.0000 -0.698947 -19.0193 + 9 1.0000 -0.607408 -16.5284 + 10 1.0000 -0.528565 -14.3830 + 11 1.0000 -0.457984 -12.4624 + 12 0.0000 0.030590 0.8324 + 13 0.0000 0.068328 1.8593 + 14 0.0000 0.091590 2.4923 + 15 0.0000 0.101713 2.7677 + 16 0.0000 0.114200 3.1075 + 17 0.0000 0.154807 4.2125 + 18 0.0000 0.157218 4.2781 + 19 0.0000 0.173338 4.7168 + 20 0.0000 0.182982 4.9792 + 21 0.0000 0.189735 5.1629 + 22 0.0000 0.201107 5.4724 + 23 0.0000 0.236599 6.4382 + 24 0.0000 0.269819 7.3422 + 25 0.0000 0.286454 7.7948 + 26 0.0000 0.304151 8.2764 + 27 0.0000 0.329393 8.9632 + 28 0.0000 0.333560 9.0766 + 29 0.0000 0.354846 9.6559 + 30 0.0000 0.425079 11.5670 + 31 0.0000 0.506088 13.7714 + 32 0.0000 0.525178 14.2908 + 33 0.0000 0.543908 14.8005 + 34 0.0000 0.572505 15.5787 + 35 0.0000 0.603274 16.4159 + 36 0.0000 0.630159 17.1475 + 37 0.0000 0.650590 17.7035 + 38 0.0000 0.699127 19.0242 + 39 0.0000 0.720694 19.6111 + 40 0.0000 0.740075 20.1385 + 41 0.0000 0.749503 20.3950 + 42 0.0000 0.769491 20.9389 + 43 0.0000 0.792393 21.5621 + 44 0.0000 0.809444 22.0261 + 45 0.0000 0.817018 22.2322 + 46 0.0000 0.855686 23.2844 + 47 0.0000 0.870175 23.6787 + 48 0.0000 0.900726 24.5100 + 49 0.0000 0.938519 25.5384 + 50 0.0000 0.957846 26.0643 + 51 0.0000 0.990718 26.9588 + 52 0.0000 0.997805 27.1517 + 53 0.0000 1.025864 27.9152 + 54 0.0000 1.048417 28.5289 + 55 0.0000 1.115596 30.3569 + 56 0.0000 1.138962 30.9927 + 57 0.0000 1.235258 33.6131 + 58 0.0000 1.247440 33.9446 + 59 0.0000 1.279526 34.8177 + 60 0.0000 1.324045 36.0291 + 61 0.0000 1.417896 38.5829 + 62 0.0000 1.435593 39.0645 + 63 0.0000 1.513867 41.1944 + 64 0.0000 1.523829 41.4655 + 65 0.0000 1.564848 42.5817 + 66 0.0000 1.583490 43.0889 + 67 0.0000 1.637203 44.5506 + 68 0.0000 1.649982 44.8983 + 69 0.0000 1.704632 46.3854 + 70 0.0000 1.775623 48.3172 + 71 0.0000 1.793369 48.8001 + 72 0.0000 1.882469 51.2246 + 73 0.0000 1.930531 52.5324 + 74 0.0000 1.975919 53.7675 + 75 0.0000 2.030372 55.2492 + 76 0.0000 2.062755 56.1304 + 77 0.0000 2.074331 56.4454 + 78 0.0000 2.143184 58.3190 + 79 0.0000 2.216688 60.3192 + 80 0.0000 2.239655 60.9441 + 81 0.0000 2.300051 62.5876 + 82 0.0000 2.307973 62.8031 + 83 0.0000 2.373557 64.5878 + 84 0.0000 2.410246 65.5861 + 85 0.0000 2.453294 66.7575 + 86 0.0000 2.461411 66.9784 + 87 0.0000 2.477020 67.4031 + 88 0.0000 2.508492 68.2595 + 89 0.0000 2.552543 69.4582 + 90 0.0000 2.562212 69.7213 + 91 0.0000 2.599224 70.7285 + 92 0.0000 2.675575 72.8061 + 93 0.0000 2.713088 73.8269 + 94 0.0000 2.757974 75.0483 + 95 0.0000 2.806399 76.3660 + 96 0.0000 2.843318 77.3706 + 97 0.0000 2.883098 78.4531 + 98 0.0000 2.952770 80.3490 + 99 0.0000 2.996116 81.5285 + 100 0.0000 3.053457 83.0888 + 101 0.0000 3.163093 86.0721 + 102 0.0000 3.234220 88.0076 + 103 0.0000 3.487023 94.8867 + 104 0.0000 3.732568 101.5683 + 105 0.0000 3.817283 103.8735 + 106 0.0000 4.053518 110.3018 + 107 0.0000 4.174662 113.5983 + 108 0.0000 4.188250 113.9681 + 109 0.0000 4.305733 117.1650 + 110 0.0000 4.344543 118.2210 + 111 0.0000 4.392954 119.5384 + 112 0.0000 4.534175 123.3812 + 113 0.0000 4.611841 125.4946 + 114 0.0000 4.674399 127.1969 + 115 0.0000 4.721300 128.4731 + 116 0.0000 4.807666 130.8232 + 117 0.0000 4.895365 133.2097 + 118 0.0000 4.933613 134.2504 + 119 0.0000 4.954704 134.8243 + 120 0.0000 5.056820 137.6031 + 121 0.0000 5.096173 138.6739 + 122 0.0000 5.179014 140.9281 + 123 0.0000 5.198775 141.4659 + 124 0.0000 5.213696 141.8719 + 125 0.0000 5.340341 145.3181 + 126 0.0000 5.371483 146.1655 + 127 0.0000 5.471752 148.8939 + 128 0.0000 5.527683 150.4159 + 129 0.0000 5.728147 155.8708 + 130 0.0000 5.752286 156.5276 + 131 0.0000 5.933677 161.4636 + 132 0.0000 6.176656 168.0754 + 133 0.0000 6.410223 174.4310 + 134 0.0000 6.487135 176.5239 + 135 0.0000 6.501117 176.9044 + 136 0.0000 6.701608 182.3600 + 137 0.0000 6.724210 182.9751 + 138 0.0000 6.772424 184.2870 + 139 0.0000 6.809211 185.2881 + 140 0.0000 6.831251 185.8878 + 141 0.0000 7.061633 192.1568 + 142 0.0000 7.104134 193.3133 + 143 0.0000 7.120553 193.7601 + 144 0.0000 7.201679 195.9677 + 145 0.0000 7.258011 197.5005 + 146 0.0000 7.281864 198.1496 + 147 0.0000 7.351468 200.0436 + 148 0.0000 7.393538 201.1884 + 149 0.0000 7.446590 202.6320 + 150 0.0000 7.461010 203.0244 + 151 0.0000 7.545509 205.3237 + 152 0.0000 7.594575 206.6589 + 153 0.0000 7.600497 206.8200 + 154 0.0000 7.762086 211.2171 + 155 0.0000 7.902953 215.0503 + 156 0.0000 7.939258 216.0382 + 157 0.0000 8.395320 228.4483 + 158 0.0000 14.073230 382.9520 + 159 0.0000 14.819677 403.2639 + 160 0.0000 16.116256 438.5456 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.376699 0.000000 + 1 N : 0.354762 0.000000 + 2 O : -0.229780 0.000000 + 3 H : 0.251717 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.869340 s : 3.869340 + pz : 1.572824 p : 4.479454 + px : 1.247511 + py : 1.659119 + dz2 : 0.004652 d : 0.023544 + dxz : 0.002497 + dyz : 0.002405 + dx2y2 : 0.010620 + dxy : 0.003370 + f0 : 0.000419 f : 0.004360 + f+1 : 0.000791 + f-1 : 0.000575 + f+2 : 0.000432 + f-2 : 0.000085 + f+3 : 0.001155 + f-3 : 0.000902 + 1 N s : 3.822008 s : 3.822008 + pz : 0.945895 p : 2.657598 + px : 0.833228 + py : 0.878475 + dz2 : 0.035583 d : 0.135179 + dxz : 0.031027 + dyz : 0.016147 + dx2y2 : 0.030639 + dxy : 0.021783 + f0 : 0.005046 f : 0.030453 + f+1 : 0.006605 + f-1 : 0.002930 + f+2 : 0.003945 + f-2 : 0.003109 + f+3 : 0.003564 + f-3 : 0.005254 + 2 O s : 3.875847 s : 3.875847 + pz : 1.196922 p : 4.282880 + px : 1.808748 + py : 1.277209 + dz2 : 0.024976 d : 0.063506 + dxz : 0.011713 + dyz : 0.015124 + dx2y2 : 0.005161 + dxy : 0.006532 + f0 : 0.002479 f : 0.007547 + f+1 : 0.001238 + f-1 : 0.001216 + f+2 : 0.000908 + f-2 : 0.001064 + f+3 : 0.000347 + f-3 : 0.000296 + 3 H s : 0.641536 s : 0.641536 + pz : 0.031772 p : 0.086315 + px : 0.021586 + py : 0.032956 + dz2 : 0.007794 d : 0.020432 + dxz : 0.005947 + dyz : 0.000165 + dx2y2 : 0.002476 + dxy : 0.004049 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.575676 0.000000 + 1 N : -0.233391 0.000000 + 2 O : 0.249271 0.000000 + 3 H : -0.591557 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.136113 s : 3.136113 + pz : 1.370012 p : 3.956415 + px : 1.172586 + py : 1.413817 + dz2 : 0.040947 d : 0.256871 + dxz : 0.056087 + dyz : 0.027902 + dx2y2 : 0.082918 + dxy : 0.049017 + f0 : 0.005427 f : 0.074925 + f+1 : 0.016469 + f-1 : 0.004653 + f+2 : 0.014580 + f-2 : 0.003131 + f+3 : 0.014411 + f-3 : 0.016255 + 1 N s : 3.035943 s : 3.035943 + pz : 1.075668 p : 2.839154 + px : 0.880157 + py : 0.883329 + dz2 : 0.194016 d : 0.920760 + dxz : 0.263473 + dyz : 0.159234 + dx2y2 : 0.169786 + dxy : 0.134251 + f0 : 0.064150 f : 0.437534 + f+1 : 0.090320 + f-1 : 0.060372 + f+2 : 0.068285 + f-2 : 0.051953 + f+3 : 0.045057 + f-3 : 0.057397 + 2 O s : 3.315785 s : 3.315785 + pz : 1.315702 p : 3.985354 + px : 1.482653 + py : 1.186999 + dz2 : 0.084133 d : 0.331439 + dxz : 0.082664 + dyz : 0.102888 + dx2y2 : 0.039875 + dxy : 0.021879 + f0 : 0.021858 f : 0.118151 + f+1 : 0.019007 + f-1 : 0.029754 + f+2 : 0.025085 + f-2 : 0.015139 + f+3 : 0.002459 + f-3 : 0.004849 + 3 H s : 0.627665 s : 0.627665 + pz : 0.223655 p : 0.572889 + px : 0.137081 + py : 0.212153 + dz2 : 0.108198 d : 0.391002 + dxz : 0.076674 + dyz : 0.098113 + dx2y2 : 0.055731 + dxy : 0.052286 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3767 8.0000 -0.3767 1.8304 1.8304 -0.0000 + 1 N 6.6452 7.0000 0.3548 2.5910 2.5910 0.0000 + 2 O 8.2298 8.0000 -0.2298 1.8080 1.8080 0.0000 + 3 H 0.7483 1.0000 0.2517 0.9841 0.9841 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8155 B( 0-O , 3-H ) : 0.9591 B( 1-N , 2-O ) : 1.7513 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.973 sec +Sum of individual times .... 0.782 sec ( 80.4%) + +Fock matrix formation .... 0.620 sec ( 63.7%) +Diagonalization .... 0.067 sec ( 6.9%) +Density matrix formation .... 0.005 sec ( 0.5%) +Population analysis .... 0.033 sec ( 3.4%) +Initial guess .... 0.010 sec ( 1.0%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.6%) +DIIS solution .... 0.047 sec ( 4.8%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.205 sec +Reference energy ... -204.706734653 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.359 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.370 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.025 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.028 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.032 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.353 sec +AO-integral generation ... 0.247 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.052 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.160 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.252 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090072425 +EMP2(bb)= -0.090072425 +EMP2(ab)= -0.517508315 + +Initial guess performed in 0.132 sec +E(0) ... -204.706734653 +E(MP2) ... -0.697653165 +Initial E(tot) ... -205.404387818 + ... 0.189615831 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.404387818 -0.697653165 -0.000000000 0.019098912 2.71 0.000002643 + *** Turning on DIIS *** + 1 -205.375944549 -0.669209896 0.028443269 0.010125282 2.76 0.055720970 + 2 -205.395495898 -0.688761246 -0.019551349 0.003763949 2.82 0.058448735 + 3 -205.399319003 -0.692584350 -0.003823104 0.001910696 2.82 0.071509245 + 4 -205.400858160 -0.694123507 -0.001539157 0.000912177 2.78 0.077327456 + 5 -205.401349612 -0.694614959 -0.000491452 0.000576294 2.86 0.081734878 + 6 -205.401430557 -0.694695904 -0.000080945 0.000395882 2.80 0.083788303 + 7 -205.401463679 -0.694729027 -0.000033122 0.000236665 2.85 0.084734396 + 8 -205.401471652 -0.694737000 -0.000007973 0.000142098 2.86 0.085153820 + 9 -205.401468310 -0.694733657 0.000003342 0.000084446 2.79 0.085320874 + 10 -205.401473279 -0.694738627 -0.000004969 0.000049966 2.75 0.085403921 + 11 -205.401469802 -0.694735149 0.000003478 0.000031015 2.78 0.085415178 + 12 -205.401472464 -0.694737811 -0.000002662 0.000018030 2.76 0.085434009 + 13 -205.401472356 -0.694737704 0.000000108 0.000010480 2.80 0.085433040 + 14 -205.401472794 -0.694738141 -0.000000438 0.000005432 2.78 0.085439095 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.706734653 +E(CORR) ... -0.694738141 +E(TOT) ... -205.401472794 +Singles norm **1/2 ... 0.085439095 ( 0.042719547, 0.042719547) +T1 diagnostic ... 0.020138188 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.058342 + 8a-> 13a 8b-> 13b 0.053955 + 9a-> 13a 8b-> 13b 0.046416 + 8a-> 13a 9b-> 13b 0.046416 + 5a-> 13a 5b-> 13b 0.029904 + 8a-> 13a -1a-> -1a 0.027751 + 8b-> 13b -1b-> -1b 0.027751 + 11a-> 13a 11b-> 13b 0.027575 + 11a-> 25a 11b-> 25b 0.022898 + 11a-> 24a 11b-> 24b 0.022565 + 9a-> 13a 9b-> 22b 0.022145 + 9a-> 22a 9b-> 13b 0.022145 + 11a-> 25a 11b-> 24b 0.021360 + 11a-> 24a 11b-> 25b 0.021360 + 11b-> 25b -1b-> -1b 0.019932 + 11a-> 25a -1a-> -1a 0.019932 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034533086 + alpha-alpha-alpha ... -0.000863496 ( 2.5%) + alpha-alpha-beta ... -0.016403047 ( 47.5%) + alpha-beta -beta ... -0.016403047 ( 47.5%) + beta -beta -beta ... -0.000863496 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034533086 + +Final correlation energy ... -0.729271227 +E(CCSD) ... -205.401472794 +E(CCSD(T)) ... -205.436005879 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210501694 sqrt= 1.100228019 +W(HF) = 0.826103759 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.315981 -0.000000 + 1 N : 0.181151 0.000000 + 2 O : -0.104678 0.000000 + 3 H : 0.239508 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.845902 s : 3.845902 + pz : 1.551893 p : 4.407218 + px : 1.235799 + py : 1.619526 + dz2 : 0.011051 d : 0.054757 + dxz : 0.009386 + dyz : 0.008652 + dx2y2 : 0.014822 + dxy : 0.010846 + f0 : 0.000988 f : 0.008104 + f+1 : 0.001243 + f-1 : 0.001225 + f+2 : 0.001002 + f-2 : 0.000774 + f+3 : 0.001438 + f-3 : 0.001435 + 1 N s : 3.876366 s : 3.876366 + pz : 0.946177 p : 2.748077 + px : 0.884059 + py : 0.917841 + dz2 : 0.035963 d : 0.164889 + dxz : 0.042177 + dyz : 0.020370 + dx2y2 : 0.036508 + dxy : 0.029871 + f0 : 0.003873 f : 0.029517 + f+1 : 0.006546 + f-1 : 0.003011 + f+2 : 0.003884 + f-2 : 0.003148 + f+3 : 0.003687 + f-3 : 0.005368 + 2 O s : 3.863062 s : 3.863062 + pz : 1.179331 p : 4.147375 + px : 1.721791 + py : 1.246253 + dz2 : 0.024923 d : 0.084323 + dxz : 0.018603 + dyz : 0.017657 + dx2y2 : 0.010978 + dxy : 0.012162 + f0 : 0.002298 f : 0.009917 + f+1 : 0.001739 + f-1 : 0.001423 + f+2 : 0.001266 + f-2 : 0.001460 + f+3 : 0.000899 + f-3 : 0.000833 + 3 H s : 0.649287 s : 0.649287 + pz : 0.032257 p : 0.093730 + px : 0.024746 + py : 0.036727 + dz2 : 0.006682 d : 0.017475 + dxz : 0.005395 + dyz : -0.000563 + dx2y2 : 0.002309 + dxy : 0.003653 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.581744 -0.000000 + 1 N : -0.277691 0.000000 + 2 O : 0.291448 0.000000 + 3 H : -0.595501 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.140355 s : 3.140355 + pz : 1.352663 p : 3.908417 + px : 1.175571 + py : 1.380183 + dz2 : 0.046841 d : 0.287704 + dxz : 0.062132 + dyz : 0.034994 + dx2y2 : 0.089594 + dxy : 0.054143 + f0 : 0.006368 f : 0.081780 + f+1 : 0.016993 + f-1 : 0.005608 + f+2 : 0.015761 + f-2 : 0.003885 + f+3 : 0.016087 + f-3 : 0.017078 + 1 N s : 3.040754 s : 3.040754 + pz : 1.071055 p : 2.879792 + px : 0.903652 + py : 0.905085 + dz2 : 0.192448 d : 0.929175 + dxz : 0.263557 + dyz : 0.162783 + dx2y2 : 0.174947 + dxy : 0.135440 + f0 : 0.062423 f : 0.427970 + f+1 : 0.088121 + f-1 : 0.060517 + f+2 : 0.065827 + f-2 : 0.049611 + f+3 : 0.046291 + f-3 : 0.055181 + 2 O s : 3.318518 s : 3.318518 + pz : 1.305877 p : 3.904217 + px : 1.426955 + py : 1.171386 + dz2 : 0.091331 d : 0.359311 + dxz : 0.086100 + dyz : 0.108256 + dx2y2 : 0.045635 + dxy : 0.027990 + f0 : 0.025273 f : 0.126505 + f+1 : 0.020052 + f-1 : 0.030212 + f+2 : 0.025587 + f-2 : 0.016622 + f+3 : 0.003445 + f-3 : 0.005313 + 3 H s : 0.627768 s : 0.627768 + pz : 0.230490 p : 0.586839 + px : 0.136826 + py : 0.219523 + dz2 : 0.104435 d : 0.380895 + dxz : 0.073610 + dyz : 0.097091 + dx2y2 : 0.055234 + dxy : 0.050525 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3160 8.0000 -0.3160 2.1746 1.7109 0.4637 + 1 N 6.8188 7.0000 0.1812 2.8555 2.3619 0.4936 + 2 O 8.1047 8.0000 -0.1047 2.1942 1.6959 0.4984 + 3 H 0.7605 1.0000 0.2395 1.0065 0.9324 0.0741 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7267 B( 0-O , 3-H ) : 0.8962 B( 1-N , 2-O ) : 1.6035 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 56.994 sec + +Fock Matrix Formation ... 0.205 sec ( 0.4%) +Initial Guess ... 0.132 sec ( 0.2%) +DIIS Solver ... 1.946 sec ( 3.4%) +State Vector Update ... 0.092 sec ( 0.2%) +Sigma-vector construction ... 39.876 sec ( 70.0%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (0-ext) ... 0.074 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (2-ext) ... 0.997 sec ( 2.5% of sigma) + (4-ext) ... 22.000 sec ( 55.2% of sigma) + ... 1.434 sec ( 3.6% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.114 sec ( 0.3% of sigma) + Fock-dressing ... 2.236 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.079 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.109 sec ( 25.4% of sigma) + Pair energies ... 0.007 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.877 sec ( 12.1% of ALL) + I/O of integral and amplitudes ... 0.779 sec ( 11.3% of (T)) + External N**7 contributions ... 3.899 sec ( 56.7% of (T)) + Internal N**7 contributions ... 0.308 sec ( 4.5% of (T)) + N**6 triples energy contributions ... 1.580 sec ( 23.0% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.436005879321 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.010.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.010.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.410800, -0.219697 -0.577079) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 1.06209 -0.14492 -0.64112 +Nuclear contribution : -0.92742 0.50023 1.19565 + ----------------------------------------- +Total Dipole Moment : 0.13467 0.35531 0.55453 + ----------------------------------------- +Magnitude (a.u.) : 0.67222 +Magnitude (Debye) : 1.70865 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.762174 0.399618 0.360618 +Rotational constants in MHz : 82807.900993 11980.235664 10811.041712 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.177062 0.225663 0.607952 +x,y,z [Debye]: -0.450055 0.573589 1.545292 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.410800, -0.219697 -0.577079) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 1.10224 -0.10890 -0.81173 +Nuclear contribution : -0.92742 0.50023 1.19565 + ----------------------------------------- +Total Dipole Moment : 0.17483 0.39133 0.38392 + ----------------------------------------- +Magnitude (a.u.) : 0.57541 +Magnitude (Debye) : 1.46257 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.762174 0.399618 0.360618 +Rotational constants in MHz : 82807.900993 11980.235664 10811.041712 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.039649 0.121048 0.561134 +x,y,z [Debye]: -0.100780 0.307678 1.426289 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 11 * + * * + * Dihedral ( 2, 1, 0, 3) : -98.18181818 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0397455794 RMS(Int)= 0.0004544572 + Iter 1: RMS(Cart)= 0.0001264895 RMS(Int)= 0.0000037671 + Iter 2: RMS(Cart)= 0.0000010485 RMS(Int)= 0.0000000313 + Iter 3: RMS(Cart)= 0.0000000087 RMS(Int)= 0.0000000003 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.5024 0.000000 + 2. B(O 2,N 1) 1.1668 0.000000 + 3. B(H 3,O 0) 0.9722 0.000000 + 4. A(N 1,O 0,H 3) 102.3729 0.000000 + 5. A(O 0,N 1,O 2) 110.4989 0.000000 + 6. D(O 2,N 1,O 0,H 3) -98.1818 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.798266 -0.235765 0.248454 + N 0.647957 -0.412759 -0.117871 + O 0.905987 0.205090 -1.073381 + H -0.755677 0.443434 0.942797 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.508504 -0.445531 0.469511 + 1 N 7.0000 0 14.007 1.224461 -0.780002 -0.222744 + 2 O 8.0000 0 15.999 1.712068 0.387564 -2.028395 + 3 H 1.0000 0 1.008 -1.428023 0.837969 1.781629 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.502068269921 0.00000000 0.00000000 + O 2 1 0 1.164727483571 110.58204511 0.00000000 + H 1 2 3 0.969505191682 102.45113132 253.63636358 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.838497664603 0.00000000 0.00000000 + O 2 1 0 2.201015964601 110.58204511 0.00000000 + H 1 2 3 1.832099297694 102.45113132 253.63636358 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2228 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2695 + la=0 lb=0: 548 shell pairs + la=1 lb=0: 535 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.369278617441 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.3692786174 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.898e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7007114908 0.000000000000 0.00153536 0.00005212 0.0198517 0.7000 + 1 -204.7016234898 -0.000911999051 0.00145403 0.00004774 0.0164595 0.7000 + ***Turning on DIIS*** + 2 -204.7024063177 -0.000782827885 0.00408173 0.00013101 0.0134050 0.0000 + 3 -204.7069834337 -0.004577115985 0.00191920 0.00005842 0.0051992 0.0000 + 4 -204.7041061021 0.002877331630 0.00091769 0.00002995 0.0020469 0.0000 + 5 -204.7060773270 -0.001971224894 0.00082185 0.00002562 0.0011718 0.0000 + 6 -204.7050742645 0.001003062470 0.00097285 0.00002970 0.0007369 0.0000 + 7 -204.7049292567 0.000145007747 0.00036103 0.00001233 0.0003809 0.0000 + 8 -204.7056725292 -0.000743272413 0.00019177 0.00000764 0.0001927 0.0000 + 9 -204.7051505313 0.000521997825 0.00015208 0.00000644 0.0001393 0.0000 + 10 -204.7053852590 -0.000234727669 0.00006208 0.00000252 0.0000594 0.0000 + 11 -204.7054656132 -0.000080354200 0.00002236 0.00000084 0.0000331 0.0000 + 12 -204.7053574053 0.000108207895 0.00000859 0.00000030 0.0000112 0.0000 + 13 -204.7053925830 -0.000035177648 0.00000245 0.00000009 0.0000036 0.0000 + 14 -204.7053828606 0.000009722340 0.00000131 0.00000004 0.0000027 0.0000 + 15 -204.7053855305 -0.000002669880 0.00000093 0.00000002 0.0000018 0.0000 + 16 -204.7053878108 -0.000002280325 0.00000063 0.00000002 0.0000012 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 17 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70538546 Eh -5570.31673 eV + +Components: +Nuclear Repulsion : 68.36927862 Eh 1860.42265 eV +Electronic Energy : -273.07466408 Eh -7430.73938 eV +One Electron Energy: -416.45581460 Eh -11332.33884 eV +Two Electron Energy: 143.38115052 Eh 3901.59946 eV + +Virial components: +Potential Energy : -408.92542225 Eh -11127.42645 eV +Kinetic Energy : 204.22003679 Eh 5557.10972 eV +Virial Ratio : 2.00237660 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.3489e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.7625e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.8337e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 4.5908e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.691385 -563.0412 + 1 1.0000 -20.616972 -561.0163 + 2 1.0000 -15.804934 -430.0741 + 3 1.0000 -1.616159 -43.9779 + 4 1.0000 -1.371574 -37.3224 + 5 1.0000 -0.954247 -25.9664 + 6 1.0000 -0.767481 -20.8842 + 7 1.0000 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0.0000 0.030644 0.8339 + 13 0.0000 0.066805 1.8179 + 14 0.0000 0.091729 2.4961 + 15 0.0000 0.102372 2.7857 + 16 0.0000 0.113325 3.0837 + 17 0.0000 0.155230 4.2240 + 18 0.0000 0.157060 4.2738 + 19 0.0000 0.173822 4.7299 + 20 0.0000 0.181691 4.9441 + 21 0.0000 0.189525 5.1572 + 22 0.0000 0.200900 5.4668 + 23 0.0000 0.236455 6.4343 + 24 0.0000 0.269395 7.3306 + 25 0.0000 0.290920 7.9163 + 26 0.0000 0.301144 8.1946 + 27 0.0000 0.330525 8.9940 + 28 0.0000 0.332475 9.0471 + 29 0.0000 0.353242 9.6122 + 30 0.0000 0.424146 11.5416 + 31 0.0000 0.505141 13.7456 + 32 0.0000 0.527204 14.3460 + 33 0.0000 0.544371 14.8131 + 34 0.0000 0.571438 15.5496 + 35 0.0000 0.600880 16.3508 + 36 0.0000 0.629104 17.1188 + 37 0.0000 0.648476 17.6459 + 38 0.0000 0.702694 19.1213 + 39 0.0000 0.718951 19.5637 + 40 0.0000 0.739905 20.1338 + 41 0.0000 0.754171 20.5220 + 42 0.0000 0.765080 20.8189 + 43 0.0000 0.792136 21.5551 + 44 0.0000 0.811810 22.0905 + 45 0.0000 0.813488 22.1361 + 46 0.0000 0.860387 23.4123 + 47 0.0000 0.869743 23.6669 + 48 0.0000 0.894633 24.3442 + 49 0.0000 0.940010 25.5790 + 50 0.0000 0.958841 26.0914 + 51 0.0000 0.985139 26.8070 + 52 0.0000 0.995373 27.0855 + 53 0.0000 1.027217 27.9520 + 54 0.0000 1.046826 28.4856 + 55 0.0000 1.113553 30.3013 + 56 0.0000 1.146375 31.1945 + 57 0.0000 1.230821 33.4923 + 58 0.0000 1.250632 34.0314 + 59 0.0000 1.269413 34.5425 + 60 0.0000 1.317986 35.8642 + 61 0.0000 1.411483 38.4084 + 62 0.0000 1.441955 39.2376 + 63 0.0000 1.518898 41.3313 + 64 0.0000 1.521350 41.3980 + 65 0.0000 1.567957 42.6663 + 66 0.0000 1.584753 43.1233 + 67 0.0000 1.633815 44.4584 + 68 0.0000 1.648514 44.8583 + 69 0.0000 1.709736 46.5243 + 70 0.0000 1.773671 48.2640 + 71 0.0000 1.790475 48.7213 + 72 0.0000 1.884917 51.2912 + 73 0.0000 1.925477 52.3949 + 74 0.0000 1.984770 54.0083 + 75 0.0000 2.021160 54.9986 + 76 0.0000 2.057658 55.9917 + 77 0.0000 2.083391 56.6919 + 78 0.0000 2.140947 58.2581 + 79 0.0000 2.211625 60.1814 + 80 0.0000 2.248756 61.1918 + 81 0.0000 2.296502 62.4910 + 82 0.0000 2.315539 63.0090 + 83 0.0000 2.365500 64.3685 + 84 0.0000 2.407310 65.5062 + 85 0.0000 2.453606 66.7660 + 86 0.0000 2.462977 67.0210 + 87 0.0000 2.476325 67.3842 + 88 0.0000 2.507083 68.2212 + 89 0.0000 2.560014 69.6615 + 90 0.0000 2.570332 69.9423 + 91 0.0000 2.598642 70.7126 + 92 0.0000 2.674555 72.7784 + 93 0.0000 2.722860 74.0928 + 94 0.0000 2.749866 74.8276 + 95 0.0000 2.800792 76.2134 + 96 0.0000 2.844943 77.4148 + 97 0.0000 2.878682 78.3329 + 98 0.0000 2.959320 80.5272 + 99 0.0000 2.989558 81.3500 + 100 0.0000 3.052865 83.0727 + 101 0.0000 3.165840 86.1469 + 102 0.0000 3.224157 87.7338 + 103 0.0000 3.485322 94.8404 + 104 0.0000 3.727409 101.4279 + 105 0.0000 3.810851 103.6985 + 106 0.0000 4.052257 110.2675 + 107 0.0000 4.172231 113.5322 + 108 0.0000 4.183490 113.8386 + 109 0.0000 4.296145 116.9040 + 110 0.0000 4.350741 118.3897 + 111 0.0000 4.392382 119.5228 + 112 0.0000 4.523194 123.0824 + 113 0.0000 4.602060 125.2284 + 114 0.0000 4.666964 126.9945 + 115 0.0000 4.717261 128.3632 + 116 0.0000 4.817264 131.0844 + 117 0.0000 4.899160 133.3129 + 118 0.0000 4.933413 134.2450 + 119 0.0000 4.945101 134.5631 + 120 0.0000 5.052519 137.4860 + 121 0.0000 5.097820 138.7187 + 122 0.0000 5.181036 140.9832 + 123 0.0000 5.196928 141.4156 + 124 0.0000 5.214124 141.8835 + 125 0.0000 5.327445 144.9672 + 126 0.0000 5.373909 146.2315 + 127 0.0000 5.482323 149.1816 + 128 0.0000 5.543125 150.8361 + 129 0.0000 5.725301 155.7934 + 130 0.0000 5.739170 156.1708 + 131 0.0000 5.934243 161.4790 + 132 0.0000 6.180674 168.1847 + 133 0.0000 6.414164 174.5383 + 134 0.0000 6.484603 176.4550 + 135 0.0000 6.503521 176.9698 + 136 0.0000 6.700906 182.3409 + 137 0.0000 6.728499 183.0918 + 138 0.0000 6.765651 184.1027 + 139 0.0000 6.814843 185.4413 + 140 0.0000 6.826306 185.7532 + 141 0.0000 7.060917 192.1373 + 142 0.0000 7.100017 193.2013 + 143 0.0000 7.119013 193.7182 + 144 0.0000 7.193040 195.7326 + 145 0.0000 7.256492 197.4592 + 146 0.0000 7.279994 198.0987 + 147 0.0000 7.341830 199.7813 + 148 0.0000 7.387941 201.0361 + 149 0.0000 7.450834 202.7475 + 150 0.0000 7.460488 203.0102 + 151 0.0000 7.551915 205.4981 + 152 0.0000 7.587859 206.4761 + 153 0.0000 7.613787 207.1817 + 154 0.0000 7.735919 210.5051 + 155 0.0000 7.897214 214.8941 + 156 0.0000 7.922985 215.5954 + 157 0.0000 8.397069 228.4959 + 158 0.0000 14.058710 382.5570 + 159 0.0000 14.797288 402.6547 + 160 0.0000 16.038946 436.4419 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.377631 0.000000 + 1 N : 0.352298 0.000000 + 2 O : -0.227190 0.000000 + 3 H : 0.252523 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.867831 s : 3.867831 + pz : 1.608402 p : 4.480925 + px : 1.248604 + py : 1.623919 + dz2 : 0.003754 d : 0.024538 + dxz : 0.003138 + dyz : 0.002700 + dx2y2 : 0.011548 + dxy : 0.003397 + f0 : 0.000512 f : 0.004337 + f+1 : 0.000777 + f-1 : 0.000487 + f+2 : 0.000467 + f-2 : 0.000086 + f+3 : 0.001141 + f-3 : 0.000866 + 1 N s : 3.821511 s : 3.821511 + pz : 0.919141 p : 2.659183 + px : 0.832053 + py : 0.907990 + dz2 : 0.036162 d : 0.136363 + dxz : 0.031140 + dyz : 0.014877 + dx2y2 : 0.032414 + dxy : 0.021769 + f0 : 0.004829 f : 0.030644 + f+1 : 0.006073 + f-1 : 0.002870 + f+2 : 0.004023 + f-2 : 0.003542 + f+3 : 0.003889 + f-3 : 0.005419 + 2 O s : 3.876168 s : 3.876168 + pz : 1.193045 p : 4.280823 + px : 1.802633 + py : 1.285145 + dz2 : 0.025505 d : 0.062697 + dxz : 0.010380 + dyz : 0.013132 + dx2y2 : 0.005937 + dxy : 0.007743 + f0 : 0.002293 f : 0.007503 + f+1 : 0.001016 + f-1 : 0.001211 + f+2 : 0.000996 + f-2 : 0.001160 + f+3 : 0.000448 + f-3 : 0.000380 + 3 H s : 0.641271 s : 0.641271 + pz : 0.033940 p : 0.086171 + px : 0.021396 + py : 0.030834 + dz2 : 0.007768 d : 0.020035 + dxz : 0.004980 + dyz : -0.000152 + dx2y2 : 0.002749 + dxy : 0.004690 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.571621 0.000000 + 1 N : -0.233342 0.000000 + 2 O : 0.248760 0.000000 + 3 H : -0.587040 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.137775 s : 3.137775 + pz : 1.381543 p : 3.959135 + px : 1.174537 + py : 1.403055 + dz2 : 0.037863 d : 0.256636 + dxz : 0.056027 + dyz : 0.029115 + dx2y2 : 0.082744 + dxy : 0.050886 + f0 : 0.005477 f : 0.074833 + f+1 : 0.016498 + f-1 : 0.003828 + f+2 : 0.014504 + f-2 : 0.003437 + f+3 : 0.014040 + f-3 : 0.017049 + 1 N s : 3.037485 s : 3.037485 + pz : 1.037379 p : 2.839525 + px : 0.878381 + py : 0.923766 + dz2 : 0.181754 d : 0.918258 + dxz : 0.254970 + dyz : 0.164394 + dx2y2 : 0.177296 + dxy : 0.139844 + f0 : 0.058511 f : 0.438074 + f+1 : 0.081909 + f-1 : 0.058828 + f+2 : 0.071752 + f-2 : 0.058992 + f+3 : 0.048294 + f-3 : 0.059788 + 2 O s : 3.316138 s : 3.316138 + pz : 1.291636 p : 3.986104 + px : 1.480042 + py : 1.214426 + dz2 : 0.072701 d : 0.331122 + dxz : 0.078504 + dyz : 0.108480 + dx2y2 : 0.045840 + dxy : 0.025597 + f0 : 0.018540 f : 0.117875 + f+1 : 0.016517 + f-1 : 0.029031 + f+2 : 0.027297 + f-2 : 0.016986 + f+3 : 0.003039 + f-3 : 0.006465 + 3 H s : 0.626183 s : 0.626183 + pz : 0.214801 p : 0.570979 + px : 0.137232 + py : 0.218946 + dz2 : 0.101243 d : 0.389878 + dxz : 0.069017 + dyz : 0.096779 + dx2y2 : 0.062096 + dxy : 0.060743 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3776 8.0000 -0.3776 1.8209 1.8209 0.0000 + 1 N 6.6477 7.0000 0.3523 2.5964 2.5964 0.0000 + 2 O 8.2272 8.0000 -0.2272 1.8105 1.8105 -0.0000 + 3 H 0.7475 1.0000 0.2525 0.9865 0.9865 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8108 B( 0-O , 3-H ) : 0.9558 B( 1-N , 2-O ) : 1.7555 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.510 sec +Sum of individual times .... 2.324 sec ( 92.6%) + +Fock matrix formation .... 1.898 sec ( 75.6%) +Diagonalization .... 0.209 sec ( 8.3%) +Density matrix formation .... 0.015 sec ( 0.6%) +Population analysis .... 0.023 sec ( 0.9%) +Initial guess .... 0.009 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.2%) +DIIS solution .... 0.169 sec ( 6.7%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.205 sec +Reference energy ... -204.705386149 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.357 sec +AO-integral generation ... 0.142 sec +Half transformation ... 0.077 sec +K-integral sorting ... 5.365 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.027 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.035 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.039 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.023 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.039 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.358 sec +AO-integral generation ... 0.252 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.052 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.156 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.250 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090044209 +EMP2(bb)= -0.090044209 +EMP2(ab)= -0.517623725 + +Initial guess performed in 0.133 sec +E(0) ... -204.705386149 +E(MP2) ... -0.697712144 +Initial E(tot) ... -205.403098294 + ... 0.189756374 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.403098294 -0.697712144 -0.000000000 0.018771974 2.73 0.000001608 + *** Turning on DIIS *** + 1 -205.374724863 -0.669338713 0.028373431 0.010857379 2.70 0.055434394 + 2 -205.394279574 -0.688893424 -0.019554711 0.003692140 2.75 0.058147529 + 3 -205.398111468 -0.692725319 -0.003831895 0.002079712 2.90 0.071013446 + 4 -205.399646214 -0.694260065 -0.001534746 0.000944105 2.96 0.076676613 + 5 -205.400126296 -0.694740147 -0.000480082 0.000377915 2.84 0.080844209 + 6 -205.400200799 -0.694814650 -0.000074503 0.000263925 2.89 0.082693022 + 7 -205.400229616 -0.694843467 -0.000028817 0.000202374 2.87 0.083486363 + 8 -205.400235817 -0.694849668 -0.000006201 0.000150425 3.17 0.083825549 + 9 -205.400232715 -0.694846565 0.000003102 0.000104332 2.84 0.083963592 + 10 -205.400237080 -0.694850931 -0.000004365 0.000056481 2.80 0.084042975 + 11 -205.400233619 -0.694847470 0.000003461 0.000026780 2.81 0.084067718 + 12 -205.400236308 -0.694850158 -0.000002689 0.000012355 2.87 0.084085689 + 13 -205.400236398 -0.694850249 -0.000000091 0.000006295 2.87 0.084087857 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.705386149 +E(CORR) ... -0.694850249 +E(TOT) ... -205.400236398 +Singles norm **1/2 ... 0.084087857 ( 0.042043928, 0.042043928) +T1 diagnostic ... 0.019819698 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.062414 + 8a-> 13a 8b-> 13b 0.053426 + 8a-> 13a 9b-> 13b 0.047358 + 9a-> 13a 8b-> 13b 0.047358 + 5a-> 13a 5b-> 13b 0.030135 + 11a-> 13a 11b-> 13b 0.027816 + 8a-> 13a -1a-> -1a 0.027263 + 8b-> 13b -1b-> -1b 0.027263 + 11a-> 25a 11b-> 25b 0.025649 + 9a-> 22a 9b-> 13b 0.023826 + 9a-> 13a 9b-> 22b 0.023826 + 11a-> 24a 11b-> 24b 0.023342 + 11a-> 25a 11b-> 24b 0.023068 + 11a-> 24a 11b-> 25b 0.023068 + 11b-> 25b -1b-> -1b 0.020858 + 11a-> 25a -1a-> -1a 0.020858 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034497284 + alpha-alpha-alpha ... -0.000860151 ( 2.5%) + alpha-alpha-beta ... -0.016388491 ( 47.5%) + alpha-beta -beta ... -0.016388491 ( 47.5%) + beta -beta -beta ... -0.000860151 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034497284 + +Final correlation energy ... -0.729347533 +E(CCSD) ... -205.400236398 +E(CCSD(T)) ... -205.434733682 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210293815 sqrt= 1.100133544 +W(HF) = 0.826245650 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.319617 0.000000 + 1 N : 0.181095 0.000000 + 2 O : -0.101455 -0.000000 + 3 H : 0.239977 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.844699 s : 3.844699 + pz : 1.586003 p : 4.411318 + px : 1.235795 + py : 1.589520 + dz2 : 0.010356 d : 0.055530 + dxz : 0.009881 + dyz : 0.008907 + dx2y2 : 0.015590 + dxy : 0.010797 + f0 : 0.001061 f : 0.008070 + f+1 : 0.001238 + f-1 : 0.001136 + f+2 : 0.001033 + f-2 : 0.000775 + f+3 : 0.001437 + f-3 : 0.001391 + 1 N s : 3.875980 s : 3.875980 + pz : 0.927434 p : 2.747386 + px : 0.881821 + py : 0.938131 + dz2 : 0.036356 d : 0.165863 + dxz : 0.042166 + dyz : 0.019454 + dx2y2 : 0.038280 + dxy : 0.029606 + f0 : 0.003785 f : 0.029676 + f+1 : 0.006074 + f-1 : 0.002888 + f+2 : 0.003917 + f-2 : 0.003521 + f+3 : 0.003988 + f-3 : 0.005504 + 2 O s : 3.863308 s : 3.863308 + pz : 1.173954 p : 4.144701 + px : 1.716682 + py : 1.254065 + dz2 : 0.025337 d : 0.083578 + dxz : 0.017283 + dyz : 0.016031 + dx2y2 : 0.011678 + dxy : 0.013248 + f0 : 0.002158 f : 0.009869 + f+1 : 0.001535 + f-1 : 0.001403 + f+2 : 0.001336 + f-2 : 0.001538 + f+3 : 0.000991 + f-3 : 0.000908 + 3 H s : 0.648971 s : 0.648971 + pz : 0.035605 p : 0.093885 + px : 0.024601 + py : 0.033678 + dz2 : 0.006806 d : 0.017166 + dxz : 0.004548 + dyz : -0.000836 + dx2y2 : 0.002434 + dxy : 0.004213 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.576611 0.000000 + 1 N : -0.276842 0.000000 + 2 O : 0.291987 -0.000000 + 3 H : -0.591756 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.141836 s : 3.141836 + pz : 1.362710 p : 3.912487 + px : 1.176310 + py : 1.373467 + dz2 : 0.043666 d : 0.287382 + dxz : 0.062118 + dyz : 0.036269 + dx2y2 : 0.089350 + dxy : 0.055979 + f0 : 0.006479 f : 0.081684 + f+1 : 0.016987 + f-1 : 0.004690 + f+2 : 0.015781 + f-2 : 0.004244 + f+3 : 0.015718 + f-3 : 0.017784 + 1 N s : 3.042333 s : 3.042333 + pz : 1.038324 p : 2.879411 + px : 0.901381 + py : 0.939706 + dz2 : 0.179608 d : 0.926391 + dxz : 0.255607 + dyz : 0.168864 + dx2y2 : 0.182178 + dxy : 0.140134 + f0 : 0.057180 f : 0.428707 + f+1 : 0.079865 + f-1 : 0.059053 + f+2 : 0.069167 + f-2 : 0.056246 + f+3 : 0.049465 + f-3 : 0.057732 + 2 O s : 3.318951 s : 3.318951 + pz : 1.280942 p : 3.904042 + px : 1.424963 + py : 1.198137 + dz2 : 0.080298 d : 0.358839 + dxz : 0.082068 + dyz : 0.113500 + dx2y2 : 0.051501 + dxy : 0.031473 + f0 : 0.021984 f : 0.126181 + f+1 : 0.017477 + f-1 : 0.029655 + f+2 : 0.027668 + f-2 : 0.018378 + f+3 : 0.004117 + f-3 : 0.006901 + 3 H s : 0.626332 s : 0.626332 + pz : 0.222193 p : 0.585516 + px : 0.136900 + py : 0.226423 + dz2 : 0.097741 d : 0.379908 + dxz : 0.066226 + dyz : 0.095915 + dx2y2 : 0.061341 + dxy : 0.058684 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3196 8.0000 -0.3196 2.1618 1.6988 0.4630 + 1 N 6.8189 7.0000 0.1811 2.8586 2.3632 0.4954 + 2 O 8.1015 8.0000 -0.1015 2.1953 1.6962 0.4991 + 3 H 0.7600 1.0000 0.2400 1.0091 0.9346 0.0744 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7199 B( 0-O , 3-H ) : 0.8939 B( 1-N , 2-O ) : 1.6069 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 54.977 sec + +Fock Matrix Formation ... 0.205 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 1.877 sec ( 3.4%) +State Vector Update ... 0.091 sec ( 0.2%) +Sigma-vector construction ... 38.027 sec ( 69.2%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (0-ext) ... 0.073 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (2-ext) ... 0.935 sec ( 2.5% of sigma) + (4-ext) ... 21.028 sec ( 55.3% of sigma) + ... 1.379 sec ( 3.6% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.108 sec ( 0.3% of sigma) + Fock-dressing ... 2.126 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.080 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.665 sec ( 25.4% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.796 sec ( 12.4% of ALL) + I/O of integral and amplitudes ... 0.825 sec ( 12.1% of (T)) + External N**7 contributions ... 3.908 sec ( 57.5% of (T)) + Internal N**7 contributions ... 0.312 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.669 sec ( 24.6% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.434733682216 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.000737375 -0.003934125 0.000683509 + 2 N : -0.001388220 -0.004661167 0.000430103 + 3 O : 0.000363752 0.004197222 -0.000207673 + 4 H : 0.000287092 0.004398069 -0.000905940 + +Norm of the cartesian gradient ... 0.008852408 +RMS gradient ... 0.002555470 +MAX gradient ... 0.004661167 + +------- +TIMINGS +------- + +Total numerical gradient time ... 347.775 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: -503.95 cm**-1 ***imaginary mode*** + 7: 550.10 cm**-1 + 8: 781.50 cm**-1 + 9: 1127.42 cm**-1 + 10: 1704.06 cm**-1 + 11: 3713.53 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 0.000939 0.595903 -0.201958 0.052665 -0.081889 -0.001604 + 1 -0.038505 0.067875 0.211723 0.029597 0.016168 -0.043391 + 2 0.056739 -0.344099 -0.193600 0.027156 0.007291 -0.045198 + 3 -0.009264 -0.284648 0.730673 0.001655 -0.056282 -0.000038 + 4 -0.060509 -0.106141 -0.292903 -0.034183 -0.425073 0.000282 + 5 -0.047208 0.236143 0.060091 -0.029209 0.609019 -0.000633 + 6 0.011447 -0.359297 -0.430066 0.008022 0.129924 -0.000501 + 7 0.045915 0.016606 0.036665 0.002614 0.354999 -0.000576 + 8 0.027262 0.162565 0.148479 -0.010368 -0.542180 0.000609 + 9 -0.067867 0.200005 -0.121809 -0.986233 0.019673 0.033943 + 10 0.723207 0.134042 0.127711 -0.036252 0.015581 0.693926 + 11 -0.677277 -0.400086 -0.118848 0.139431 0.026951 0.716509 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 7: 550.10 0.026202 132.41 0.014864 (-0.103093 -0.003400 0.064995) + 8: 781.50 0.022372 113.06 0.008933 ( 0.085233 -0.007416 -0.040170) + 9: 1127.42 0.013547 68.46 0.003750 (-0.054687 0.014978 0.023124) + 10: 1704.06 0.032807 165.80 0.006008 (-0.058388 -0.012398 0.049449) + 11: 3713.53 0.011791 59.59 0.000991 (-0.013117 0.016658 0.023266) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 7 +The total number of vibrations considered is 5 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 550.10 E(vib) ... 0.12 +freq. 781.50 E(vib) ... 0.05 +freq. 1127.42 E(vib) ... 0.01 +freq. 1704.06 E(vib) ... 0.00 +freq. 3713.53 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.43473368 Eh +Zero point energy ... 0.01794423 Eh 11.26 kcal/mol +Thermal vibrational correction ... 0.00029800 Eh 0.19 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.41365890 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00313054 Eh 1.96 kcal/mol +Non-thermal (ZPE) correction 0.01794423 Eh 11.26 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02107478 Eh 13.22 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.41365890 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.41271470 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.716832 0.400534 0.361417 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00039361 Eh 0.25 kcal/mol +Rotational entropy ... 0.00995137 Eh 6.24 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02814729 Eh 17.66 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00995137 Eh 6.24 kcal/mol| +| sn= 2 | S(rot)= 0.00929691 Eh 5.83 kcal/mol| +| sn= 3 | S(rot)= 0.00891408 Eh 5.59 kcal/mol| +| sn= 4 | S(rot)= 0.00864246 Eh 5.42 kcal/mol| +| sn= 5 | S(rot)= 0.00843177 Eh 5.29 kcal/mol| +| sn= 6 | S(rot)= 0.00825963 Eh 5.18 kcal/mol| +| sn= 7 | S(rot)= 0.00811408 Eh 5.09 kcal/mol| +| sn= 8 | S(rot)= 0.00798800 Eh 5.01 kcal/mol| +| sn= 9 | S(rot)= 0.00787679 Eh 4.94 kcal/mol| +| sn=10 | S(rot)= 0.00777731 Eh 4.88 kcal/mol| +| sn=11 | S(rot)= 0.00768732 Eh 4.82 kcal/mol| +| sn=12 | S(rot)= 0.00760517 Eh 4.77 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.41271470 Eh +Total entropy correction ... -0.02814729 Eh -17.66 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44086199 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00612831 Eh -3.85 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.434733682 Eh +Current gradient norm .... 0.008852409 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + -0.029197290 0.096741823 0.159544579 0.471774032 0.497662568 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999917182 +Lowest eigenvalues of augmented Hessian: + -0.000046513 0.096707370 0.159388605 0.471524306 0.497667236 +Length of the computed step .... 0.012870801 +The final length of the internal step .... 0.012870801 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0052544827 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0041396814 RMS(Int)= 0.0052571861 + Iter 1: RMS(Cart)= 0.0000047407 RMS(Int)= 0.0000081839 + Iter 2: RMS(Cart)= 0.0000000258 RMS(Int)= 0.0000000240 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0017813032 0.0001000000 NO + MAX gradient 0.0024734143 0.0003000000 NO + RMS step 0.0052544827 0.0020000000 NO + MAX step 0.0088053710 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0047 Max(Angles) 0.28 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.5024 -0.000986 0.0047 1.5070 + 2. B(O 2,N 1) 1.1668 0.002473 -0.0024 1.1643 + 3. B(H 3,O 0) 0.9722 0.002438 -0.0027 0.9696 + 4. A(N 1,O 0,H 3) 102.37 -0.000942 0.28 102.65 + 5. A(O 0,N 1,O 2) 110.50 -0.002262 0.24 110.74 + 6. D(O 2,N 1,O 0,H 3) -98.18 0.006727 0.00 -98.18 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.799566 -0.234189 0.251393 + N 0.649839 -0.411915 -0.121089 + O 0.908973 0.203551 -1.074867 + H -0.759245 0.442553 0.944563 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.510961 -0.442553 0.475065 + 1 N 7.0000 0 14.007 1.228017 -0.778406 -0.228825 + 2 O 8.0000 0 15.999 1.717709 0.384655 -2.031205 + 3 H 1.0000 0 1.008 -1.434764 0.836304 1.784965 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.507018123588 0.00000000 0.00000000 + O 2 1 0 1.164319931816 110.74350448 0.00000000 + H 1 2 3 0.969582079140 102.65145550 261.81818198 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.847851532438 0.00000000 0.00000000 + O 2 1 0 2.200245803398 110.74350448 0.00000000 + H 1 2 3 1.832244593932 102.65145550 261.81818198 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2228 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2695 + la=0 lb=0: 548 shell pairs + la=1 lb=0: 535 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.326195203159 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.899e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7054470187 0.000000000000 0.00017206 0.00000514 0.0009084 0.7000 + 1 -204.7054533419 -0.000006323177 0.00013807 0.00000438 0.0006695 0.7000 + ***Turning on DIIS*** + 2 -204.7054586175 -0.000005275550 0.00034574 0.00001192 0.0005182 0.0000 + 3 -204.7051195993 0.000339018199 0.00018286 0.00000552 0.0001923 0.0000 + 4 -204.7055658771 -0.000446277814 0.00005793 0.00000259 0.0000818 0.0000 + 5 -204.7057155208 -0.000149643700 0.00003718 0.00000122 0.0000723 0.0000 + 6 -204.7053860981 0.000329422714 0.00002726 0.00000108 0.0000340 0.0000 + 7 -204.7055147230 -0.000128624967 0.00001514 0.00000071 0.0000177 0.0000 + 8 -204.7054780233 0.000036699720 0.00001302 0.00000050 0.0000108 0.0000 + 9 -204.7054453623 0.000032661023 0.00000604 0.00000026 0.0000068 0.0000 + 10 -204.7054874236 -0.000042061347 0.00000400 0.00000015 0.0000030 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + +Total Energy : -204.70547379 Eh -5570.31913 eV + Last Energy change ... 1.3635e-05 Tolerance : 1.0000e-08 + Last MAX-Density change ... 9.2024e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.204 sec +Reference energy ... -204.705477404 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.381 sec +AO-integral generation ... 0.142 sec +Half transformation ... 0.077 sec +K-integral sorting ... 5.387 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.024 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.029 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.036 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.353 sec +AO-integral generation ... 0.238 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.055 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.152 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.251 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090036555 +EMP2(bb)= -0.090036555 +EMP2(ab)= -0.517587235 + +Initial guess performed in 0.133 sec +E(0) ... -204.705477404 +E(MP2) ... -0.697660345 +Initial E(tot) ... -205.403137749 + ... 0.189743343 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.403137749 -0.697660345 -0.000000000 0.018789996 2.74 0.000001262 + *** Turning on DIIS *** + 1 -205.374731053 -0.669253649 0.028406695 0.010620432 2.72 0.055512273 + 2 -205.394290056 -0.688812652 -0.019559002 0.003682426 2.78 0.058191736 + 3 -205.398117244 -0.692639840 -0.003827189 0.002030090 2.82 0.071066363 + 4 -205.399652207 -0.694174803 -0.001534963 0.000946495 2.80 0.076733708 + 5 -205.400132587 -0.694655183 -0.000480380 0.000393693 2.87 0.080912002 + 6 -205.400207188 -0.694729784 -0.000074602 0.000265079 2.78 0.082774766 + 7 -205.400236344 -0.694758940 -0.000029156 0.000202667 2.84 0.083580390 + 8 -205.400242605 -0.694765201 -0.000006261 0.000150413 2.86 0.083923803 + 9 -205.400239476 -0.694762072 0.000003129 0.000104289 2.84 0.084062046 + 10 -205.400243864 -0.694766460 -0.000004388 0.000056396 2.75 0.084141578 + 11 -205.400240372 -0.694762968 0.000003493 0.000026718 2.76 0.084166005 + 12 -205.400243094 -0.694765690 -0.000002723 0.000012233 2.75 0.084184129 + 13 -205.400243174 -0.694765770 -0.000000080 0.000006301 2.88 0.084186122 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.705477404 +E(CORR) ... -0.694765770 +E(TOT) ... -205.400243174 +Singles norm **1/2 ... 0.084186122 ( 0.042093061, 0.042093061) +T1 diagnostic ... 0.019842859 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.060525 + 8a-> 13a 8b-> 13b 0.054809 + 9a-> 13a 8b-> 13b 0.047209 + 8a-> 13a 9b-> 13b 0.047209 + 5a-> 13a 5b-> 13b 0.030174 + 11a-> 13a 11b-> 13b 0.027648 + 8a-> 13a -1a-> -1a 0.027161 + 8b-> 13b -1b-> -1b 0.027161 + 11a-> 24a 11b-> 24b 0.025877 + 11a-> 25a 11b-> 25b 0.024729 + 11a-> 24a 11b-> 25b 0.023893 + 11a-> 25a 11b-> 24b 0.023893 + 9a-> 13a 9b-> 22b 0.023207 + 9a-> 22a 9b-> 13b 0.023207 + 11a-> 24a -1a-> -1a 0.020391 + 11b-> 24b -1b-> -1b 0.020391 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034513824 + alpha-alpha-alpha ... -0.000860018 ( 2.5%) + alpha-alpha-beta ... -0.016396894 ( 47.5%) + alpha-beta -beta ... -0.016396894 ( 47.5%) + beta -beta -beta ... -0.000860018 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034513824 + +Final correlation energy ... -0.729279594 +E(CCSD) ... -205.400243174 +E(CCSD(T)) ... -205.434756998 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210274389 sqrt= 1.100124715 +W(HF) = 0.826258912 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 54.337 sec + +Fock Matrix Formation ... 0.204 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 1.760 sec ( 3.2%) +State Vector Update ... 0.086 sec ( 0.2%) +Sigma-vector construction ... 37.348 sec ( 68.7%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.024 sec ( 0.1% of sigma) + (0-ext) ... 0.069 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (2-ext) ... 0.930 sec ( 2.5% of sigma) + (4-ext) ... 20.375 sec ( 54.6% of sigma) + ... 1.357 sec ( 3.6% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.106 sec ( 0.3% of sigma) + Fock-dressing ... 2.111 sec ( 5.7% of sigma) + (ik|jl)-dressing ... 0.075 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.634 sec ( 25.8% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.962 sec ( 12.8% of ALL) + I/O of integral and amplitudes ... 0.813 sec ( 11.7% of (T)) + External N**7 contributions ... 3.906 sec ( 56.1% of (T)) + Internal N**7 contributions ... 0.309 sec ( 4.4% of (T)) + N**6 triples energy contributions ... 1.699 sec ( 24.4% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.434756998488 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.000597785 -0.002316207 0.003414955 + 2 N : -0.001029657 -0.002805469 -0.002731245 + 3 O : 0.000750854 0.002489980 0.001891459 + 4 H : -0.000318982 0.002631696 -0.002575169 + +Norm of the cartesian gradient ... 0.007600993 +RMS gradient ... 0.002194218 +MAX gradient ... 0.003414955 + +------- +TIMINGS +------- + +Total numerical gradient time ... 346.039 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.434756998 Eh +Current gradient norm .... 0.007600993 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999980 +Lowest eigenvalues of augmented Hessian: + -0.000000013 0.096806707 0.158022739 0.468491487 0.499903773 +Length of the computed step .... 0.000198680 +The final length of the internal step .... 0.000198680 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0000811110 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0000919958 RMS(Int)= 0.0000811113 + Iter 1: RMS(Cart)= 0.0000000032 RMS(Int)= 0.0000000060 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000233165 0.0000050000 NO + RMS gradient 0.0000354434 0.0001000000 YES + MAX gradient 0.0000658158 0.0003000000 YES + RMS step 0.0000811110 0.0020000000 YES + MAX step 0.0001644417 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0000 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.5070 -0.000024 0.0000 1.5071 + 2. B(O 2,N 1) 1.1643 -0.000066 0.0000 1.1644 + 3. B(H 3,O 0) 0.9696 -0.000017 0.0000 0.9696 + 4. A(N 1,O 0,H 3) 102.65 -0.000028 0.01 102.66 + 5. A(O 0,N 1,O 2) 110.74 -0.000039 0.00 110.75 + 6. D(O 2,N 1,O 0,H 3) -98.18 0.006610 0.00 -98.18 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.799556 -0.234171 0.251428 + N 0.649860 -0.411930 -0.121131 + O 0.909042 0.203539 -1.074932 + H -0.759345 0.442562 0.944635 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.510941 -0.442520 0.475131 + 1 N 7.0000 0 14.007 1.228057 -0.778435 -0.228904 + 2 O 8.0000 0 15.999 1.717840 0.384633 -2.031328 + 3 H 1.0000 0 1.008 -1.434954 0.836322 1.785101 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.507051564134 0.00000000 0.00000000 + O 2 1 0 1.164351590876 110.74709339 0.00000000 + H 1 2 3 0.969598274082 102.66087731 261.81818198 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.847914725912 0.00000000 0.00000000 + O 2 1 0 2.200305630351 110.74709339 0.00000000 + H 1 2 3 1.832275197938 102.66087731 261.81818198 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2228 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2695 + la=0 lb=0: 548 shell pairs + la=1 lb=0: 535 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.324013850456 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.3240138505 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.899e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7054688740 0.000000000000 0.00000238 0.00000007 0.0000158 0.7000 + 1 -204.7054688760 -0.000000001981 0.00000225 0.00000006 0.0000125 0.7000 + ***Turning on DIIS*** + 2 -204.7054688778 -0.000000001831 0.00000604 0.00000017 0.0000097 0.0000 + 3 -204.7054764867 -0.000007608898 0.00000218 0.00000008 0.0000029 0.0000 + 4 -204.7054681577 0.000008329001 0.00000094 0.00000004 0.0000016 0.0000 + 5 -204.7054640482 0.000004109537 0.00000071 0.00000004 0.0000010 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 6 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70547162 Eh -5570.31907 eV + +Components: +Nuclear Repulsion : 68.32401385 Eh 1859.19094 eV +Electronic Energy : -273.02948547 Eh -7429.51001 eV +One Electron Energy: -416.35939237 Eh -11329.71506 eV +Two Electron Energy: 143.32990690 Eh 3900.20505 eV + +Virial components: +Potential Energy : -408.93316428 Eh -11127.63712 eV +Kinetic Energy : 204.22769266 Eh 5557.31805 eV +Virial Ratio : 2.00233944 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -7.5704e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.3355e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.0459e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.3584e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.692541 -563.0727 + 1 1.0000 -20.615601 -560.9790 + 2 1.0000 -15.805381 -430.0863 + 3 1.0000 -1.618431 -44.0397 + 4 1.0000 -1.370583 -37.2955 + 5 1.0000 -0.954456 -25.9721 + 6 1.0000 -0.768174 -20.9031 + 7 1.0000 -0.732121 -19.9220 + 8 1.0000 -0.699668 -19.0389 + 9 1.0000 -0.606422 -16.5016 + 10 1.0000 -0.528476 -14.3806 + 11 1.0000 -0.457939 -12.4612 + 12 0.0000 0.030803 0.8382 + 13 0.0000 0.067120 1.8264 + 14 0.0000 0.091522 2.4904 + 15 0.0000 0.102397 2.7864 + 16 0.0000 0.113510 3.0888 + 17 0.0000 0.155219 4.2237 + 18 0.0000 0.157285 4.2799 + 19 0.0000 0.173742 4.7278 + 20 0.0000 0.181484 4.9384 + 21 0.0000 0.189677 5.1614 + 22 0.0000 0.200840 5.4651 + 23 0.0000 0.236143 6.4258 + 24 0.0000 0.268604 7.3091 + 25 0.0000 0.290066 7.8931 + 26 0.0000 0.301175 8.1954 + 27 0.0000 0.330333 8.9888 + 28 0.0000 0.332300 9.0423 + 29 0.0000 0.353200 9.6111 + 30 0.0000 0.425257 11.5718 + 31 0.0000 0.505184 13.7467 + 32 0.0000 0.527115 14.3435 + 33 0.0000 0.543869 14.7994 + 34 0.0000 0.571481 15.5508 + 35 0.0000 0.600958 16.3529 + 36 0.0000 0.630086 17.1455 + 37 0.0000 0.649407 17.6713 + 38 0.0000 0.702399 19.1132 + 39 0.0000 0.719089 19.5674 + 40 0.0000 0.739452 20.1215 + 41 0.0000 0.753439 20.5021 + 42 0.0000 0.764967 20.8158 + 43 0.0000 0.791773 21.5452 + 44 0.0000 0.811808 22.0904 + 45 0.0000 0.813382 22.1333 + 46 0.0000 0.860251 23.4086 + 47 0.0000 0.869851 23.6698 + 48 0.0000 0.894747 24.3473 + 49 0.0000 0.940654 25.5965 + 50 0.0000 0.958826 26.0910 + 51 0.0000 0.985974 26.8297 + 52 0.0000 0.995642 27.0928 + 53 0.0000 1.027710 27.9654 + 54 0.0000 1.047397 28.5011 + 55 0.0000 1.113120 30.2895 + 56 0.0000 1.145285 31.1648 + 57 0.0000 1.230886 33.4941 + 58 0.0000 1.250156 34.0185 + 59 0.0000 1.270005 34.5586 + 60 0.0000 1.316656 35.8280 + 61 0.0000 1.413189 38.4548 + 62 0.0000 1.443330 39.2750 + 63 0.0000 1.518882 41.3309 + 64 0.0000 1.522578 41.4315 + 65 0.0000 1.567331 42.6493 + 66 0.0000 1.584440 43.1148 + 67 0.0000 1.633287 44.4440 + 68 0.0000 1.648584 44.8603 + 69 0.0000 1.709895 46.5286 + 70 0.0000 1.772983 48.2453 + 71 0.0000 1.790143 48.7123 + 72 0.0000 1.885077 51.2955 + 73 0.0000 1.925997 52.4090 + 74 0.0000 1.984079 53.9895 + 75 0.0000 2.020023 54.9676 + 76 0.0000 2.056065 55.9484 + 77 0.0000 2.082429 56.6658 + 78 0.0000 2.139632 58.2224 + 79 0.0000 2.211509 60.1782 + 80 0.0000 2.247409 61.1551 + 81 0.0000 2.296565 62.4927 + 82 0.0000 2.315340 63.0036 + 83 0.0000 2.365800 64.3767 + 84 0.0000 2.407461 65.5103 + 85 0.0000 2.452667 66.7405 + 86 0.0000 2.461119 66.9705 + 87 0.0000 2.476997 67.4025 + 88 0.0000 2.506002 68.1918 + 89 0.0000 2.559366 69.6439 + 90 0.0000 2.568780 69.9001 + 91 0.0000 2.598444 70.7073 + 92 0.0000 2.676253 72.8245 + 93 0.0000 2.721031 74.0430 + 94 0.0000 2.750362 74.8412 + 95 0.0000 2.800756 76.2124 + 96 0.0000 2.847010 77.4711 + 97 0.0000 2.878248 78.3211 + 98 0.0000 2.954910 80.4072 + 99 0.0000 2.987654 81.2982 + 100 0.0000 3.050978 83.0213 + 101 0.0000 3.164087 86.0992 + 102 0.0000 3.227884 87.8352 + 103 0.0000 3.486184 94.8639 + 104 0.0000 3.730400 101.5093 + 105 0.0000 3.809816 103.6704 + 106 0.0000 4.053414 110.2990 + 107 0.0000 4.176548 113.6497 + 108 0.0000 4.187060 113.9357 + 109 0.0000 4.298246 116.9612 + 110 0.0000 4.350543 118.3843 + 111 0.0000 4.392997 119.5395 + 112 0.0000 4.524485 123.1175 + 113 0.0000 4.604806 125.3031 + 114 0.0000 4.665249 126.9479 + 115 0.0000 4.719847 128.4336 + 116 0.0000 4.820527 131.1732 + 117 0.0000 4.900476 133.3487 + 118 0.0000 4.932523 134.2208 + 119 0.0000 4.948420 134.6533 + 120 0.0000 5.051815 137.4669 + 121 0.0000 5.099372 138.7610 + 122 0.0000 5.186251 141.1251 + 123 0.0000 5.196258 141.3974 + 124 0.0000 5.212073 141.8277 + 125 0.0000 5.333798 145.1400 + 126 0.0000 5.373327 146.2156 + 127 0.0000 5.479724 149.1109 + 128 0.0000 5.541694 150.7971 + 129 0.0000 5.725823 155.8076 + 130 0.0000 5.737299 156.1198 + 131 0.0000 5.928239 161.3156 + 132 0.0000 6.179757 168.1597 + 133 0.0000 6.414746 174.5541 + 134 0.0000 6.483432 176.4232 + 135 0.0000 6.501786 176.9226 + 136 0.0000 6.701302 182.3517 + 137 0.0000 6.728363 183.0881 + 138 0.0000 6.769362 184.2037 + 139 0.0000 6.812726 185.3837 + 140 0.0000 6.824689 185.7092 + 141 0.0000 7.063195 192.1993 + 142 0.0000 7.099813 193.1957 + 143 0.0000 7.119236 193.7243 + 144 0.0000 7.198862 195.8910 + 145 0.0000 7.257684 197.4916 + 146 0.0000 7.282824 198.1757 + 147 0.0000 7.347076 199.9241 + 148 0.0000 7.388932 201.0631 + 149 0.0000 7.448761 202.6911 + 150 0.0000 7.460753 203.0174 + 151 0.0000 7.553268 205.5349 + 152 0.0000 7.586381 206.4359 + 153 0.0000 7.611112 207.1089 + 154 0.0000 7.735833 210.5027 + 155 0.0000 7.902340 215.0336 + 156 0.0000 7.919433 215.4987 + 157 0.0000 8.397536 228.5086 + 158 0.0000 14.065085 382.7304 + 159 0.0000 14.830280 403.5524 + 160 0.0000 16.099668 438.0942 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.692541 -563.0727 + 1 1.0000 -20.615601 -560.9790 + 2 1.0000 -15.805381 -430.0863 + 3 1.0000 -1.618431 -44.0397 + 4 1.0000 -1.370583 -37.2955 + 5 1.0000 -0.954456 -25.9721 + 6 1.0000 -0.768174 -20.9031 + 7 1.0000 -0.732121 -19.9220 + 8 1.0000 -0.699668 -19.0389 + 9 1.0000 -0.606422 -16.5016 + 10 1.0000 -0.528476 -14.3806 + 11 1.0000 -0.457939 -12.4612 + 12 0.0000 0.030803 0.8382 + 13 0.0000 0.067120 1.8264 + 14 0.0000 0.091522 2.4904 + 15 0.0000 0.102397 2.7864 + 16 0.0000 0.113510 3.0888 + 17 0.0000 0.155219 4.2237 + 18 0.0000 0.157285 4.2799 + 19 0.0000 0.173742 4.7278 + 20 0.0000 0.181484 4.9384 + 21 0.0000 0.189677 5.1614 + 22 0.0000 0.200840 5.4651 + 23 0.0000 0.236143 6.4258 + 24 0.0000 0.268604 7.3091 + 25 0.0000 0.290066 7.8931 + 26 0.0000 0.301175 8.1954 + 27 0.0000 0.330333 8.9888 + 28 0.0000 0.332300 9.0423 + 29 0.0000 0.353200 9.6111 + 30 0.0000 0.425257 11.5718 + 31 0.0000 0.505184 13.7467 + 32 0.0000 0.527115 14.3435 + 33 0.0000 0.543869 14.7994 + 34 0.0000 0.571481 15.5508 + 35 0.0000 0.600958 16.3529 + 36 0.0000 0.630086 17.1455 + 37 0.0000 0.649407 17.6713 + 38 0.0000 0.702399 19.1132 + 39 0.0000 0.719089 19.5674 + 40 0.0000 0.739452 20.1215 + 41 0.0000 0.753439 20.5021 + 42 0.0000 0.764967 20.8158 + 43 0.0000 0.791773 21.5452 + 44 0.0000 0.811808 22.0904 + 45 0.0000 0.813382 22.1333 + 46 0.0000 0.860251 23.4086 + 47 0.0000 0.869851 23.6698 + 48 0.0000 0.894747 24.3473 + 49 0.0000 0.940654 25.5965 + 50 0.0000 0.958826 26.0910 + 51 0.0000 0.985974 26.8297 + 52 0.0000 0.995642 27.0928 + 53 0.0000 1.027710 27.9654 + 54 0.0000 1.047397 28.5011 + 55 0.0000 1.113120 30.2895 + 56 0.0000 1.145285 31.1648 + 57 0.0000 1.230886 33.4941 + 58 0.0000 1.250156 34.0185 + 59 0.0000 1.270005 34.5586 + 60 0.0000 1.316656 35.8280 + 61 0.0000 1.413189 38.4548 + 62 0.0000 1.443330 39.2750 + 63 0.0000 1.518882 41.3309 + 64 0.0000 1.522578 41.4315 + 65 0.0000 1.567331 42.6493 + 66 0.0000 1.584440 43.1148 + 67 0.0000 1.633287 44.4440 + 68 0.0000 1.648584 44.8603 + 69 0.0000 1.709895 46.5286 + 70 0.0000 1.772983 48.2453 + 71 0.0000 1.790143 48.7123 + 72 0.0000 1.885077 51.2955 + 73 0.0000 1.925997 52.4090 + 74 0.0000 1.984079 53.9895 + 75 0.0000 2.020023 54.9676 + 76 0.0000 2.056065 55.9484 + 77 0.0000 2.082429 56.6658 + 78 0.0000 2.139632 58.2224 + 79 0.0000 2.211509 60.1782 + 80 0.0000 2.247409 61.1551 + 81 0.0000 2.296565 62.4927 + 82 0.0000 2.315340 63.0036 + 83 0.0000 2.365800 64.3767 + 84 0.0000 2.407461 65.5103 + 85 0.0000 2.452667 66.7405 + 86 0.0000 2.461119 66.9705 + 87 0.0000 2.476997 67.4025 + 88 0.0000 2.506002 68.1918 + 89 0.0000 2.559366 69.6439 + 90 0.0000 2.568780 69.9001 + 91 0.0000 2.598444 70.7073 + 92 0.0000 2.676253 72.8245 + 93 0.0000 2.721031 74.0430 + 94 0.0000 2.750362 74.8412 + 95 0.0000 2.800756 76.2124 + 96 0.0000 2.847010 77.4711 + 97 0.0000 2.878248 78.3211 + 98 0.0000 2.954910 80.4072 + 99 0.0000 2.987654 81.2982 + 100 0.0000 3.050978 83.0213 + 101 0.0000 3.164087 86.0992 + 102 0.0000 3.227884 87.8352 + 103 0.0000 3.486184 94.8639 + 104 0.0000 3.730400 101.5093 + 105 0.0000 3.809816 103.6704 + 106 0.0000 4.053414 110.2990 + 107 0.0000 4.176548 113.6497 + 108 0.0000 4.187060 113.9357 + 109 0.0000 4.298246 116.9612 + 110 0.0000 4.350543 118.3843 + 111 0.0000 4.392997 119.5395 + 112 0.0000 4.524485 123.1175 + 113 0.0000 4.604806 125.3031 + 114 0.0000 4.665249 126.9479 + 115 0.0000 4.719847 128.4336 + 116 0.0000 4.820527 131.1732 + 117 0.0000 4.900476 133.3487 + 118 0.0000 4.932523 134.2208 + 119 0.0000 4.948420 134.6533 + 120 0.0000 5.051815 137.4669 + 121 0.0000 5.099372 138.7610 + 122 0.0000 5.186251 141.1251 + 123 0.0000 5.196258 141.3974 + 124 0.0000 5.212073 141.8277 + 125 0.0000 5.333798 145.1400 + 126 0.0000 5.373327 146.2156 + 127 0.0000 5.479724 149.1109 + 128 0.0000 5.541694 150.7971 + 129 0.0000 5.725823 155.8076 + 130 0.0000 5.737299 156.1198 + 131 0.0000 5.928239 161.3156 + 132 0.0000 6.179757 168.1597 + 133 0.0000 6.414746 174.5541 + 134 0.0000 6.483432 176.4232 + 135 0.0000 6.501786 176.9226 + 136 0.0000 6.701302 182.3517 + 137 0.0000 6.728363 183.0881 + 138 0.0000 6.769362 184.2037 + 139 0.0000 6.812726 185.3837 + 140 0.0000 6.824689 185.7092 + 141 0.0000 7.063195 192.1993 + 142 0.0000 7.099813 193.1957 + 143 0.0000 7.119236 193.7243 + 144 0.0000 7.198862 195.8910 + 145 0.0000 7.257684 197.4916 + 146 0.0000 7.282824 198.1757 + 147 0.0000 7.347076 199.9241 + 148 0.0000 7.388932 201.0631 + 149 0.0000 7.448761 202.6911 + 150 0.0000 7.460753 203.0174 + 151 0.0000 7.553268 205.5349 + 152 0.0000 7.586381 206.4359 + 153 0.0000 7.611112 207.1089 + 154 0.0000 7.735833 210.5027 + 155 0.0000 7.902340 215.0336 + 156 0.0000 7.919433 215.4987 + 157 0.0000 8.397536 228.5086 + 158 0.0000 14.065085 382.7304 + 159 0.0000 14.830280 403.5524 + 160 0.0000 16.099668 438.0942 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.378568 0.000000 + 1 N : 0.354501 0.000000 + 2 O : -0.225318 0.000000 + 3 H : 0.249384 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.867619 s : 3.867619 + pz : 1.606482 p : 4.482392 + px : 1.251577 + py : 1.624334 + dz2 : 0.003688 d : 0.024269 + dxz : 0.003152 + dyz : 0.002616 + dx2y2 : 0.011449 + dxy : 0.003363 + f0 : 0.000504 f : 0.004288 + f+1 : 0.000770 + f-1 : 0.000482 + f+2 : 0.000460 + f-2 : 0.000084 + f+3 : 0.001135 + f-3 : 0.000853 + 1 N s : 3.821662 s : 3.821662 + pz : 0.919073 p : 2.657215 + px : 0.830022 + py : 0.908120 + dz2 : 0.036002 d : 0.136079 + dxz : 0.031223 + dyz : 0.014903 + dx2y2 : 0.032331 + dxy : 0.021620 + f0 : 0.004789 f : 0.030543 + f+1 : 0.006083 + f-1 : 0.002877 + f+2 : 0.003995 + f-2 : 0.003542 + f+3 : 0.003867 + f-3 : 0.005391 + 2 O s : 3.875181 s : 3.875181 + pz : 1.193557 p : 4.279329 + px : 1.798447 + py : 1.287325 + dz2 : 0.025624 d : 0.063283 + dxz : 0.010607 + dyz : 0.013223 + dx2y2 : 0.005997 + dxy : 0.007832 + f0 : 0.002301 f : 0.007525 + f+1 : 0.001026 + f-1 : 0.001209 + f+2 : 0.000995 + f-2 : 0.001165 + f+3 : 0.000447 + f-3 : 0.000383 + 3 H s : 0.643297 s : 0.643297 + pz : 0.034089 p : 0.087075 + px : 0.021920 + py : 0.031066 + dz2 : 0.007840 d : 0.020244 + dxz : 0.005024 + dyz : -0.000111 + dx2y2 : 0.002777 + dxy : 0.004715 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.573745 0.000000 + 1 N : -0.230678 0.000000 + 2 O : 0.250016 0.000000 + 3 H : -0.593082 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.137747 s : 3.137747 + pz : 1.381432 p : 3.960353 + px : 1.174528 + py : 1.404393 + dz2 : 0.037575 d : 0.254299 + dxz : 0.055430 + dyz : 0.028983 + dx2y2 : 0.082238 + dxy : 0.050074 + f0 : 0.005385 f : 0.073856 + f+1 : 0.016321 + f-1 : 0.003814 + f+2 : 0.014276 + f-2 : 0.003420 + f+3 : 0.013892 + f-3 : 0.016748 + 1 N s : 3.038615 s : 3.038615 + pz : 1.038746 p : 2.838864 + px : 0.875406 + py : 0.924712 + dz2 : 0.181585 d : 0.916991 + dxz : 0.255327 + dyz : 0.164426 + dx2y2 : 0.177151 + dxy : 0.138501 + f0 : 0.058240 f : 0.436208 + f+1 : 0.081894 + f-1 : 0.058764 + f+2 : 0.071439 + f-2 : 0.058875 + f+3 : 0.047877 + f-3 : 0.059118 + 2 O s : 3.315370 s : 3.315370 + pz : 1.293037 p : 3.984902 + px : 1.476118 + py : 1.215747 + dz2 : 0.072974 d : 0.331684 + dxz : 0.078559 + dyz : 0.108761 + dx2y2 : 0.045963 + dxy : 0.025428 + f0 : 0.018614 f : 0.118028 + f+1 : 0.016546 + f-1 : 0.029132 + f+2 : 0.027373 + f-2 : 0.016896 + f+3 : 0.003031 + f-3 : 0.006437 + 3 H s : 0.628040 s : 0.628040 + pz : 0.216197 p : 0.574572 + px : 0.138079 + py : 0.220296 + dz2 : 0.101741 d : 0.390470 + dxz : 0.069138 + dyz : 0.096984 + dx2y2 : 0.062158 + dxy : 0.060448 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3786 8.0000 -0.3786 1.8230 1.8230 0.0000 + 1 N 6.6455 7.0000 0.3545 2.5968 2.5968 -0.0000 + 2 O 8.2253 8.0000 -0.2253 1.8143 1.8143 0.0000 + 3 H 0.7506 1.0000 0.2494 0.9893 0.9893 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8086 B( 0-O , 3-H ) : 0.9585 B( 1-N , 2-O ) : 1.7578 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.031 sec +Sum of individual times .... 0.859 sec ( 83.3%) + +Fock matrix formation .... 0.671 sec ( 65.1%) +Diagonalization .... 0.082 sec ( 8.0%) +Density matrix formation .... 0.006 sec ( 0.6%) +Population analysis .... 0.022 sec ( 2.2%) +Initial guess .... 0.010 sec ( 0.9%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.5%) +DIIS solution .... 0.068 sec ( 6.6%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.205 sec +Reference energy ... -204.705468879 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.358 sec +AO-integral generation ... 0.140 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.370 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.022 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.024 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.029 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.346 sec +AO-integral generation ... 0.237 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.053 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.169 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.255 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090037602 +EMP2(bb)= -0.090037602 +EMP2(ab)= -0.517593888 + +Initial guess performed in 0.133 sec +E(0) ... -204.705468879 +E(MP2) ... -0.697669091 +Initial E(tot) ... -205.403137971 + ... 0.189751982 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.403137971 -0.697669091 -0.000000000 0.018791666 2.67 0.000001768 + *** Turning on DIIS *** + 1 -205.374726989 -0.669258110 0.028410981 0.010621582 2.68 0.055516602 + 2 -205.394287548 -0.688818669 -0.019560559 0.003682854 2.75 0.058195411 + 3 -205.398115003 -0.692646124 -0.003827455 0.002030409 2.78 0.071071316 + 4 -205.399650173 -0.694181294 -0.001535170 0.000946888 2.77 0.076739342 + 5 -205.400130667 -0.694661787 -0.000480493 0.000393845 2.86 0.080918442 + 6 -205.400205284 -0.694736405 -0.000074618 0.000265228 2.82 0.082781615 + 7 -205.400234450 -0.694765570 -0.000029165 0.000202785 2.85 0.083587509 + 8 -205.400240715 -0.694771835 -0.000006265 0.000150497 2.85 0.083931102 + 9 -205.400237585 -0.694768706 0.000003129 0.000104341 2.78 0.084069459 + 10 -205.400241977 -0.694773097 -0.000004391 0.000056418 2.75 0.084149071 + 11 -205.400238483 -0.694769603 0.000003494 0.000026726 2.74 0.084173530 + 12 -205.400241206 -0.694772327 -0.000002724 0.000012236 2.75 0.084191668 + 13 -205.400241286 -0.694772407 -0.000000080 0.000006304 2.75 0.084193663 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.705468879 +E(CORR) ... -0.694772407 +E(TOT) ... -205.400241286 +Singles norm **1/2 ... 0.084193663 ( 0.042096832, 0.042096832) +T1 diagnostic ... 0.019844637 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.060530 + 8a-> 13a 8b-> 13b 0.054818 + 9a-> 13a 8b-> 13b 0.047215 + 8a-> 13a 9b-> 13b 0.047215 + 5a-> 13a 5b-> 13b 0.030176 + 11a-> 13a 11b-> 13b 0.027649 + 8a-> 13a -1a-> -1a 0.027165 + 8b-> 13b -1b-> -1b 0.027165 + 11a-> 24a 11b-> 24b 0.025896 + 11a-> 25a 11b-> 25b 0.024715 + 11a-> 24a 11b-> 25b 0.023895 + 11a-> 25a 11b-> 24b 0.023895 + 9a-> 13a 9b-> 22b 0.023206 + 9a-> 22a 9b-> 13b 0.023206 + 11a-> 24a -1a-> -1a 0.020400 + 11b-> 24b -1b-> -1b 0.020400 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034515714 + alpha-alpha-alpha ... -0.000860042 ( 2.5%) + alpha-alpha-beta ... -0.016397815 ( 47.5%) + alpha-beta -beta ... -0.016397815 ( 47.5%) + beta -beta -beta ... -0.000860042 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034515714 + +Final correlation energy ... -0.729288121 +E(CCSD) ... -205.400241286 +E(CCSD(T)) ... -205.434757000 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210285191 sqrt= 1.100129624 +W(HF) = 0.826251538 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.320835 0.000000 + 1 N : 0.182783 0.000000 + 2 O : -0.099296 -0.000000 + 3 H : 0.237348 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.844835 s : 3.844835 + pz : 1.584349 p : 4.412651 + px : 1.238301 + py : 1.590001 + dz2 : 0.010311 d : 0.055322 + dxz : 0.009877 + dyz : 0.008832 + dx2y2 : 0.015536 + dxy : 0.010766 + f0 : 0.001052 f : 0.008027 + f+1 : 0.001235 + f-1 : 0.001131 + f+2 : 0.001024 + f-2 : 0.000772 + f+3 : 0.001432 + f-3 : 0.001382 + 1 N s : 3.875989 s : 3.875989 + pz : 0.927169 p : 2.746212 + px : 0.881207 + py : 0.937836 + dz2 : 0.036238 d : 0.165473 + dxz : 0.042153 + dyz : 0.019455 + dx2y2 : 0.038188 + dxy : 0.029440 + f0 : 0.003747 f : 0.029543 + f+1 : 0.006072 + f-1 : 0.002895 + f+2 : 0.003883 + f-2 : 0.003506 + f+3 : 0.003965 + f-3 : 0.005475 + 2 O s : 3.862449 s : 3.862449 + pz : 1.174630 p : 4.142885 + px : 1.711906 + py : 1.256349 + dz2 : 0.025432 d : 0.084083 + dxz : 0.017477 + dyz : 0.016125 + dx2y2 : 0.011745 + dxy : 0.013304 + f0 : 0.002162 f : 0.009879 + f+1 : 0.001543 + f-1 : 0.001402 + f+2 : 0.001334 + f-2 : 0.001540 + f+3 : 0.000987 + f-3 : 0.000910 + 3 H s : 0.650648 s : 0.650648 + pz : 0.035709 p : 0.094707 + px : 0.025074 + py : 0.033924 + dz2 : 0.006855 d : 0.017298 + dxz : 0.004576 + dyz : -0.000809 + dx2y2 : 0.002449 + dxy : 0.004227 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.578694 0.000000 + 1 N : -0.274336 0.000000 + 2 O : 0.293181 -0.000000 + 3 H : -0.597539 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.141773 s : 3.141773 + pz : 1.362767 p : 3.913681 + px : 1.176141 + py : 1.374772 + dz2 : 0.043393 d : 0.285133 + dxz : 0.061548 + dyz : 0.036136 + dx2y2 : 0.088866 + dxy : 0.055191 + f0 : 0.006393 f : 0.080719 + f+1 : 0.016809 + f-1 : 0.004674 + f+2 : 0.015574 + f-2 : 0.004227 + f+3 : 0.015568 + f-3 : 0.017473 + 1 N s : 3.043413 s : 3.043413 + pz : 1.039531 p : 2.879168 + px : 0.899384 + py : 0.940253 + dz2 : 0.179519 d : 0.924917 + dxz : 0.255781 + dyz : 0.168876 + dx2y2 : 0.181865 + dxy : 0.138877 + f0 : 0.056967 f : 0.426838 + f+1 : 0.079792 + f-1 : 0.058977 + f+2 : 0.068833 + f-2 : 0.056134 + f+3 : 0.049048 + f-3 : 0.057088 + 2 O s : 3.318193 s : 3.318193 + pz : 1.282471 p : 3.902875 + px : 1.420811 + py : 1.199594 + dz2 : 0.080547 d : 0.359377 + dxz : 0.082157 + dyz : 0.113758 + dx2y2 : 0.051581 + dxy : 0.031335 + f0 : 0.022052 f : 0.126374 + f+1 : 0.017535 + f-1 : 0.029741 + f+2 : 0.027729 + f-2 : 0.018332 + f+3 : 0.004110 + f-3 : 0.006875 + 3 H s : 0.628069 s : 0.628069 + pz : 0.223585 p : 0.589076 + px : 0.137666 + py : 0.227826 + dz2 : 0.098198 d : 0.380394 + dxz : 0.066314 + dyz : 0.096109 + dx2y2 : 0.061388 + dxy : 0.058385 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3208 8.0000 -0.3208 2.1640 1.7001 0.4639 + 1 N 6.8172 7.0000 0.1828 2.8584 2.3635 0.4950 + 2 O 8.0993 8.0000 -0.0993 2.1990 1.7007 0.4983 + 3 H 0.7627 1.0000 0.2373 1.0113 0.9369 0.0744 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7171 B( 0-O , 3-H ) : 0.8962 B( 1-N , 2-O ) : 1.6098 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 53.914 sec + +Fock Matrix Formation ... 0.205 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 1.684 sec ( 3.1%) +State Vector Update ... 0.084 sec ( 0.2%) +Sigma-vector construction ... 37.041 sec ( 68.7%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.023 sec ( 0.1% of sigma) + (0-ext) ... 0.071 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (2-ext) ... 0.944 sec ( 2.5% of sigma) + (4-ext) ... 20.250 sec ( 54.7% of sigma) + ... 1.326 sec ( 3.6% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.107 sec ( 0.3% of sigma) + Fock-dressing ... 2.139 sec ( 5.8% of sigma) + (ik|jl)-dressing ... 0.076 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.483 sec ( 25.6% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.914 sec ( 12.8% of ALL) + I/O of integral and amplitudes ... 0.838 sec ( 12.1% of (T)) + External N**7 contributions ... 3.971 sec ( 57.4% of (T)) + Internal N**7 contributions ... 0.331 sec ( 4.8% of (T)) + N**6 triples energy contributions ... 1.693 sec ( 24.5% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.434757000300 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.011.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.011.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.405529, -0.233694 -0.559515) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 1.06882 -0.14664 -0.65353 +Nuclear contribution : -0.91606 0.53284 1.16155 + ----------------------------------------- +Total Dipole Moment : 0.15276 0.38620 0.50803 + ----------------------------------------- +Magnitude (a.u.) : 0.65618 +Magnitude (Debye) : 1.66788 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.734946 0.398414 0.359906 +Rotational constants in MHz : 81991.604318 11944.154054 10789.698715 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.123406 -0.132652 0.630674 +x,y,z [Debye]: -0.313672 -0.337174 1.603046 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.405529, -0.233694 -0.559515) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 1.11566 -0.10446 -0.82163 +Nuclear contribution : -0.91606 0.53284 1.16155 + ----------------------------------------- +Total Dipole Moment : 0.19960 0.42838 0.33993 + ----------------------------------------- +Magnitude (a.u.) : 0.58215 +Magnitude (Debye) : 1.47971 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.734946 0.398414 0.359906 +Rotational constants in MHz : 81991.604318 11944.154054 10789.698715 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.019096 -0.035533 0.580753 +x,y,z [Debye]: 0.048538 -0.090317 1.476156 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 12 * + * * + * Dihedral ( 2, 1, 0, 3) : -90.00000000 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0394801254 RMS(Int)= 0.0005172584 + Iter 1: RMS(Cart)= 0.0001430075 RMS(Int)= 0.0000047701 + Iter 2: RMS(Cart)= 0.0000013188 RMS(Int)= 0.0000000439 + Iter 3: RMS(Cart)= 0.0000000121 RMS(Int)= 0.0000000117 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.5074 0.000000 + 2. B(O 2,N 1) 1.1663 0.000000 + 3. B(H 3,O 0) 0.9723 0.000000 + 4. A(N 1,O 0,H 3) 102.5710 0.000000 + 5. A(O 0,N 1,O 2) 110.6556 0.000000 + 6. D(O 2,N 1,O 0,H 3) -90.0000 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.797652 -0.258936 0.270744 + N 0.643029 -0.441196 -0.133652 + O 0.901176 0.231515 -1.050797 + H -0.746553 0.468618 0.913706 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.507343 -0.489319 0.511631 + 1 N 7.0000 0 14.007 1.215149 -0.833740 -0.252566 + 2 O 8.0000 0 15.999 1.702976 0.437500 -1.985719 + 3 H 1.0000 0 1.008 -1.410780 0.885559 1.726654 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.507051564134 0.00000000 0.00000000 + O 2 1 0 1.164351590876 110.74709339 0.00000000 + H 1 2 3 0.969598274082 102.66087731 261.81818198 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.847914725912 0.00000000 0.00000000 + O 2 1 0 2.200305630351 110.74709339 0.00000000 + H 1 2 3 1.832275197938 102.66087731 261.81818198 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2229 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2696 + la=0 lb=0: 549 shell pairs + la=1 lb=0: 535 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.293039052457 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.2930390525 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.871e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.6998900465 0.000000000000 0.00160233 0.00005165 0.0196748 0.7000 + 1 -204.7007934450 -0.000903398513 0.00151800 0.00004740 0.0163172 0.7000 + ***Turning on DIIS*** + 2 -204.7015697810 -0.000776335938 0.00426271 0.00013028 0.0132933 0.0000 + 3 -204.7061035219 -0.004533740958 0.00200485 0.00005882 0.0051036 0.0000 + 4 -204.7032440792 0.002859442758 0.00095228 0.00003051 0.0019897 0.0000 + 5 -204.7052902451 -0.002046165965 0.00086612 0.00002632 0.0011724 0.0000 + 6 -204.7041604156 0.001129829528 0.00100261 0.00003072 0.0006935 0.0000 + 7 -204.7041504460 0.000009969623 0.00036408 0.00001278 0.0003379 0.0000 + 8 -204.7048408027 -0.000690356700 0.00018802 0.00000774 0.0001839 0.0000 + 9 -204.7042909707 0.000549832017 0.00015053 0.00000644 0.0001293 0.0000 + 10 -204.7045552387 -0.000264268027 0.00006273 0.00000238 0.0000537 0.0000 + 11 -204.7046056929 -0.000050454194 0.00001932 0.00000079 0.0000298 0.0000 + 12 -204.7045171570 0.000088535929 0.00000867 0.00000029 0.0000107 0.0000 + 13 -204.7045475382 -0.000030381248 0.00000216 0.00000009 0.0000035 0.0000 + 14 -204.7045398640 0.000007674239 0.00000133 0.00000004 0.0000027 0.0000 + 15 -204.7045422144 -0.000002350465 0.00000098 0.00000003 0.0000018 0.0000 + 16 -204.7045440139 -0.000001799483 0.00000065 0.00000002 0.0000012 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 17 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70454232 Eh -5570.29378 eV + +Components: +Nuclear Repulsion : 68.29303905 Eh 1858.34807 eV +Electronic Energy : -272.99758137 Eh -7428.64185 eV +One Electron Energy: -416.29751061 Eh -11328.03117 eV +Two Electron Energy: 143.29992924 Eh 3899.38932 eV + +Virial components: +Potential Energy : -408.92127028 Eh -11127.31347 eV +Kinetic Energy : 204.21672796 Eh 5557.01968 eV +Virial Ratio : 2.00238871 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.6959e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.0055e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.9085e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 4.4811e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.692812 -563.0800 + 1 1.0000 -20.616161 -560.9943 + 2 1.0000 -15.805953 -430.1019 + 3 1.0000 -1.617342 -44.0101 + 4 1.0000 -1.369815 -37.2746 + 5 1.0000 -0.955251 -25.9937 + 6 1.0000 -0.766424 -20.8555 + 7 1.0000 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0.0000 0.030892 0.8406 + 13 0.0000 0.065782 1.7900 + 14 0.0000 0.091675 2.4946 + 15 0.0000 0.103105 2.8056 + 16 0.0000 0.113036 3.0759 + 17 0.0000 0.155501 4.2314 + 18 0.0000 0.157154 4.2764 + 19 0.0000 0.174238 4.7412 + 20 0.0000 0.180149 4.9021 + 21 0.0000 0.189552 5.1580 + 22 0.0000 0.200793 5.4639 + 23 0.0000 0.235721 6.4143 + 24 0.0000 0.268224 7.2988 + 25 0.0000 0.292161 7.9501 + 26 0.0000 0.299524 8.1505 + 27 0.0000 0.331549 9.0219 + 28 0.0000 0.332317 9.0428 + 29 0.0000 0.352188 9.5835 + 30 0.0000 0.424302 11.5458 + 31 0.0000 0.505263 13.7489 + 32 0.0000 0.528655 14.3854 + 33 0.0000 0.544107 14.8059 + 34 0.0000 0.568749 15.4765 + 35 0.0000 0.599373 16.3098 + 36 0.0000 0.629689 17.1347 + 37 0.0000 0.647021 17.6063 + 38 0.0000 0.706521 19.2254 + 39 0.0000 0.717411 19.5218 + 40 0.0000 0.738375 20.0922 + 41 0.0000 0.757281 20.6067 + 42 0.0000 0.761281 20.7155 + 43 0.0000 0.791316 21.5328 + 44 0.0000 0.809013 22.0144 + 45 0.0000 0.815365 22.1872 + 46 0.0000 0.862892 23.4805 + 47 0.0000 0.869014 23.6471 + 48 0.0000 0.892588 24.2886 + 49 0.0000 0.945269 25.7221 + 50 0.0000 0.960492 26.1363 + 51 0.0000 0.980000 26.6672 + 52 0.0000 0.993518 27.0350 + 53 0.0000 1.028699 27.9923 + 54 0.0000 1.044954 28.4347 + 55 0.0000 1.106828 30.1183 + 56 0.0000 1.152180 31.3524 + 57 0.0000 1.225272 33.3414 + 58 0.0000 1.254837 34.1458 + 59 0.0000 1.258707 34.2512 + 60 0.0000 1.315995 35.8100 + 61 0.0000 1.408265 38.3208 + 62 0.0000 1.451892 39.5080 + 63 0.0000 1.517782 41.3010 + 64 0.0000 1.526173 41.5293 + 65 0.0000 1.569375 42.7049 + 66 0.0000 1.585263 43.1372 + 67 0.0000 1.631534 44.3963 + 68 0.0000 1.648569 44.8598 + 69 0.0000 1.715788 46.6890 + 70 0.0000 1.768504 48.1234 + 71 0.0000 1.784049 48.5464 + 72 0.0000 1.890528 51.4439 + 73 0.0000 1.922826 52.3227 + 74 0.0000 1.985576 54.0303 + 75 0.0000 2.013213 54.7823 + 76 0.0000 2.047620 55.7186 + 77 0.0000 2.092226 56.9324 + 78 0.0000 2.137273 58.1581 + 79 0.0000 2.202325 59.9283 + 80 0.0000 2.262848 61.5752 + 81 0.0000 2.292818 62.3907 + 82 0.0000 2.323574 63.2277 + 83 0.0000 2.357925 64.1624 + 84 0.0000 2.404446 65.4283 + 85 0.0000 2.452598 66.7386 + 86 0.0000 2.463715 67.0411 + 87 0.0000 2.477027 67.4033 + 88 0.0000 2.507704 68.2381 + 89 0.0000 2.569739 69.9261 + 90 0.0000 2.572241 69.9942 + 91 0.0000 2.601099 70.7795 + 92 0.0000 2.671212 72.6874 + 93 0.0000 2.727767 74.2263 + 94 0.0000 2.741973 74.6129 + 95 0.0000 2.776713 75.5582 + 96 0.0000 2.845148 77.4204 + 97 0.0000 2.887337 78.5684 + 98 0.0000 2.959808 80.5405 + 99 0.0000 2.985533 81.2405 + 100 0.0000 3.053298 83.0845 + 101 0.0000 3.167336 86.1876 + 102 0.0000 3.220831 87.6433 + 103 0.0000 3.483253 94.7841 + 104 0.0000 3.722951 101.3066 + 105 0.0000 3.808608 103.6375 + 106 0.0000 4.049973 110.2054 + 107 0.0000 4.169834 113.4670 + 108 0.0000 4.189929 114.0138 + 109 0.0000 4.288248 116.6892 + 110 0.0000 4.355981 118.5323 + 111 0.0000 4.392663 119.5304 + 112 0.0000 4.519457 122.9807 + 113 0.0000 4.601354 125.2092 + 114 0.0000 4.660273 126.8125 + 115 0.0000 4.716550 128.3438 + 116 0.0000 4.827831 131.3720 + 117 0.0000 4.899456 133.3210 + 118 0.0000 4.930299 134.1603 + 119 0.0000 4.944708 134.5523 + 120 0.0000 5.048673 137.3814 + 121 0.0000 5.100292 138.7860 + 122 0.0000 5.181668 141.0004 + 123 0.0000 5.194787 141.3574 + 124 0.0000 5.221873 142.0944 + 125 0.0000 5.316334 144.6648 + 126 0.0000 5.379459 146.3825 + 127 0.0000 5.481486 149.1588 + 128 0.0000 5.552698 151.0966 + 129 0.0000 5.706186 155.2732 + 130 0.0000 5.738315 156.1475 + 131 0.0000 5.931038 161.3918 + 132 0.0000 6.179510 168.1530 + 133 0.0000 6.415518 174.5751 + 134 0.0000 6.481158 176.3613 + 135 0.0000 6.504054 176.9843 + 136 0.0000 6.699585 182.3050 + 137 0.0000 6.726787 183.0452 + 138 0.0000 6.766844 184.1352 + 139 0.0000 6.819104 185.5573 + 140 0.0000 6.823611 185.6799 + 141 0.0000 7.059943 192.1108 + 142 0.0000 7.098959 193.1725 + 143 0.0000 7.115909 193.6337 + 144 0.0000 7.192245 195.7109 + 145 0.0000 7.256174 197.4505 + 146 0.0000 7.279385 198.0821 + 147 0.0000 7.338681 199.6957 + 148 0.0000 7.383578 200.9174 + 149 0.0000 7.454102 202.8364 + 150 0.0000 7.460057 202.9985 + 151 0.0000 7.559851 205.7140 + 152 0.0000 7.577610 206.1973 + 153 0.0000 7.625410 207.4980 + 154 0.0000 7.711982 209.8537 + 155 0.0000 7.892013 214.7526 + 156 0.0000 7.912832 215.3191 + 157 0.0000 8.395628 228.4566 + 158 0.0000 14.047557 382.2534 + 159 0.0000 14.800868 402.7521 + 160 0.0000 16.044338 436.5886 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.379658 0.000000 + 1 N : 0.352810 0.000000 + 2 O : -0.224188 0.000000 + 3 H : 0.251036 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.866014 s : 3.866014 + pz : 1.640293 p : 4.484049 + px : 1.254837 + py : 1.588919 + dz2 : 0.003010 d : 0.025346 + dxz : 0.003753 + dyz : 0.002776 + dx2y2 : 0.012270 + dxy : 0.003537 + f0 : 0.000595 f : 0.004249 + f+1 : 0.000763 + f-1 : 0.000377 + f+2 : 0.000498 + f-2 : 0.000082 + f+3 : 0.001105 + f-3 : 0.000830 + 1 N s : 3.822108 s : 3.822108 + pz : 0.891679 p : 2.657071 + px : 0.827014 + py : 0.938377 + dz2 : 0.036149 d : 0.137292 + dxz : 0.031376 + dyz : 0.014245 + dx2y2 : 0.034005 + dxy : 0.021517 + f0 : 0.004478 f : 0.030719 + f+1 : 0.005576 + f-1 : 0.002958 + f+2 : 0.003993 + f-2 : 0.003933 + f+3 : 0.004214 + f-3 : 0.005566 + 2 O s : 3.875859 s : 3.875859 + pz : 1.190534 p : 4.278320 + px : 1.790712 + py : 1.297074 + dz2 : 0.025617 d : 0.062518 + dxz : 0.009381 + dyz : 0.011753 + dx2y2 : 0.006694 + dxy : 0.009074 + f0 : 0.002046 f : 0.007492 + f+1 : 0.000822 + f-1 : 0.001291 + f+2 : 0.001069 + f-2 : 0.001231 + f+3 : 0.000562 + f-3 : 0.000470 + 3 H s : 0.642347 s : 0.642347 + pz : 0.035863 p : 0.086732 + px : 0.021822 + py : 0.029046 + dz2 : 0.007467 d : 0.019886 + dxz : 0.004088 + dyz : 0.000040 + dx2y2 : 0.002921 + dxy : 0.005370 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.570161 0.000000 + 1 N : -0.230135 0.000000 + 2 O : 0.249141 0.000000 + 3 H : -0.589167 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.139541 s : 3.139541 + pz : 1.391995 p : 3.962296 + px : 1.177561 + py : 1.392740 + dz2 : 0.035205 d : 0.254224 + dxz : 0.055735 + dyz : 0.029483 + dx2y2 : 0.081988 + dxy : 0.051813 + f0 : 0.005708 f : 0.073777 + f+1 : 0.016175 + f-1 : 0.002877 + f+2 : 0.014140 + f-2 : 0.003834 + f+3 : 0.013490 + f-3 : 0.017553 + 1 N s : 3.040167 s : 3.040167 + pz : 0.999337 p : 2.838445 + px : 0.872343 + py : 0.966764 + dz2 : 0.170762 d : 0.914724 + dxz : 0.246469 + dyz : 0.168143 + dx2y2 : 0.185230 + dxy : 0.144121 + f0 : 0.053109 f : 0.436800 + f+1 : 0.073932 + f-1 : 0.057113 + f+2 : 0.074267 + f-2 : 0.065131 + f+3 : 0.051502 + f-3 : 0.061745 + 2 O s : 3.315367 s : 3.315367 + pz : 1.269016 p : 3.986370 + px : 1.472127 + py : 1.245227 + dz2 : 0.062805 d : 0.331400 + dxz : 0.074191 + dyz : 0.112495 + dx2y2 : 0.052612 + dxy : 0.029297 + f0 : 0.015927 f : 0.117722 + f+1 : 0.014128 + f-1 : 0.027866 + f+2 : 0.029218 + f-2 : 0.018502 + f+3 : 0.003747 + f-3 : 0.008334 + 3 H s : 0.626627 s : 0.626627 + pz : 0.207351 p : 0.572698 + px : 0.138363 + py : 0.226984 + dz2 : 0.094016 d : 0.389841 + dxz : 0.061656 + dyz : 0.096960 + dx2y2 : 0.068313 + dxy : 0.068897 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3797 8.0000 -0.3797 1.8173 1.8173 0.0000 + 1 N 6.6472 7.0000 0.3528 2.5993 2.5993 0.0000 + 2 O 8.2242 8.0000 -0.2242 1.8138 1.8138 0.0000 + 3 H 0.7490 1.0000 0.2510 0.9906 0.9906 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8065 B( 0-O , 3-H ) : 0.9553 B( 1-N , 2-O ) : 1.7578 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.492 sec +Sum of individual times .... 2.297 sec ( 92.2%) + +Fock matrix formation .... 1.869 sec ( 75.0%) +Diagonalization .... 0.209 sec ( 8.4%) +Density matrix formation .... 0.015 sec ( 0.6%) +Population analysis .... 0.024 sec ( 1.0%) +Initial guess .... 0.009 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.2%) +DIIS solution .... 0.171 sec ( 6.9%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.206 sec +Reference energy ... -204.704542875 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.392 sec +AO-integral generation ... 0.140 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.402 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.026 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.024 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.030 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.036 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.025 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.354 sec +AO-integral generation ... 0.244 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.055 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.158 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.251 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090059726 +EMP2(bb)= -0.090059726 +EMP2(ab)= -0.517829376 + +Initial guess performed in 0.133 sec +E(0) ... -204.704542875 +E(MP2) ... -0.697948828 +Initial E(tot) ... -205.402491702 + ... 0.190034894 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.402491702 -0.697948828 -0.000000000 0.018743444 2.66 0.000001654 + *** Turning on DIIS *** + 1 -205.374004361 -0.669461486 0.028487342 0.010942650 2.71 0.055491613 + 2 -205.393605345 -0.689062470 -0.019600984 0.003688092 2.74 0.058166199 + 3 -205.397444552 -0.692901677 -0.003839207 0.002103145 2.77 0.071001923 + 4 -205.398982870 -0.694439996 -0.001538318 0.000957521 2.76 0.076635832 + 5 -205.399461757 -0.694918883 -0.000478887 0.000401726 2.86 0.080751414 + 6 -205.399534650 -0.694991775 -0.000072892 0.000304416 2.79 0.082558438 + 7 -205.399562620 -0.695019745 -0.000027970 0.000232025 2.79 0.083321363 + 8 -205.399568404 -0.695025529 -0.000005784 0.000171234 2.83 0.083644003 + 9 -205.399565383 -0.695022508 0.000003021 0.000118166 2.77 0.083774350 + 10 -205.399569613 -0.695026739 -0.000004231 0.000060889 2.73 0.083854201 + 11 -205.399566086 -0.695023212 0.000003527 0.000022623 2.72 0.083887049 + 12 -205.399568738 -0.695025864 -0.000002652 0.000011319 2.71 0.083905457 + 13 -205.399568947 -0.695026073 -0.000000209 0.000003819 2.72 0.083908504 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.704542875 +E(CORR) ... -0.695026073 +E(TOT) ... -205.399568947 +Singles norm **1/2 ... 0.083908504 ( 0.041954252, 0.041954252) +T1 diagnostic ... 0.019777424 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.062319 + 8a-> 13a 8b-> 13b 0.054918 + 8a-> 13a 9b-> 13b 0.047441 + 9a-> 13a 8b-> 13b 0.047441 + 5a-> 13a 5b-> 13b 0.030309 + 11a-> 25a 11b-> 25b 0.028307 + 11a-> 13a 11b-> 13b 0.027839 + 8a-> 13a -1a-> -1a 0.027261 + 8b-> 13b -1b-> -1b 0.027261 + 11a-> 24a 11b-> 24b 0.025952 + 11a-> 25a 11b-> 24b 0.025708 + 11a-> 24a 11b-> 25b 0.025708 + 9a-> 13a 9b-> 22b 0.023915 + 9a-> 22a 9b-> 13b 0.023915 + 11b-> 25b -1b-> -1b 0.020691 + 11a-> 25a -1a-> -1a 0.020691 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034553560 + alpha-alpha-alpha ... -0.000859750 ( 2.5%) + alpha-alpha-beta ... -0.016417030 ( 47.5%) + alpha-beta -beta ... -0.016417030 ( 47.5%) + beta -beta -beta ... -0.000859750 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034553560 + +Final correlation energy ... -0.729579633 +E(CCSD) ... -205.399568947 +E(CCSD(T)) ... -205.434122508 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210508852 sqrt= 1.100231272 +W(HF) = 0.826098874 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.322997 -0.000000 + 1 N : 0.182173 0.000000 + 2 O : -0.097779 -0.000000 + 3 H : 0.238602 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.843890 s : 3.843890 + pz : 1.615845 p : 4.414889 + px : 1.240676 + py : 1.558368 + dz2 : 0.009800 d : 0.056232 + dxz : 0.010348 + dyz : 0.008991 + dx2y2 : 0.016231 + dxy : 0.010862 + f0 : 0.001128 f : 0.007986 + f+1 : 0.001240 + f-1 : 0.001026 + f+2 : 0.001054 + f-2 : 0.000768 + f+3 : 0.001417 + f-3 : 0.001353 + 1 N s : 3.876271 s : 3.876271 + pz : 0.908833 p : 2.745395 + px : 0.877049 + py : 0.959513 + dz2 : 0.036442 d : 0.166463 + dxz : 0.042104 + dyz : 0.019017 + dx2y2 : 0.039840 + dxy : 0.029061 + f0 : 0.003629 f : 0.029697 + f+1 : 0.005623 + f-1 : 0.002851 + f+2 : 0.003853 + f-2 : 0.003851 + f+3 : 0.004275 + f-3 : 0.005615 + 2 O s : 3.862950 s : 3.862950 + pz : 1.170010 p : 4.141567 + px : 1.705248 + py : 1.266310 + dz2 : 0.025472 d : 0.083416 + dxz : 0.016258 + dyz : 0.014889 + dx2y2 : 0.012392 + dxy : 0.014405 + f0 : 0.001982 f : 0.009846 + f+1 : 0.001357 + f-1 : 0.001439 + f+2 : 0.001399 + f-2 : 0.001594 + f+3 : 0.001089 + f-3 : 0.000987 + 3 H s : 0.649914 s : 0.649914 + pz : 0.038587 p : 0.094466 + px : 0.025057 + py : 0.030822 + dz2 : 0.006639 d : 0.017017 + dxz : 0.003761 + dyz : -0.000640 + dx2y2 : 0.002453 + dxy : 0.004805 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.574758 -0.000000 + 1 N : -0.273543 0.000000 + 2 O : 0.292876 0.000000 + 3 H : -0.594091 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.143545 s : 3.143545 + pz : 1.371378 p : 3.915980 + px : 1.178147 + py : 1.366455 + dz2 : 0.040972 d : 0.285065 + dxz : 0.061910 + dyz : 0.036665 + dx2y2 : 0.088572 + dxy : 0.056945 + f0 : 0.006782 f : 0.080653 + f+1 : 0.016641 + f-1 : 0.003644 + f+2 : 0.015523 + f-2 : 0.004691 + f+3 : 0.015163 + f-3 : 0.018209 + 1 N s : 3.044977 s : 3.044977 + pz : 1.006227 p : 2.878705 + px : 0.895700 + py : 0.976778 + dz2 : 0.168487 d : 0.922295 + dxz : 0.247366 + dyz : 0.173401 + dx2y2 : 0.189625 + dxy : 0.143417 + f0 : 0.052280 f : 0.427566 + f+1 : 0.071868 + f-1 : 0.057393 + f+2 : 0.071595 + f-2 : 0.062077 + f+3 : 0.052569 + f-3 : 0.059784 + 2 O s : 3.318202 s : 3.318202 + pz : 1.257429 p : 3.903710 + px : 1.417540 + py : 1.228740 + dz2 : 0.070882 d : 0.359153 + dxz : 0.077909 + dyz : 0.117264 + dx2y2 : 0.058082 + dxy : 0.035016 + f0 : 0.019256 f : 0.126059 + f+1 : 0.015036 + f-1 : 0.028856 + f+2 : 0.029413 + f-2 : 0.019843 + f+3 : 0.004921 + f-3 : 0.008732 + 3 H s : 0.626797 s : 0.626797 + pz : 0.215147 p : 0.587510 + px : 0.137905 + py : 0.234459 + dz2 : 0.090837 d : 0.379784 + dxz : 0.059119 + dyz : 0.095997 + dx2y2 : 0.067292 + dxy : 0.066540 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3230 8.0000 -0.3230 2.1579 1.6939 0.4640 + 1 N 6.8178 7.0000 0.1822 2.8602 2.3639 0.4964 + 2 O 8.0978 8.0000 -0.0978 2.1980 1.6991 0.4989 + 3 H 0.7614 1.0000 0.2386 1.0127 0.9380 0.0747 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7146 B( 0-O , 3-H ) : 0.8934 B( 1-N , 2-O ) : 1.6089 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 53.585 sec + +Fock Matrix Formation ... 0.206 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 1.599 sec ( 3.0%) +State Vector Update ... 0.082 sec ( 0.2%) +Sigma-vector construction ... 36.897 sec ( 68.9%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.024 sec ( 0.1% of sigma) + (0-ext) ... 0.067 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.025 sec ( 0.1% of sigma) + (2-ext) ... 0.922 sec ( 2.5% of sigma) + (4-ext) ... 20.348 sec ( 55.1% of sigma) + ... 1.334 sec ( 3.6% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.106 sec ( 0.3% of sigma) + Fock-dressing ... 2.047 sec ( 5.5% of sigma) + (ik|jl)-dressing ... 0.073 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.347 sec ( 25.3% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.782 sec ( 12.7% of ALL) + I/O of integral and amplitudes ... 0.633 sec ( 9.3% of (T)) + External N**7 contributions ... 3.873 sec ( 57.1% of (T)) + Internal N**7 contributions ... 0.309 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.548 sec ( 22.8% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.434122507520 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.000413316 -0.002094650 -0.001304376 + 2 N : 0.000323493 -0.002876207 0.001759535 + 3 O : -0.000369110 0.002416518 -0.001127312 + 4 H : 0.000458934 0.002554339 0.000672153 + +Norm of the cartesian gradient ... 0.005671565 +RMS gradient ... 0.001637240 +MAX gradient ... 0.002876207 + +------- +TIMINGS +------- + +Total numerical gradient time ... 345.452 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: -528.05 cm**-1 ***imaginary mode*** + 7: 542.47 cm**-1 + 8: 774.38 cm**-1 + 9: 1123.92 cm**-1 + 10: 1705.21 cm**-1 + 11: 3712.56 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 0.015128 0.602753 -0.194773 0.051591 -0.076398 -0.002240 + 1 -0.036478 0.079378 0.201280 0.036878 0.019317 -0.046579 + 2 0.058208 -0.363634 -0.171295 0.017171 0.011105 -0.041856 + 3 -0.024256 -0.298193 0.677098 0.016141 -0.058060 -0.000025 + 4 -0.056412 -0.100741 -0.294350 -0.038914 -0.463627 0.000123 + 5 -0.048669 0.247183 0.035162 -0.030697 0.578395 -0.000540 + 6 0.012717 -0.360214 -0.409417 -0.003954 0.130422 -0.000492 + 7 0.043735 0.006681 0.041166 -0.000139 0.385942 -0.000464 + 8 0.030172 0.166428 0.156055 -0.001203 -0.520076 0.000574 + 9 -0.104913 0.294058 0.180873 -0.980398 -0.050684 0.043694 + 10 0.668702 0.033954 0.242116 -0.042381 0.010209 0.744949 + 11 -0.726470 -0.304746 -0.246702 0.173125 0.041129 0.662733 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 7: 542.47 0.026559 134.22 0.015279 (-0.101914 -0.008413 0.069435) + 8: 774.38 0.025256 127.63 0.010178 ( 0.089769 -0.006819 -0.045526) + 9: 1123.92 0.010358 52.34 0.002876 (-0.046995 0.014783 0.021185) + 10: 1705.21 0.033724 170.43 0.006172 (-0.059078 -0.013614 0.049962) + 11: 3712.56 0.011235 56.78 0.000944 (-0.012634 0.017048 0.022229) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 7 +The total number of vibrations considered is 5 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 542.47 E(vib) ... 0.12 +freq. 774.38 E(vib) ... 0.05 +freq. 1123.92 E(vib) ... 0.01 +freq. 1705.21 E(vib) ... 0.00 +freq. 3712.56 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.43412251 Eh +Zero point energy ... 0.01790307 Eh 11.23 kcal/mol +Thermal vibrational correction ... 0.00030545 Eh 0.19 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.41308144 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00313799 Eh 1.97 kcal/mol +Non-thermal (ZPE) correction 0.01790307 Eh 11.23 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02104107 Eh 13.20 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.41308144 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.41213723 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.692132 0.399682 0.360443 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00040460 Eh 0.25 kcal/mol +Rotational entropy ... 0.00995796 Eh 6.25 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02816488 Eh 17.67 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00995796 Eh 6.25 kcal/mol| +| sn= 2 | S(rot)= 0.00930351 Eh 5.84 kcal/mol| +| sn= 3 | S(rot)= 0.00892067 Eh 5.60 kcal/mol| +| sn= 4 | S(rot)= 0.00864905 Eh 5.43 kcal/mol| +| sn= 5 | S(rot)= 0.00843836 Eh 5.30 kcal/mol| +| sn= 6 | S(rot)= 0.00826622 Eh 5.19 kcal/mol| +| sn= 7 | S(rot)= 0.00812067 Eh 5.10 kcal/mol| +| sn= 8 | S(rot)= 0.00799459 Eh 5.02 kcal/mol| +| sn= 9 | S(rot)= 0.00788338 Eh 4.95 kcal/mol| +| sn=10 | S(rot)= 0.00778390 Eh 4.88 kcal/mol| +| sn=11 | S(rot)= 0.00769391 Eh 4.83 kcal/mol| +| sn=12 | S(rot)= 0.00761176 Eh 4.78 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.41213723 Eh +Total entropy correction ... -0.02816488 Eh -17.67 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44030212 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00617961 Eh -3.88 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.434122507 Eh +Current gradient norm .... 0.005671566 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + -0.031223294 0.093215664 0.160688065 0.467572502 0.497801870 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999945999 +Lowest eigenvalues of augmented Hessian: + -0.000039624 0.093101387 0.160652161 0.467210385 0.497816942 +Length of the computed step .... 0.010392816 +The final length of the internal step .... 0.010392816 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0042428495 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0036070526 RMS(Int)= 0.0042423971 + Iter 1: RMS(Cart)= 0.0000109522 RMS(Int)= 0.0000140576 + Iter 2: RMS(Cart)= 0.0000000534 RMS(Int)= 0.0000000704 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000009 RMS(Int)= 0.0000000032 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0017437799 0.0001000000 NO + MAX gradient 0.0026359169 0.0003000000 NO + RMS step 0.0042428495 0.0020000000 NO + MAX step 0.0063101693 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0026 Max(Angles) 0.36 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.5074 -0.000158 0.0004 1.5078 + 2. B(O 2,N 1) 1.1663 0.002199 -0.0017 1.1646 + 3. B(H 3,O 0) 0.9723 0.002380 -0.0026 0.9697 + 4. A(N 1,O 0,H 3) 102.57 -0.000879 0.36 102.93 + 5. A(O 0,N 1,O 2) 110.66 -0.002636 0.33 110.99 + 6. D(O 2,N 1,O 0,H 3) -90.00 0.002043 0.00 -90.00 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.796963 -0.257490 0.273035 + N 0.642746 -0.439909 -0.136074 + O 0.904101 0.229905 -1.052259 + H -0.749882 0.467493 0.915298 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.506042 -0.486586 0.515962 + 1 N 7.0000 0 14.007 1.214613 -0.831307 -0.257144 + 2 O 8.0000 0 15.999 1.708503 0.434458 -1.988481 + 3 H 1.0000 0 1.008 -1.417072 0.883435 1.729663 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.507782774462 0.00000000 0.00000000 + O 2 1 0 1.164624862785 110.98651767 0.00000000 + H 1 2 3 0.969700825302 102.93256526 269.99999985 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.849296513177 0.00000000 0.00000000 + O 2 1 0 2.200822039420 110.98651767 0.00000000 + H 1 2 3 1.832468991658 102.93256526 269.99999985 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2229 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2696 + la=0 lb=0: 549 shell pairs + la=1 lb=0: 535 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.307256651982 Eh + +SHARK setup successfully completed in 0.5 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.867e-04 +Time for diagonalization ... 0.006 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.007 sec +Total time needed ... 0.077 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7048909442 0.000000000000 0.00017821 0.00000475 0.0007644 0.7000 + 1 -204.7048956819 -0.000004737709 0.00014142 0.00000396 0.0006256 0.7000 + ***Turning on DIIS*** + 2 -204.7048996250 -0.000003943110 0.00034196 0.00001058 0.0005022 0.0000 + 3 -204.7045599648 0.000339660207 0.00011852 0.00000469 0.0001864 0.0000 + 4 -204.7049741210 -0.000414156178 0.00004858 0.00000212 0.0000698 0.0000 + 5 -204.7051522320 -0.000178111067 0.00003107 0.00000114 0.0000644 0.0000 + 6 -204.7048115204 0.000340711617 0.00002482 0.00000105 0.0000312 0.0000 + 7 -204.7049359545 -0.000124434133 0.00001464 0.00000069 0.0000170 0.0000 + 8 -204.7049115410 0.000024413520 0.00001213 0.00000048 0.0000093 0.0000 + 9 -204.7048839740 0.000027567054 0.00000578 0.00000024 0.0000062 0.0000 + 10 -204.7049238793 -0.000039905283 0.00000358 0.00000013 0.0000027 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + +Total Energy : -204.70491130 Eh -5570.30383 eV + Last Energy change ... 1.2577e-05 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.6932e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 6 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.567 sec +Reference energy ... -204.704913704 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 11.031 sec +AO-integral generation ... 0.398 sec +Half transformation ... 0.182 sec +K-integral sorting ... 8.610 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.067 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.070 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.084 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.099 s ( 0.001 ms/b) +: 159120 b 0 skpd 0.052 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.105 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.080 s ( 0.001 ms/b) + 87516 b 0 skpd 0.062 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.105 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.061 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.901 sec +AO-integral generation ... 0.695 sec +Half transformation ... 0.095 sec +J-integral sorting ... 0.084 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.248 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.483 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090017224 +EMP2(bb)= -0.090017224 +EMP2(ab)= -0.517557804 + +Initial guess performed in 0.356 sec +E(0) ... -204.704913704 +E(MP2) ... -0.697592252 +Initial E(tot) ... -205.402505956 + ... 0.189732088 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.402505956 -0.697592252 -0.000000000 0.018765773 5.90 0.000001196 + *** Turning on DIIS *** + 1 -205.374134866 -0.669221163 0.028371089 0.010815990 6.88 0.055445733 + 2 -205.393692311 -0.688778607 -0.019557444 0.003688989 7.05 0.058118447 + 3 -205.397519879 -0.692606175 -0.003827568 0.002076208 6.62 0.070937816 + 4 -205.399053888 -0.694140184 -0.001534009 0.000959147 6.37 0.076566965 + 5 -205.399531138 -0.694617434 -0.000477250 0.000403990 6.74 0.080679890 + 6 -205.399603942 -0.694690239 -0.000072804 0.000305795 7.14 0.082490429 + 7 -205.399631998 -0.694718295 -0.000028056 0.000232666 6.48 0.083255483 + 8 -205.399637754 -0.694724051 -0.000005756 0.000171522 6.50 0.083578314 + 9 -205.399634755 -0.694721052 0.000002999 0.000118117 6.61 0.083708880 + 10 -205.399638983 -0.694725280 -0.000004228 0.000060498 7.56 0.083789155 + 11 -205.399635466 -0.694721763 0.000003517 0.000022271 6.70 0.083822125 + 12 -205.399638117 -0.694724413 -0.000002651 0.000011249 8.66 0.083840358 + 13 -205.399638330 -0.694724626 -0.000000213 0.000003785 7.38 0.083843384 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.704913704 +E(CORR) ... -0.694724626 +E(TOT) ... -205.399638330 +Singles norm **1/2 ... 0.083843384 ( 0.041921692, 0.041921692) +T1 diagnostic ... 0.019762075 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.061310 + 8a-> 13a 8b-> 13b 0.055533 + 8a-> 13a 9b-> 13b 0.047230 + 9a-> 13a 8b-> 13b 0.047230 + 5a-> 13a 5b-> 13b 0.030237 + 11a-> 25a 11b-> 25b 0.028113 + 11a-> 13a 11b-> 13b 0.027910 + 8b-> 13b -1b-> -1b 0.027247 + 8a-> 13a -1a-> -1a 0.027247 + 11a-> 24a 11b-> 24b 0.026327 + 11a-> 25a 11b-> 24b 0.025811 + 11a-> 24a 11b-> 25b 0.025811 + 9a-> 22a 9b-> 13b 0.023622 + 9a-> 13a 9b-> 22b 0.023622 + 11a-> 24a -1a-> -1a 0.020673 + 11b-> 24b -1b-> -1b 0.020673 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034504059 + alpha-alpha-alpha ... -0.000859113 ( 2.5%) + alpha-alpha-beta ... -0.016392917 ( 47.5%) + alpha-beta -beta ... -0.016392917 ( 47.5%) + beta -beta -beta ... -0.000859113 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034504059 + +Final correlation energy ... -0.729228685 +E(CCSD) ... -205.399638330 +E(CCSD(T)) ... -205.434142389 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210179182 sqrt= 1.100081443 +W(HF) = 0.826323915 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 129.438 sec + +Fock Matrix Formation ... 0.567 sec ( 0.4%) +Initial Guess ... 0.356 sec ( 0.3%) +DIIS Solver ... 6.752 sec ( 5.2%) +State Vector Update ... 0.263 sec ( 0.2%) +Sigma-vector construction ... 89.560 sec ( 69.2%) + <0|H|D> ... 0.010 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.057 sec ( 0.1% of sigma) + (0-ext) ... 0.177 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.064 sec ( 0.1% of sigma) + (2-ext) ... 2.270 sec ( 2.5% of sigma) + (4-ext) ... 51.389 sec ( 57.4% of sigma) + ... 5.065 sec ( 5.7% of sigma) + ... 0.007 sec ( 0.0% of sigma) + (1-ext) ... 0.023 sec ( 0.0% of sigma) + (1-ext) ... 0.267 sec ( 0.3% of sigma) + Fock-dressing ... 5.770 sec ( 6.4% of sigma) + (ik|jl)-dressing ... 0.279 sec ( 0.3% of sigma) + (ij|ab),(ia|jb)-dressing ... 19.722 sec ( 22.0% of sigma) + Pair energies ... 0.034 sec ( 0.0% of sigma) +Total Time for computing (T) ... 17.268 sec ( 13.3% of ALL) + I/O of integral and amplitudes ... 1.666 sec ( 9.7% of (T)) + External N**7 contributions ... 9.186 sec ( 53.2% of (T)) + Internal N**7 contributions ... 0.914 sec ( 5.3% of (T)) + N**6 triples energy contributions ... 3.457 sec ( 20.0% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.434142388726 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.000220002 -0.000620892 0.001082461 + 2 N : -0.000334113 -0.000768231 -0.000884918 + 3 O : 0.000237339 0.000680816 0.000621832 + 4 H : -0.000123229 0.000708307 -0.000819376 + +Norm of the cartesian gradient ... 0.002277124 +RMS gradient ... 0.000657349 +MAX gradient ... 0.001082461 + +------- +TIMINGS +------- + +Total numerical gradient time ... 923.972 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.434142389 Eh +Current gradient norm .... 0.002277124 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999981 +Lowest eigenvalues of augmented Hessian: + -0.000000008 0.092978516 0.159630869 0.465133313 0.500641574 +Length of the computed step .... 0.000194643 +The final length of the internal step .... 0.000194643 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0000794627 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0000779351 RMS(Int)= 0.0000794631 + Iter 1: RMS(Cart)= 0.0000000038 RMS(Int)= 0.0000000073 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000009 RMS(Int)= 0.0000000179 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000198817 0.0000050000 NO + RMS gradient 0.0000246444 0.0001000000 YES + MAX gradient 0.0000441152 0.0003000000 YES + RMS step 0.0000794627 0.0020000000 YES + MAX step 0.0001795029 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0000 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.5078 -0.000011 -0.0000 1.5078 + 2. B(O 2,N 1) 1.1646 -0.000044 0.0000 1.1647 + 3. B(H 3,O 0) 0.9697 -0.000019 0.0000 0.9697 + 4. A(N 1,O 0,H 3) 102.93 -0.000027 0.01 102.94 + 5. A(O 0,N 1,O 2) 110.99 -0.000023 0.00 110.99 + 6. D(O 2,N 1,O 0,H 3) -90.00 0.001949 0.00 -90.00 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.796927 -0.257472 0.273052 + N 0.642752 -0.439926 -0.136107 + O 0.904149 0.229894 -1.052307 + H -0.749973 0.467504 0.915361 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.505974 -0.486551 0.515994 + 1 N 7.0000 0 14.007 1.214626 -0.831340 -0.257204 + 2 O 8.0000 0 15.999 1.708594 0.434438 -1.988571 + 3 H 1.0000 0 1.008 -1.417244 0.883454 1.729782 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.507772085030 0.00000000 0.00000000 + O 2 1 0 1.164650321611 110.98892665 0.00000000 + H 1 2 3 0.969718958702 102.94285002 269.99999985 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.849276313078 0.00000000 0.00000000 + O 2 1 0 2.200870149629 110.98892665 0.00000000 + H 1 2 3 1.832503258818 102.94285002 269.99999985 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2229 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2696 + la=0 lb=0: 549 shell pairs + la=1 lb=0: 535 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.306231902020 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.3062319020 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.867e-04 +Time for diagonalization ... 0.005 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.004 sec +Total time needed ... 0.010 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7049103754 0.000000000000 0.00000152 0.00000006 0.0000184 0.7000 + 1 -204.7049103771 -0.000000001653 0.00000153 0.00000006 0.0000146 0.7000 + ***Turning on DIIS*** + 2 -204.7049103785 -0.000000001404 0.00000458 0.00000015 0.0000113 0.0000 + 3 -204.7049176086 -0.000007230107 0.00000200 0.00000007 0.0000027 0.0000 + 4 -204.7049100157 0.000007592914 0.00000086 0.00000004 0.0000014 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70490620 Eh -5570.30369 eV + +Components: +Nuclear Repulsion : 68.30623190 Eh 1858.70706 eV +Electronic Energy : -273.01113810 Eh -7429.01075 eV +One Electron Energy: -416.31771789 Eh -11328.58104 eV +Two Electron Energy: 143.30657979 Eh 3899.57029 eV + +Virial components: +Potential Energy : -408.93164072 Eh -11127.59566 eV +Kinetic Energy : 204.22673452 Eh 5557.29197 eV +Virial Ratio : 2.00234138 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.8158e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.5552e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.4017e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.7361e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.693155 -563.0894 + 1 1.0000 -20.615496 -560.9762 + 2 1.0000 -15.805832 -430.0985 + 3 1.0000 -1.618796 -44.0497 + 4 1.0000 -1.370228 -37.2858 + 5 1.0000 -0.955365 -25.9968 + 6 1.0000 -0.767544 -20.8859 + 7 1.0000 -0.733169 -19.9505 + 8 1.0000 -0.699937 -19.0462 + 9 1.0000 -0.605612 -16.4796 + 10 1.0000 -0.528777 -14.3887 + 11 1.0000 -0.458371 -12.4729 + 12 0.0000 0.030942 0.8420 + 13 0.0000 0.066318 1.8046 + 14 0.0000 0.091592 2.4923 + 15 0.0000 0.103238 2.8092 + 16 0.0000 0.113144 3.0788 + 17 0.0000 0.155430 4.2295 + 18 0.0000 0.157323 4.2810 + 19 0.0000 0.174183 4.7398 + 20 0.0000 0.180069 4.8999 + 21 0.0000 0.189711 5.1623 + 22 0.0000 0.200850 5.4654 + 23 0.0000 0.235660 6.4126 + 24 0.0000 0.268335 7.3018 + 25 0.0000 0.292244 7.9524 + 26 0.0000 0.299494 8.1496 + 27 0.0000 0.331631 9.0241 + 28 0.0000 0.332134 9.0378 + 29 0.0000 0.352155 9.5826 + 30 0.0000 0.425163 11.5693 + 31 0.0000 0.505368 13.7518 + 32 0.0000 0.528679 14.3861 + 33 0.0000 0.543858 14.7991 + 34 0.0000 0.569056 15.4848 + 35 0.0000 0.599658 16.3175 + 36 0.0000 0.630357 17.1529 + 37 0.0000 0.647834 17.6285 + 38 0.0000 0.706541 19.2260 + 39 0.0000 0.717418 19.5219 + 40 0.0000 0.738228 20.0882 + 41 0.0000 0.756892 20.5961 + 42 0.0000 0.760833 20.7033 + 43 0.0000 0.790745 21.5173 + 44 0.0000 0.808829 22.0093 + 45 0.0000 0.815359 22.1871 + 46 0.0000 0.862814 23.4784 + 47 0.0000 0.869019 23.6472 + 48 0.0000 0.892742 24.2927 + 49 0.0000 0.945965 25.7410 + 50 0.0000 0.960458 26.1354 + 51 0.0000 0.980825 26.6896 + 52 0.0000 0.993454 27.0333 + 53 0.0000 1.029158 28.0048 + 54 0.0000 1.045468 28.4486 + 55 0.0000 1.106606 30.1123 + 56 0.0000 1.151449 31.3325 + 57 0.0000 1.225722 33.3536 + 58 0.0000 1.254489 34.1364 + 59 0.0000 1.259931 34.2845 + 60 0.0000 1.314370 35.7658 + 61 0.0000 1.409972 38.3673 + 62 0.0000 1.452106 39.5138 + 63 0.0000 1.517995 41.3067 + 64 0.0000 1.528071 41.5809 + 65 0.0000 1.568806 42.6894 + 66 0.0000 1.585514 43.1440 + 67 0.0000 1.631254 44.3887 + 68 0.0000 1.648843 44.8673 + 69 0.0000 1.716421 46.7062 + 70 0.0000 1.768879 48.1336 + 71 0.0000 1.784306 48.5534 + 72 0.0000 1.891884 51.4808 + 73 0.0000 1.923793 52.3491 + 74 0.0000 1.986045 54.0430 + 75 0.0000 2.012604 54.7657 + 76 0.0000 2.047191 55.7069 + 77 0.0000 2.091753 56.9195 + 78 0.0000 2.136511 58.1374 + 79 0.0000 2.202638 59.9368 + 80 0.0000 2.262045 61.5534 + 81 0.0000 2.292606 62.3850 + 82 0.0000 2.324209 63.2449 + 83 0.0000 2.358003 64.1645 + 84 0.0000 2.405067 65.4452 + 85 0.0000 2.451868 66.7187 + 86 0.0000 2.463256 67.0286 + 87 0.0000 2.477767 67.4235 + 88 0.0000 2.506374 68.2019 + 89 0.0000 2.568815 69.9010 + 90 0.0000 2.571108 69.9634 + 91 0.0000 2.600203 70.7551 + 92 0.0000 2.672294 72.7168 + 93 0.0000 2.727823 74.2278 + 94 0.0000 2.743784 74.6622 + 95 0.0000 2.779017 75.6209 + 96 0.0000 2.847230 77.4771 + 97 0.0000 2.889957 78.6397 + 98 0.0000 2.956977 80.4634 + 99 0.0000 2.985325 81.2348 + 100 0.0000 3.054846 83.1266 + 101 0.0000 3.165696 86.1430 + 102 0.0000 3.224290 87.7374 + 103 0.0000 3.485427 94.8433 + 104 0.0000 3.725830 101.3850 + 105 0.0000 3.809061 103.6498 + 106 0.0000 4.050354 110.2157 + 107 0.0000 4.173592 113.5692 + 108 0.0000 4.193418 114.1087 + 109 0.0000 4.290431 116.7486 + 110 0.0000 4.357447 118.5722 + 111 0.0000 4.393452 119.5519 + 112 0.0000 4.519948 122.9941 + 113 0.0000 4.604876 125.3050 + 114 0.0000 4.661578 126.8480 + 115 0.0000 4.718777 128.4044 + 116 0.0000 4.832000 131.4854 + 117 0.0000 4.900101 133.3385 + 118 0.0000 4.930970 134.1785 + 119 0.0000 4.947976 134.6413 + 120 0.0000 5.048912 137.3879 + 121 0.0000 5.102548 138.8474 + 122 0.0000 5.185728 141.1108 + 123 0.0000 5.194777 141.3571 + 124 0.0000 5.221616 142.0874 + 125 0.0000 5.321944 144.8175 + 126 0.0000 5.380201 146.4027 + 127 0.0000 5.482205 149.1784 + 128 0.0000 5.553678 151.1233 + 129 0.0000 5.706476 155.2811 + 130 0.0000 5.738435 156.1508 + 131 0.0000 5.929368 161.3463 + 132 0.0000 6.178185 168.1170 + 133 0.0000 6.417953 174.6414 + 134 0.0000 6.480550 176.3447 + 135 0.0000 6.503337 176.9648 + 136 0.0000 6.699528 182.3034 + 137 0.0000 6.726672 183.0421 + 138 0.0000 6.769114 184.1969 + 139 0.0000 6.816815 185.4950 + 140 0.0000 6.823930 185.6886 + 141 0.0000 7.066096 192.2783 + 142 0.0000 7.099094 193.1762 + 143 0.0000 7.117671 193.6817 + 144 0.0000 7.197503 195.8540 + 145 0.0000 7.256808 197.4678 + 146 0.0000 7.282670 198.1715 + 147 0.0000 7.342979 199.8126 + 148 0.0000 7.385455 200.9684 + 149 0.0000 7.453618 202.8233 + 150 0.0000 7.460473 203.0098 + 151 0.0000 7.561428 205.7569 + 152 0.0000 7.577487 206.1939 + 153 0.0000 7.624474 207.4725 + 154 0.0000 7.715311 209.9443 + 155 0.0000 7.896395 214.8718 + 156 0.0000 7.917520 215.4467 + 157 0.0000 8.397666 228.5121 + 158 0.0000 14.058081 382.5398 + 159 0.0000 14.845566 403.9684 + 160 0.0000 16.088837 437.7995 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.693155 -563.0894 + 1 1.0000 -20.615496 -560.9762 + 2 1.0000 -15.805832 -430.0985 + 3 1.0000 -1.618796 -44.0497 + 4 1.0000 -1.370228 -37.2858 + 5 1.0000 -0.955365 -25.9968 + 6 1.0000 -0.767544 -20.8859 + 7 1.0000 -0.733169 -19.9505 + 8 1.0000 -0.699937 -19.0462 + 9 1.0000 -0.605612 -16.4796 + 10 1.0000 -0.528777 -14.3887 + 11 1.0000 -0.458371 -12.4729 + 12 0.0000 0.030942 0.8420 + 13 0.0000 0.066318 1.8046 + 14 0.0000 0.091592 2.4923 + 15 0.0000 0.103238 2.8092 + 16 0.0000 0.113144 3.0788 + 17 0.0000 0.155430 4.2295 + 18 0.0000 0.157323 4.2810 + 19 0.0000 0.174183 4.7398 + 20 0.0000 0.180069 4.8999 + 21 0.0000 0.189711 5.1623 + 22 0.0000 0.200850 5.4654 + 23 0.0000 0.235660 6.4126 + 24 0.0000 0.268335 7.3018 + 25 0.0000 0.292244 7.9524 + 26 0.0000 0.299494 8.1496 + 27 0.0000 0.331631 9.0241 + 28 0.0000 0.332134 9.0378 + 29 0.0000 0.352155 9.5826 + 30 0.0000 0.425163 11.5693 + 31 0.0000 0.505368 13.7518 + 32 0.0000 0.528679 14.3861 + 33 0.0000 0.543858 14.7991 + 34 0.0000 0.569056 15.4848 + 35 0.0000 0.599658 16.3175 + 36 0.0000 0.630357 17.1529 + 37 0.0000 0.647834 17.6285 + 38 0.0000 0.706541 19.2260 + 39 0.0000 0.717418 19.5219 + 40 0.0000 0.738228 20.0882 + 41 0.0000 0.756892 20.5961 + 42 0.0000 0.760833 20.7033 + 43 0.0000 0.790745 21.5173 + 44 0.0000 0.808829 22.0093 + 45 0.0000 0.815359 22.1871 + 46 0.0000 0.862814 23.4784 + 47 0.0000 0.869019 23.6472 + 48 0.0000 0.892742 24.2927 + 49 0.0000 0.945965 25.7410 + 50 0.0000 0.960458 26.1354 + 51 0.0000 0.980825 26.6896 + 52 0.0000 0.993454 27.0333 + 53 0.0000 1.029158 28.0048 + 54 0.0000 1.045468 28.4486 + 55 0.0000 1.106606 30.1123 + 56 0.0000 1.151449 31.3325 + 57 0.0000 1.225722 33.3536 + 58 0.0000 1.254489 34.1364 + 59 0.0000 1.259931 34.2845 + 60 0.0000 1.314370 35.7658 + 61 0.0000 1.409972 38.3673 + 62 0.0000 1.452106 39.5138 + 63 0.0000 1.517995 41.3067 + 64 0.0000 1.528071 41.5809 + 65 0.0000 1.568806 42.6894 + 66 0.0000 1.585514 43.1440 + 67 0.0000 1.631254 44.3887 + 68 0.0000 1.648843 44.8673 + 69 0.0000 1.716421 46.7062 + 70 0.0000 1.768879 48.1336 + 71 0.0000 1.784306 48.5534 + 72 0.0000 1.891884 51.4808 + 73 0.0000 1.923793 52.3491 + 74 0.0000 1.986045 54.0430 + 75 0.0000 2.012604 54.7657 + 76 0.0000 2.047191 55.7069 + 77 0.0000 2.091753 56.9195 + 78 0.0000 2.136511 58.1374 + 79 0.0000 2.202638 59.9368 + 80 0.0000 2.262045 61.5534 + 81 0.0000 2.292606 62.3850 + 82 0.0000 2.324209 63.2449 + 83 0.0000 2.358003 64.1645 + 84 0.0000 2.405067 65.4452 + 85 0.0000 2.451868 66.7187 + 86 0.0000 2.463256 67.0286 + 87 0.0000 2.477767 67.4235 + 88 0.0000 2.506374 68.2019 + 89 0.0000 2.568815 69.9010 + 90 0.0000 2.571108 69.9634 + 91 0.0000 2.600203 70.7551 + 92 0.0000 2.672294 72.7168 + 93 0.0000 2.727823 74.2278 + 94 0.0000 2.743784 74.6622 + 95 0.0000 2.779017 75.6209 + 96 0.0000 2.847230 77.4771 + 97 0.0000 2.889957 78.6397 + 98 0.0000 2.956977 80.4634 + 99 0.0000 2.985325 81.2348 + 100 0.0000 3.054846 83.1266 + 101 0.0000 3.165696 86.1430 + 102 0.0000 3.224290 87.7374 + 103 0.0000 3.485427 94.8433 + 104 0.0000 3.725830 101.3850 + 105 0.0000 3.809061 103.6498 + 106 0.0000 4.050354 110.2157 + 107 0.0000 4.173592 113.5692 + 108 0.0000 4.193418 114.1087 + 109 0.0000 4.290431 116.7486 + 110 0.0000 4.357447 118.5722 + 111 0.0000 4.393452 119.5519 + 112 0.0000 4.519948 122.9941 + 113 0.0000 4.604876 125.3050 + 114 0.0000 4.661578 126.8480 + 115 0.0000 4.718777 128.4044 + 116 0.0000 4.832000 131.4854 + 117 0.0000 4.900101 133.3385 + 118 0.0000 4.930970 134.1785 + 119 0.0000 4.947976 134.6413 + 120 0.0000 5.048912 137.3879 + 121 0.0000 5.102548 138.8474 + 122 0.0000 5.185728 141.1108 + 123 0.0000 5.194777 141.3571 + 124 0.0000 5.221616 142.0874 + 125 0.0000 5.321944 144.8175 + 126 0.0000 5.380201 146.4027 + 127 0.0000 5.482205 149.1784 + 128 0.0000 5.553678 151.1233 + 129 0.0000 5.706476 155.2811 + 130 0.0000 5.738435 156.1508 + 131 0.0000 5.929368 161.3463 + 132 0.0000 6.178185 168.1170 + 133 0.0000 6.417953 174.6414 + 134 0.0000 6.480550 176.3447 + 135 0.0000 6.503337 176.9648 + 136 0.0000 6.699528 182.3034 + 137 0.0000 6.726672 183.0421 + 138 0.0000 6.769114 184.1969 + 139 0.0000 6.816815 185.4950 + 140 0.0000 6.823930 185.6886 + 141 0.0000 7.066096 192.2783 + 142 0.0000 7.099094 193.1762 + 143 0.0000 7.117671 193.6817 + 144 0.0000 7.197503 195.8540 + 145 0.0000 7.256808 197.4678 + 146 0.0000 7.282670 198.1715 + 147 0.0000 7.342979 199.8126 + 148 0.0000 7.385455 200.9684 + 149 0.0000 7.453618 202.8233 + 150 0.0000 7.460473 203.0098 + 151 0.0000 7.561428 205.7569 + 152 0.0000 7.577487 206.1939 + 153 0.0000 7.624474 207.4725 + 154 0.0000 7.715311 209.9443 + 155 0.0000 7.896395 214.8718 + 156 0.0000 7.917520 215.4467 + 157 0.0000 8.397666 228.5121 + 158 0.0000 14.058081 382.5398 + 159 0.0000 14.845566 403.9684 + 160 0.0000 16.088837 437.7995 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.378212 0.000000 + 1 N : 0.353955 0.000000 + 2 O : -0.223850 0.000000 + 3 H : 0.248107 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.864920 s : 3.864920 + pz : 1.637997 p : 4.483885 + px : 1.256785 + py : 1.589103 + dz2 : 0.002981 d : 0.025177 + dxz : 0.003788 + dyz : 0.002681 + dx2y2 : 0.012171 + dxy : 0.003556 + f0 : 0.000588 f : 0.004230 + f+1 : 0.000764 + f-1 : 0.000373 + f+2 : 0.000494 + f-2 : 0.000079 + f+3 : 0.001103 + f-3 : 0.000829 + 1 N s : 3.822083 s : 3.822083 + pz : 0.891736 p : 2.656093 + px : 0.825039 + py : 0.939319 + dz2 : 0.036064 d : 0.137173 + dxz : 0.031398 + dyz : 0.014311 + dx2y2 : 0.033929 + dxy : 0.021471 + f0 : 0.004455 f : 0.030696 + f+1 : 0.005601 + f-1 : 0.002959 + f+2 : 0.004000 + f-2 : 0.003924 + f+3 : 0.004184 + f-3 : 0.005572 + 2 O s : 3.875060 s : 3.875060 + pz : 1.191024 p : 4.278320 + px : 1.787447 + py : 1.299849 + dz2 : 0.025711 d : 0.062968 + dxz : 0.009566 + dyz : 0.011799 + dx2y2 : 0.006737 + dxy : 0.009155 + f0 : 0.002053 f : 0.007502 + f+1 : 0.000831 + f-1 : 0.001286 + f+2 : 0.001067 + f-2 : 0.001233 + f+3 : 0.000560 + f-3 : 0.000471 + 3 H s : 0.644016 s : 0.644016 + pz : 0.036096 p : 0.087714 + px : 0.022377 + py : 0.029241 + dz2 : 0.007553 d : 0.020163 + dxz : 0.004151 + dyz : 0.000079 + dx2y2 : 0.002951 + dxy : 0.005428 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.573203 0.000000 + 1 N : -0.230258 0.000000 + 2 O : 0.250196 0.000000 + 3 H : -0.593141 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.137974 s : 3.137974 + pz : 1.390594 p : 3.961660 + px : 1.177917 + py : 1.393149 + dz2 : 0.035197 d : 0.253631 + dxz : 0.055614 + dyz : 0.029455 + dx2y2 : 0.081823 + dxy : 0.051542 + f0 : 0.005677 f : 0.073532 + f+1 : 0.016167 + f-1 : 0.002880 + f+2 : 0.014068 + f-2 : 0.003859 + f+3 : 0.013411 + f-3 : 0.017471 + 1 N s : 3.039569 s : 3.039569 + pz : 0.999983 p : 2.838399 + px : 0.871064 + py : 0.967353 + dz2 : 0.171130 d : 0.916029 + dxz : 0.247564 + dyz : 0.168169 + dx2y2 : 0.185600 + dxy : 0.143566 + f0 : 0.053015 f : 0.436261 + f+1 : 0.074152 + f-1 : 0.057045 + f+2 : 0.074358 + f-2 : 0.064973 + f+3 : 0.051187 + f-3 : 0.061531 + 2 O s : 3.314799 s : 3.314799 + pz : 1.269987 p : 3.985635 + px : 1.469077 + py : 1.246571 + dz2 : 0.062989 d : 0.331511 + dxz : 0.074187 + dyz : 0.112557 + dx2y2 : 0.052717 + dxy : 0.029061 + f0 : 0.015980 f : 0.117858 + f+1 : 0.014195 + f-1 : 0.027899 + f+2 : 0.029340 + f-2 : 0.018391 + f+3 : 0.003738 + f-3 : 0.008315 + 3 H s : 0.627886 s : 0.627886 + pz : 0.208426 p : 0.575176 + px : 0.138787 + py : 0.227963 + dz2 : 0.094427 d : 0.390078 + dxz : 0.061694 + dyz : 0.097048 + dx2y2 : 0.068382 + dxy : 0.068527 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3782 8.0000 -0.3782 1.8187 1.8187 -0.0000 + 1 N 6.6460 7.0000 0.3540 2.5979 2.5979 0.0000 + 2 O 8.2238 8.0000 -0.2238 1.8150 1.8150 0.0000 + 3 H 0.7519 1.0000 0.2481 0.9936 0.9936 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8045 B( 0-O , 3-H ) : 0.9577 B( 1-N , 2-O ) : 1.7581 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.499 sec +Sum of individual times .... 2.090 sec ( 83.6%) + +Fock matrix formation .... 1.744 sec ( 69.8%) +Diagonalization .... 0.139 sec ( 5.6%) +Density matrix formation .... 0.011 sec ( 0.4%) +Population analysis .... 0.063 sec ( 2.5%) +Initial guess .... 0.019 sec ( 0.8%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.011 sec ( 0.4%) +DIIS solution .... 0.115 sec ( 4.6%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.675 sec +Reference energy ... -204.704910381 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 12.341 sec +AO-integral generation ... 0.342 sec +Half transformation ... 0.172 sec +K-integral sorting ... 9.356 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.067 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.071 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.089 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.096 s ( 0.001 ms/b) + 159120 b 0 skpd 0.050 s ( 0.000 ms/b) +: : 218790 b 0 skpd 0.108 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.085 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.067 s ( 0.001 ms/b) + 87516 b 0 skpd 0.118 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.082 s ( 0.003 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.973 sec +AO-integral generation ... 0.728 sec +Half transformation ... 0.114 sec +J-integral sorting ... 0.090 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.268 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.515 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090017618 +EMP2(bb)= -0.090017618 +EMP2(ab)= -0.517560221 + +Initial guess performed in 0.198 sec +E(0) ... -204.704910381 +E(MP2) ... -0.697595457 +Initial E(tot) ... -205.402505838 + ... 0.189735485 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.402505838 -0.697595457 -0.000000000 0.018766814 6.37 0.000003384 + *** Turning on DIIS *** + 1 -205.374133155 -0.669222775 0.028372682 0.010817118 5.70 0.055447708 + 2 -205.393691241 -0.688780860 -0.019558085 0.003689269 5.63 0.058120324 + 3 -205.397518941 -0.692608560 -0.003827700 0.002076537 6.73 0.070940446 + 4 -205.399053055 -0.694142675 -0.001534115 0.000959124 5.66 0.076570094 + 5 -205.399530370 -0.694619990 -0.000477315 0.000404406 7.37 0.080683612 + 6 -205.399603189 -0.694692808 -0.000072819 0.000306113 7.95 0.082494527 + 7 -205.399631254 -0.694720873 -0.000028065 0.000232906 8.74 0.083259850 + 8 -205.399637014 -0.694726634 -0.000005761 0.000171688 6.54 0.083582921 + 9 -205.399634016 -0.694723635 0.000002999 0.000118208 6.40 0.083713693 + 10 -205.399638249 -0.694727869 -0.000004234 0.000060513 7.58 0.083794139 + 11 -205.399634731 -0.694724350 0.000003518 0.000022263 7.94 0.083827182 + 12 -205.399637383 -0.694727002 -0.000002652 0.000011254 6.03 0.083845435 + 13 -205.399637596 -0.694727216 -0.000000213 0.000003787 5.85 0.083848464 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.704910381 +E(CORR) ... -0.694727216 +E(TOT) ... -205.399637596 +Singles norm **1/2 ... 0.083848464 ( 0.041924232, 0.041924232) +T1 diagnostic ... 0.019763272 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.061316 + 8a-> 13a 8b-> 13b 0.055537 + 9a-> 13a 8b-> 13b 0.047234 + 8a-> 13a 9b-> 13b 0.047234 + 5a-> 13a 5b-> 13b 0.030238 + 11a-> 25a 11b-> 25b 0.028113 + 11a-> 13a 11b-> 13b 0.027913 + 8a-> 13a -1a-> -1a 0.027250 + 8b-> 13b -1b-> -1b 0.027250 + 11a-> 24a 11b-> 24b 0.026323 + 11a-> 25a 11b-> 24b 0.025809 + 11a-> 24a 11b-> 25b 0.025809 + 9a-> 22a 9b-> 13b 0.023622 + 9a-> 13a 9b-> 22b 0.023622 + 11b-> 24b -1b-> -1b 0.020672 + 11a-> 24a -1a-> -1a 0.020672 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034504797 + alpha-alpha-alpha ... -0.000859125 ( 2.5%) + alpha-alpha-beta ... -0.016393273 ( 47.5%) + alpha-beta -beta ... -0.016393273 ( 47.5%) + beta -beta -beta ... -0.000859125 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034504797 + +Final correlation energy ... -0.729232012 +E(CCSD) ... -205.399637596 +E(CCSD(T)) ... -205.434142393 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210184414 sqrt= 1.100083821 +W(HF) = 0.826320343 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.321805 0.000000 + 1 N : 0.182926 -0.000000 + 2 O : -0.097370 0.000000 + 3 H : 0.236249 -0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.843003 s : 3.843003 + pz : 1.613762 p : 4.414736 + px : 1.242365 + py : 1.558608 + dz2 : 0.009786 d : 0.056100 + dxz : 0.010365 + dyz : 0.008906 + dx2y2 : 0.016157 + dxy : 0.010886 + f0 : 0.001120 f : 0.007966 + f+1 : 0.001242 + f-1 : 0.001022 + f+2 : 0.001048 + f-2 : 0.000764 + f+3 : 0.001417 + f-3 : 0.001353 + 1 N s : 3.876360 s : 3.876360 + pz : 0.908804 p : 2.744720 + px : 0.875640 + py : 0.960275 + dz2 : 0.036401 d : 0.166350 + dxz : 0.042085 + dyz : 0.019074 + dx2y2 : 0.039806 + dxy : 0.028984 + f0 : 0.003606 f : 0.029645 + f+1 : 0.005637 + f-1 : 0.002856 + f+2 : 0.003852 + f-2 : 0.003831 + f+3 : 0.004243 + f-3 : 0.005619 + 2 O s : 3.862232 s : 3.862232 + pz : 1.170562 p : 4.141482 + px : 1.701891 + py : 1.269029 + dz2 : 0.025554 d : 0.083805 + dxz : 0.016402 + dyz : 0.014953 + dx2y2 : 0.012453 + dxy : 0.014443 + f0 : 0.001987 f : 0.009852 + f+1 : 0.001364 + f-1 : 0.001436 + f+2 : 0.001398 + f-2 : 0.001594 + f+3 : 0.001084 + f-3 : 0.000990 + 3 H s : 0.651214 s : 0.651214 + pz : 0.038742 p : 0.095307 + px : 0.025562 + py : 0.031003 + dz2 : 0.006704 d : 0.017230 + dxz : 0.003813 + dyz : -0.000613 + dx2y2 : 0.002474 + dxy : 0.004852 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.577741 -0.000000 + 1 N : -0.273603 0.000000 + 2 O : 0.293786 0.000000 + 3 H : -0.597924 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.141996 s : 3.141996 + pz : 1.370154 p : 3.915351 + px : 1.178336 + py : 1.366862 + dz2 : 0.040965 d : 0.284495 + dxz : 0.061808 + dyz : 0.036635 + dx2y2 : 0.088397 + dxy : 0.056691 + f0 : 0.006754 f : 0.080417 + f+1 : 0.016628 + f-1 : 0.003647 + f+2 : 0.015466 + f-2 : 0.004718 + f+3 : 0.015082 + f-3 : 0.018122 + 1 N s : 3.044405 s : 3.044405 + pz : 1.006786 p : 2.878671 + px : 0.894699 + py : 0.977186 + dz2 : 0.168916 d : 0.923541 + dxz : 0.248408 + dyz : 0.173385 + dx2y2 : 0.189917 + dxy : 0.142914 + f0 : 0.052217 f : 0.426986 + f+1 : 0.072044 + f-1 : 0.057314 + f+2 : 0.071629 + f-2 : 0.061958 + f+3 : 0.052253 + f-3 : 0.059572 + 2 O s : 3.317645 s : 3.317645 + pz : 1.258454 p : 3.903107 + px : 1.414562 + py : 1.230092 + dz2 : 0.071059 d : 0.359260 + dxz : 0.077929 + dyz : 0.117309 + dx2y2 : 0.058151 + dxy : 0.034810 + f0 : 0.019311 f : 0.126202 + f+1 : 0.015120 + f-1 : 0.028871 + f+2 : 0.029514 + f-2 : 0.019760 + f+3 : 0.004913 + f-3 : 0.008713 + 3 H s : 0.627984 s : 0.627984 + pz : 0.216166 p : 0.589949 + px : 0.138333 + py : 0.235450 + dz2 : 0.091219 d : 0.379990 + dxz : 0.059153 + dyz : 0.096082 + dx2y2 : 0.067352 + dxy : 0.066184 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3218 8.0000 -0.3218 2.1588 1.6952 0.4636 + 1 N 6.8171 7.0000 0.1829 2.8586 2.3632 0.4953 + 2 O 8.0974 8.0000 -0.0974 2.1989 1.7007 0.4982 + 3 H 0.7638 1.0000 0.2362 1.0150 0.9404 0.0746 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7130 B( 0-O , 3-H ) : 0.8955 B( 1-N , 2-O ) : 1.6096 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 127.663 sec + +Fock Matrix Formation ... 0.675 sec ( 0.5%) +Initial Guess ... 0.198 sec ( 0.2%) +DIIS Solver ... 5.985 sec ( 4.7%) +State Vector Update ... 0.275 sec ( 0.2%) +Sigma-vector construction ... 88.214 sec ( 69.1%) + <0|H|D> ... 0.009 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.046 sec ( 0.1% of sigma) + (0-ext) ... 0.148 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.055 sec ( 0.1% of sigma) + (2-ext) ... 1.946 sec ( 2.2% of sigma) + (4-ext) ... 49.985 sec ( 56.7% of sigma) + ... 5.204 sec ( 5.9% of sigma) + ... 0.007 sec ( 0.0% of sigma) + (1-ext) ... 0.021 sec ( 0.0% of sigma) + (1-ext) ... 0.272 sec ( 0.3% of sigma) + Fock-dressing ... 6.029 sec ( 6.8% of sigma) + (ik|jl)-dressing ... 0.163 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 19.773 sec ( 22.4% of sigma) + Pair energies ... 0.037 sec ( 0.0% of sigma) +Total Time for computing (T) ... 16.263 sec ( 12.7% of ALL) + I/O of integral and amplitudes ... 2.096 sec ( 12.9% of (T)) + External N**7 contributions ... 9.501 sec ( 58.4% of (T)) + Internal N**7 contributions ... 0.968 sec ( 6.0% of (T)) + N**6 triples energy contributions ... 3.523 sec ( 21.7% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.434142392894 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.012.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.012.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.400451, -0.246481 -0.540676) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 1.06214 -0.14884 -0.65855 +Nuclear contribution : -0.90473 0.56272 1.12496 + ----------------------------------------- +Total Dipole Moment : 0.15741 0.41388 0.46641 + ----------------------------------------- +Magnitude (a.u.) : 0.64313 +Magnitude (Debye) : 1.63471 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.717877 0.398432 0.359769 +Rotational constants in MHz : 81479.914680 11944.681197 10785.593645 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.083630 -0.035259 0.636694 +x,y,z [Debye]: -0.212571 -0.089621 1.618346 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.400451, -0.246481 -0.540676) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 1.11214 -0.10059 -0.82199 +Nuclear contribution : -0.90473 0.56272 1.12496 + ----------------------------------------- +Total Dipole Moment : 0.20742 0.46212 0.30297 + ----------------------------------------- +Magnitude (a.u.) : 0.59023 +Magnitude (Debye) : 1.50024 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.717877 0.398432 0.359769 +Rotational constants in MHz : 81479.914680 11944.681197 10785.593645 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.060197 0.054945 0.584575 +x,y,z [Debye]: 0.153009 0.139658 1.485871 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 13 * + * * + * Dihedral ( 2, 1, 0, 3) : -81.81818182 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0390817220 RMS(Int)= 0.0005861144 + Iter 1: RMS(Cart)= 0.0001604091 RMS(Int)= 0.0000060064 + Iter 2: RMS(Cart)= 0.0000016438 RMS(Int)= 0.0000000618 + Iter 3: RMS(Cart)= 0.0000000169 RMS(Int)= 0.0000000006 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.5082 0.000000 + 2. B(O 2,N 1) 1.1666 0.000000 + 3. B(H 3,O 0) 0.9724 0.000000 + 4. A(N 1,O 0,H 3) 102.8404 0.000000 + 5. A(O 0,N 1,O 2) 110.8884 0.000000 + 6. D(O 2,N 1,O 0,H 3) -81.8182 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.793868 -0.280314 0.294170 + N 0.635182 -0.467543 -0.150259 + O 0.896382 0.256427 -1.026927 + H -0.737694 0.491430 0.883017 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.500194 -0.529716 0.555900 + 1 N 7.0000 0 14.007 1.200320 -0.883529 -0.283949 + 2 O 8.0000 0 15.999 1.693917 0.484577 -1.940611 + 3 H 1.0000 0 1.008 -1.394041 0.928668 1.668661 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.507772085030 0.00000000 0.00000000 + O 2 1 0 1.164650321611 110.98892665 0.00000000 + H 1 2 3 0.969718958702 102.94285002 269.99999985 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.849276313078 0.00000000 0.00000000 + O 2 1 0 2.200870149629 110.98892665 0.00000000 + H 1 2 3 1.832503258818 102.94285002 269.99999985 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.1 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.2 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2229 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2697 + la=0 lb=0: 549 shell pairs + la=1 lb=0: 535 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.278517411377 Eh + +SHARK setup successfully completed in 0.7 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.2785174114 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.834e-04 +Time for diagonalization ... 0.018 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.007 sec +Total time needed ... 0.026 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.6998228049 0.000000000000 0.00163421 0.00005109 0.0193961 0.7000 + 1 -204.7007135489 -0.000890744058 0.00154878 0.00004697 0.0160916 0.7000 + ***Turning on DIIS*** + 2 -204.7014799773 -0.000766428343 0.00435012 0.00012933 0.0131145 0.0000 + 3 -204.7059512069 -0.004471229624 0.00204577 0.00005915 0.0050488 0.0000 + 4 -204.7031223645 0.002828842354 0.00096560 0.00003095 0.0019613 0.0000 + 5 -204.7052237851 -0.002101420553 0.00088767 0.00002683 0.0011628 0.0000 + 6 -204.7040440306 0.001179754457 0.00100327 0.00003143 0.0006529 0.0000 + 7 -204.7040686621 -0.000024631444 0.00035918 0.00001339 0.0002891 0.0000 + 8 -204.7047139702 -0.000645308075 0.00018106 0.00000808 0.0001749 0.0000 + 9 -204.7041935151 0.000520455099 0.00014068 0.00000648 0.0001156 0.0000 + 10 -204.7044782407 -0.000284725601 0.00006416 0.00000235 0.0000502 0.0000 + 11 -204.7044547041 0.000023536513 0.00001263 0.00000052 0.0000279 0.0000 + 12 -204.7044097614 0.000044942720 0.00000842 0.00000025 0.0000132 0.0000 + 13 -204.7044371270 -0.000027365532 0.00000212 0.00000009 0.0000044 0.0000 + 14 -204.7044306315 0.000006495450 0.00000124 0.00000004 0.0000025 0.0000 + 15 -204.7044325845 -0.000001952959 0.00000097 0.00000003 0.0000016 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 16 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70443428 Eh -5570.29084 eV + +Components: +Nuclear Repulsion : 68.27851741 Eh 1857.95292 eV +Electronic Energy : -272.98295169 Eh -7428.24376 eV +One Electron Energy: -416.26073703 Eh -11327.03051 eV +Two Electron Energy: 143.27778534 Eh 3898.78675 eV + +Virial components: +Potential Energy : -408.91873753 Eh -11127.24455 eV +Kinetic Energy : 204.21430325 Eh 5556.95370 eV +Virial Ratio : 2.00240008 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.6986e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.2705e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.9622e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.9025e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.693144 -563.0891 + 1 1.0000 -20.616515 -561.0039 + 2 1.0000 -15.806681 -430.1217 + 3 1.0000 -1.617744 -44.0211 + 4 1.0000 -1.369652 -37.2701 + 5 1.0000 -0.956187 -26.0192 + 6 1.0000 -0.765954 -20.8427 + 7 1.0000 -0.733792 -19.9675 + 8 1.0000 -0.699446 -19.0329 + 9 1.0000 -0.604965 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2.4967 + 15 0.0000 0.104012 2.8303 + 16 0.0000 0.113035 3.0758 + 17 0.0000 0.155573 4.2334 + 18 0.0000 0.157291 4.2801 + 19 0.0000 0.174439 4.7467 + 20 0.0000 0.178924 4.8688 + 21 0.0000 0.189679 5.1614 + 22 0.0000 0.200908 5.4670 + 23 0.0000 0.235058 6.3963 + 24 0.0000 0.267951 7.2913 + 25 0.0000 0.289542 7.8788 + 26 0.0000 0.301619 8.2075 + 27 0.0000 0.331666 9.0251 + 28 0.0000 0.334002 9.0886 + 29 0.0000 0.352134 9.5821 + 30 0.0000 0.424195 11.5429 + 31 0.0000 0.506336 13.7781 + 32 0.0000 0.529841 14.4177 + 33 0.0000 0.543532 14.7903 + 34 0.0000 0.565225 15.3805 + 35 0.0000 0.599161 16.3040 + 36 0.0000 0.630568 17.1586 + 37 0.0000 0.645696 17.5703 + 38 0.0000 0.708769 19.2866 + 39 0.0000 0.716666 19.5015 + 40 0.0000 0.736055 20.0291 + 41 0.0000 0.756495 20.5853 + 42 0.0000 0.761262 20.7150 + 43 0.0000 0.789658 21.4877 + 44 0.0000 0.807368 21.9696 + 45 0.0000 0.817737 22.2517 + 46 0.0000 0.860041 23.4029 + 47 0.0000 0.873440 23.7675 + 48 0.0000 0.892826 24.2950 + 49 0.0000 0.952994 25.9323 + 50 0.0000 0.961903 26.1747 + 51 0.0000 0.975177 26.5359 + 52 0.0000 0.991574 26.9821 + 53 0.0000 1.028080 27.9755 + 54 0.0000 1.043757 28.4021 + 55 0.0000 1.099967 29.9316 + 56 0.0000 1.154793 31.4235 + 57 0.0000 1.220810 33.2199 + 58 0.0000 1.245876 33.9020 + 59 0.0000 1.263209 34.3737 + 60 0.0000 1.317100 35.8401 + 61 0.0000 1.407933 38.3118 + 62 0.0000 1.460705 39.7478 + 63 0.0000 1.514548 41.2129 + 64 0.0000 1.528870 41.6027 + 65 0.0000 1.572517 42.7904 + 66 0.0000 1.588490 43.2250 + 67 0.0000 1.630607 44.3711 + 68 0.0000 1.649629 44.8887 + 69 0.0000 1.722525 46.8723 + 70 0.0000 1.759768 47.8857 + 71 0.0000 1.778744 48.4021 + 72 0.0000 1.899468 51.6872 + 73 0.0000 1.923207 52.3331 + 74 0.0000 1.978130 53.8276 + 75 0.0000 2.010230 54.7011 + 76 0.0000 2.041967 55.5647 + 77 0.0000 2.094829 57.0032 + 78 0.0000 2.135666 58.1144 + 79 0.0000 2.194913 59.7266 + 80 0.0000 2.273448 61.8637 + 81 0.0000 2.291114 62.3444 + 82 0.0000 2.331608 63.4463 + 83 0.0000 2.352779 64.0224 + 84 0.0000 2.404991 65.4431 + 85 0.0000 2.452441 66.7343 + 86 0.0000 2.465398 67.0869 + 87 0.0000 2.476394 67.3861 + 88 0.0000 2.510387 68.3111 + 89 0.0000 2.565054 69.7987 + 90 0.0000 2.585567 70.3568 + 91 0.0000 2.601730 70.7967 + 92 0.0000 2.664228 72.4973 + 93 0.0000 2.718436 73.9724 + 94 0.0000 2.747917 74.7746 + 95 0.0000 2.758981 75.0757 + 96 0.0000 2.839428 77.2648 + 97 0.0000 2.904015 79.0223 + 98 0.0000 2.958614 80.5080 + 99 0.0000 2.980808 81.1119 + 100 0.0000 3.060769 83.2878 + 101 0.0000 3.168700 86.2247 + 102 0.0000 3.220343 87.6300 + 103 0.0000 3.482049 94.7514 + 104 0.0000 3.715770 101.1113 + 105 0.0000 3.813041 103.7581 + 106 0.0000 4.045369 110.0801 + 107 0.0000 4.167466 113.4025 + 108 0.0000 4.199043 114.2618 + 109 0.0000 4.280683 116.4833 + 110 0.0000 4.362005 118.6962 + 111 0.0000 4.391463 119.4978 + 112 0.0000 4.523710 123.0964 + 113 0.0000 4.607100 125.3656 + 114 0.0000 4.657876 126.7473 + 115 0.0000 4.716716 128.3484 + 116 0.0000 4.833862 131.5361 + 117 0.0000 4.894567 133.1879 + 118 0.0000 4.926967 134.0696 + 119 0.0000 4.950105 134.6992 + 120 0.0000 5.047522 137.3501 + 121 0.0000 5.102469 138.8452 + 122 0.0000 5.180596 140.9712 + 123 0.0000 5.194251 141.3428 + 124 0.0000 5.231631 142.3599 + 125 0.0000 5.304915 144.3541 + 126 0.0000 5.384806 146.5280 + 127 0.0000 5.482959 149.1989 + 128 0.0000 5.543343 150.8420 + 129 0.0000 5.695453 154.9812 + 130 0.0000 5.739355 156.1758 + 131 0.0000 5.933008 161.4454 + 132 0.0000 6.175145 168.0342 + 133 0.0000 6.413931 174.5319 + 134 0.0000 6.479226 176.3087 + 135 0.0000 6.505720 177.0296 + 136 0.0000 6.696749 182.2278 + 137 0.0000 6.720606 182.8770 + 138 0.0000 6.772002 184.2755 + 139 0.0000 6.817873 185.5237 + 140 0.0000 6.829427 185.8382 + 141 0.0000 7.059840 192.1080 + 142 0.0000 7.101082 193.2303 + 143 0.0000 7.113257 193.5616 + 144 0.0000 7.195933 195.8113 + 145 0.0000 7.255918 197.4436 + 146 0.0000 7.277777 198.0384 + 147 0.0000 7.335773 199.6165 + 148 0.0000 7.380571 200.8355 + 149 0.0000 7.453533 202.8209 + 150 0.0000 7.463932 203.1039 + 151 0.0000 7.564704 205.8461 + 152 0.0000 7.568809 205.9578 + 153 0.0000 7.633581 207.7203 + 154 0.0000 7.694188 209.3695 + 155 0.0000 7.886927 214.6142 + 156 0.0000 7.920954 215.5401 + 157 0.0000 8.391723 228.3504 + 158 0.0000 14.038280 382.0010 + 159 0.0000 14.808176 402.9510 + 160 0.0000 16.052362 436.8070 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.379406 0.000000 + 1 N : 0.353553 0.000000 + 2 O : -0.224665 0.000000 + 3 H : 0.250518 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.863215 s : 3.863215 + pz : 1.668619 p : 4.485703 + px : 1.262672 + py : 1.554412 + dz2 : 0.002568 d : 0.026294 + dxz : 0.004371 + dyz : 0.002674 + dx2y2 : 0.012876 + dxy : 0.003805 + f0 : 0.000667 f : 0.004193 + f+1 : 0.000764 + f-1 : 0.000274 + f+2 : 0.000527 + f-2 : 0.000086 + f+3 : 0.001061 + f-3 : 0.000815 + 1 N s : 3.823514 s : 3.823514 + pz : 0.864282 p : 2.653867 + px : 0.819895 + py : 0.969690 + dz2 : 0.035725 d : 0.138218 + dxz : 0.031476 + dyz : 0.014312 + dx2y2 : 0.035396 + dxy : 0.021308 + f0 : 0.004053 f : 0.030849 + f+1 : 0.005149 + f-1 : 0.003170 + f+2 : 0.003920 + f-2 : 0.004258 + f+3 : 0.004549 + f-3 : 0.005750 + 2 O s : 3.875904 s : 3.875904 + pz : 1.190236 p : 4.278968 + px : 1.778076 + py : 1.310656 + dz2 : 0.025202 d : 0.062309 + dxz : 0.008464 + dyz : 0.010899 + dx2y2 : 0.007341 + dxy : 0.010402 + f0 : 0.001755 f : 0.007484 + f+1 : 0.000651 + f-1 : 0.001429 + f+2 : 0.001133 + f-2 : 0.001268 + f+3 : 0.000687 + f-3 : 0.000561 + 3 H s : 0.642480 s : 0.642480 + pz : 0.037438 p : 0.087160 + px : 0.022392 + py : 0.027330 + dz2 : 0.006879 d : 0.019842 + dxz : 0.003253 + dyz : 0.000651 + dx2y2 : 0.002952 + dxy : 0.006107 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.570102 0.000000 + 1 N : -0.229177 0.000000 + 2 O : 0.249012 0.000000 + 3 H : -0.589937 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.139899 s : 3.139899 + pz : 1.399654 p : 3.962821 + px : 1.182174 + py : 1.380993 + dz2 : 0.033549 d : 0.253704 + dxz : 0.056311 + dyz : 0.029343 + dx2y2 : 0.081432 + dxy : 0.053068 + f0 : 0.006143 f : 0.073474 + f+1 : 0.015844 + f-1 : 0.001975 + f+2 : 0.013875 + f-2 : 0.004406 + f+3 : 0.012969 + f-3 : 0.018262 + 1 N s : 3.041147 s : 3.041147 + pz : 0.960569 p : 2.837184 + px : 0.866596 + py : 1.010018 + dz2 : 0.162149 d : 0.913987 + dxz : 0.238517 + dyz : 0.170289 + dx2y2 : 0.194025 + dxy : 0.149006 + f0 : 0.048314 f : 0.436859 + f+1 : 0.066927 + f-1 : 0.055506 + f+2 : 0.076397 + f-2 : 0.070212 + f+3 : 0.055085 + f-3 : 0.064418 + 2 O s : 3.314409 s : 3.314409 + pz : 1.247317 p : 3.987803 + px : 1.463508 + py : 1.276978 + dz2 : 0.054448 d : 0.331263 + dxz : 0.069726 + dyz : 0.114166 + dx2y2 : 0.059970 + dxy : 0.032953 + f0 : 0.013916 f : 0.117514 + f+1 : 0.011925 + f-1 : 0.026253 + f+2 : 0.030677 + f-2 : 0.019674 + f+3 : 0.004590 + f-3 : 0.010478 + 3 H s : 0.626555 s : 0.626555 + pz : 0.199715 p : 0.573301 + px : 0.139155 + py : 0.234432 + dz2 : 0.086175 d : 0.390080 + dxz : 0.054584 + dyz : 0.098280 + dx2y2 : 0.074227 + dxy : 0.076814 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3794 8.0000 -0.3794 1.8162 1.8162 -0.0000 + 1 N 6.6464 7.0000 0.3536 2.5975 2.5975 -0.0000 + 2 O 8.2247 8.0000 -0.2247 1.8114 1.8114 -0.0000 + 3 H 0.7495 1.0000 0.2505 0.9940 0.9940 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8047 B( 0-O , 3-H ) : 0.9544 B( 1-N , 2-O ) : 1.7538 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 11 sec + +Total time .... 11.971 sec +Sum of individual times .... 11.241 sec ( 93.9%) + +Fock matrix formation .... 6.142 sec ( 51.3%) +Diagonalization .... 2.871 sec ( 24.0%) +Density matrix formation .... 0.082 sec ( 0.7%) +Population analysis .... 0.059 sec ( 0.5%) +Initial guess .... 0.031 sec ( 0.3%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.023 sec ( 0.2%) +DIIS solution .... 2.056 sec ( 17.2%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.820 sec +Reference energy ... -204.704433487 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 11.568 sec +AO-integral generation ... 0.397 sec +Half transformation ... 0.181 sec +K-integral sorting ... 8.806 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.069 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.084 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.079 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.089 s ( 0.001 ms/b) +: 159120 b 0 skpd 0.048 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.088 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.081 s ( 0.001 ms/b) + 87516 b 0 skpd 0.059 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.103 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.061 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.901 sec +AO-integral generation ... 0.674 sec +Half transformation ... 0.091 sec +J-integral sorting ... 0.105 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.432 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.398 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090093109 +EMP2(bb)= -0.090093109 +EMP2(ab)= -0.517920303 + +Initial guess performed in 0.204 sec +E(0) ... -204.704433487 +E(MP2) ... -0.698106520 +Initial E(tot) ... -205.402540007 + ... 0.190168599 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.402540007 -0.698106520 -0.000000000 0.019009080 8.04 0.000002563 + *** Turning on DIIS *** + 1 -205.373936415 -0.669502928 0.028603592 0.010708096 6.51 0.055708381 + 2 -205.393574516 -0.689141029 -0.019638101 0.003773017 5.76 0.058390777 + 3 -205.397417608 -0.692984121 -0.003843092 0.002048445 6.23 0.071342795 + 4 -205.398963181 -0.694529694 -0.001545573 0.000974510 6.22 0.077074459 + 5 -205.399449625 -0.695016139 -0.000486445 0.000440164 5.63 0.081321501 + 6 -205.399526001 -0.695092514 -0.000076375 0.000329890 6.51 0.083245045 + 7 -205.399556466 -0.695122979 -0.000030465 0.000245766 7.35 0.084094400 + 8 -205.399563299 -0.695129812 -0.000006833 0.000175595 7.43 0.084472937 + 9 -205.399560219 -0.695126732 0.000003080 0.000116028 7.54 0.084630472 + 10 -205.399565005 -0.695131518 -0.000004786 0.000059306 8.05 0.084717514 + 11 -205.399561443 -0.695127956 0.000003562 0.000026143 6.32 0.084746999 + 12 -205.399564029 -0.695130542 -0.000002586 0.000012773 6.41 0.084763969 + 13 -205.399564133 -0.695130646 -0.000000104 0.000009016 7.81 0.084767338 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.704433487 +E(CORR) ... -0.695130646 +E(TOT) ... -205.399564133 +Singles norm **1/2 ... 0.084767338 ( 0.042383669, 0.042383669) +T1 diagnostic ... 0.019979853 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.060778 + 8a-> 13a 8b-> 13b 0.056208 + 8a-> 13a 9b-> 13b 0.046744 + 9a-> 13a 8b-> 13b 0.046744 + 5a-> 13a 5b-> 13b 0.030277 + 11a-> 13a 11b-> 13b 0.028016 + 8a-> 13a -1a-> -1a 0.027944 + 8b-> 13b -1b-> -1b 0.027944 + 11a-> 24a 11b-> 24b 0.026105 + 9a-> 22a 9b-> 13b 0.023349 + 9a-> 13a 9b-> 22b 0.023349 + 11a-> 24a 11b-> 25b 0.022953 + 11a-> 25a 11b-> 24b 0.022953 + 11a-> 25a 11b-> 25b 0.022334 + 11a-> 24a -1a-> -1a 0.020988 + 11b-> 24b -1b-> -1b 0.020988 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034621709 + alpha-alpha-alpha ... -0.000862189 ( 2.5%) + alpha-alpha-beta ... -0.016448665 ( 47.5%) + alpha-beta -beta ... -0.016448665 ( 47.5%) + beta -beta -beta ... -0.000862189 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034621709 + +Final correlation energy ... -0.729752354 +E(CCSD) ... -205.399564133 +E(CCSD(T)) ... -205.434185841 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210889618 sqrt= 1.100404297 +W(HF) = 0.825839106 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.322229 -0.000000 + 1 N : 0.182089 -0.000000 + 2 O : -0.098060 -0.000000 + 3 H : 0.238199 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.842242 s : 3.842242 + pz : 1.641015 p : 4.414950 + px : 1.247599 + py : 1.526337 + dz2 : 0.009500 d : 0.057103 + dxz : 0.010830 + dyz : 0.008937 + dx2y2 : 0.016766 + dxy : 0.011070 + f0 : 0.001188 f : 0.007934 + f+1 : 0.001260 + f-1 : 0.000922 + f+2 : 0.001068 + f-2 : 0.000765 + f+3 : 0.001393 + f-3 : 0.001339 + 1 N s : 3.877378 s : 3.877378 + pz : 0.891549 p : 2.743556 + px : 0.869572 + py : 0.982436 + dz2 : 0.036377 d : 0.167183 + dxz : 0.041884 + dyz : 0.019151 + dx2y2 : 0.041238 + dxy : 0.028532 + f0 : 0.003434 f : 0.029794 + f+1 : 0.005237 + f-1 : 0.002908 + f+2 : 0.003762 + f-2 : 0.004137 + f+3 : 0.004554 + f-3 : 0.005761 + 2 O s : 3.862849 s : 3.862849 + pz : 1.168163 p : 4.142089 + px : 1.693732 + py : 1.280194 + dz2 : 0.025261 d : 0.083282 + dxz : 0.015308 + dyz : 0.014139 + dx2y2 : 0.013040 + dxy : 0.015535 + f0 : 0.001784 f : 0.009839 + f+1 : 0.001199 + f-1 : 0.001516 + f+2 : 0.001459 + f-2 : 0.001622 + f+3 : 0.001192 + f-3 : 0.001067 + 3 H s : 0.650176 s : 0.650176 + pz : 0.041053 p : 0.094640 + px : 0.025684 + py : 0.027904 + dz2 : 0.006179 d : 0.016985 + dxz : 0.003037 + dyz : -0.000044 + dx2y2 : 0.002354 + dxy : 0.005459 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.575077 0.000000 + 1 N : -0.272898 0.000000 + 2 O : 0.292633 -0.000000 + 3 H : -0.594812 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.144065 s : 3.144065 + pz : 1.376744 p : 3.915795 + px : 1.181784 + py : 1.357267 + dz2 : 0.039309 d : 0.284673 + dxz : 0.062587 + dyz : 0.036529 + dx2y2 : 0.087997 + dxy : 0.058250 + f0 : 0.007276 f : 0.080390 + f+1 : 0.016305 + f-1 : 0.002662 + f+2 : 0.015350 + f-2 : 0.005310 + f+3 : 0.014629 + f-3 : 0.018858 + 1 N s : 3.045966 s : 3.045966 + pz : 0.974125 p : 2.878180 + px : 0.889687 + py : 1.014368 + dz2 : 0.160066 d : 0.921102 + dxz : 0.239724 + dyz : 0.176159 + dx2y2 : 0.197973 + dxy : 0.147180 + f0 : 0.047957 f : 0.427651 + f+1 : 0.064715 + f-1 : 0.055811 + f+2 : 0.073719 + f-2 : 0.066990 + f+3 : 0.056015 + f-3 : 0.062442 + 2 O s : 3.317198 s : 3.317198 + pz : 1.234758 p : 3.904976 + px : 1.409884 + py : 1.260334 + dz2 : 0.063144 d : 0.359300 + dxz : 0.073584 + dyz : 0.118767 + dx2y2 : 0.065216 + dxy : 0.038589 + f0 : 0.017016 f : 0.125894 + f+1 : 0.012782 + f-1 : 0.027780 + f+2 : 0.030687 + f-2 : 0.020944 + f+3 : 0.005868 + f-3 : 0.010817 + 3 H s : 0.626887 s : 0.626887 + pz : 0.207647 p : 0.588047 + px : 0.138689 + py : 0.241710 + dz2 : 0.083370 d : 0.379878 + dxz : 0.052338 + dyz : 0.097000 + dx2y2 : 0.072986 + dxy : 0.074184 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3222 8.0000 -0.3222 2.1595 1.6950 0.4645 + 1 N 6.8179 7.0000 0.1821 2.8591 2.3629 0.4963 + 2 O 8.0981 8.0000 -0.0981 2.1960 1.6971 0.4989 + 3 H 0.7618 1.0000 0.2382 1.0152 0.9403 0.0749 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7148 B( 0-O , 3-H ) : 0.8922 B( 1-N , 2-O ) : 1.6045 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 128.780 sec + +Fock Matrix Formation ... 0.820 sec ( 0.6%) +Initial Guess ... 0.204 sec ( 0.2%) +DIIS Solver ... 5.302 sec ( 4.1%) +State Vector Update ... 0.274 sec ( 0.2%) +Sigma-vector construction ... 90.226 sec ( 70.1%) + <0|H|D> ... 0.008 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.050 sec ( 0.1% of sigma) + (0-ext) ... 0.165 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.061 sec ( 0.1% of sigma) + (2-ext) ... 2.031 sec ( 2.3% of sigma) + (4-ext) ... 51.915 sec ( 57.5% of sigma) + ... 4.755 sec ( 5.3% of sigma) + ... 0.007 sec ( 0.0% of sigma) + (1-ext) ... 0.022 sec ( 0.0% of sigma) + (1-ext) ... 0.226 sec ( 0.3% of sigma) + Fock-dressing ... 5.919 sec ( 6.6% of sigma) + (ik|jl)-dressing ... 0.163 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 20.349 sec ( 22.6% of sigma) + Pair energies ... 0.028 sec ( 0.0% of sigma) +Total Time for computing (T) ... 16.618 sec ( 12.9% of ALL) + I/O of integral and amplitudes ... 1.339 sec ( 8.1% of (T)) + External N**7 contributions ... 9.107 sec ( 54.8% of (T)) + Internal N**7 contributions ... 0.812 sec ( 4.9% of (T)) + N**6 triples energy contributions ... 2.946 sec ( 17.7% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.434185841146 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.001850542 -0.000425979 -0.003549473 + 2 N : 0.002252266 -0.001263267 0.003319671 + 3 O : -0.001199231 0.000770166 -0.002265596 + 4 H : 0.000797507 0.000919080 0.002495398 + +Norm of the cartesian gradient ... 0.006983228 +RMS gradient ... 0.002015884 +MAX gradient ... 0.003549473 + +------- +TIMINGS +------- + +Total numerical gradient time ... 889.967 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: -529.07 cm**-1 ***imaginary mode*** + 7: 540.42 cm**-1 + 8: 767.96 cm**-1 + 9: 1132.51 cm**-1 + 10: 1704.30 cm**-1 + 11: 3710.78 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 -0.029953 0.586288 -0.179695 -0.050753 -0.071334 -0.002694 + 1 0.034198 0.090680 0.174998 -0.044213 0.023115 -0.049491 + 2 -0.058371 -0.377711 -0.129498 -0.008191 0.013939 -0.038329 + 3 0.039568 -0.289166 0.579893 -0.029338 -0.059543 0.000016 + 4 0.051955 -0.097598 -0.270005 0.043568 -0.497510 -0.000011 + 5 0.049068 0.254473 0.005770 0.033164 0.543134 -0.000463 + 6 -0.013838 -0.357784 -0.352149 0.015137 0.130887 -0.000485 + 7 -0.041233 -0.001962 0.042184 0.003300 0.412196 -0.000359 + 8 -0.033035 0.166835 0.146628 -0.007837 -0.493337 0.000552 + 9 0.145229 0.391386 0.383338 0.972979 -0.117828 0.050231 + 10 -0.610302 -0.051928 0.304816 0.043962 0.004055 0.791376 + 11 0.768967 -0.189085 -0.352072 -0.206451 0.061719 0.606031 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 7: 540.42 0.025841 130.59 0.014922 (-0.097173 -0.013148 0.072845) + 8: 767.96 0.028584 144.45 0.011615 ( 0.094119 -0.006339 -0.052119) + 9: 1132.51 0.007540 38.10 0.002078 ( 0.038999 -0.014601 -0.018535) + 10: 1704.30 0.034307 173.37 0.006282 (-0.059360 -0.014818 0.050384) + 11: 3710.78 0.010800 54.58 0.000908 (-0.012201 0.017412 0.021357) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 7 +The total number of vibrations considered is 5 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 540.42 E(vib) ... 0.12 +freq. 767.96 E(vib) ... 0.06 +freq. 1132.51 E(vib) ... 0.01 +freq. 1704.30 E(vib) ... 0.00 +freq. 3710.78 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.43418584 Eh +Zero point energy ... 0.01789723 Eh 11.23 kcal/mol +Thermal vibrational correction ... 0.00030808 Eh 0.19 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.41314799 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00314063 Eh 1.97 kcal/mol +Non-thermal (ZPE) correction 0.01789723 Eh 11.23 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02103785 Eh 13.20 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.41314799 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.41220378 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.677832 0.400033 0.360026 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00040854 Eh 0.26 kcal/mol +Rotational entropy ... 0.00996061 Eh 6.25 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02817147 Eh 17.68 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00996061 Eh 6.25 kcal/mol| +| sn= 2 | S(rot)= 0.00930615 Eh 5.84 kcal/mol| +| sn= 3 | S(rot)= 0.00892332 Eh 5.60 kcal/mol| +| sn= 4 | S(rot)= 0.00865170 Eh 5.43 kcal/mol| +| sn= 5 | S(rot)= 0.00844101 Eh 5.30 kcal/mol| +| sn= 6 | S(rot)= 0.00826886 Eh 5.19 kcal/mol| +| sn= 7 | S(rot)= 0.00812332 Eh 5.10 kcal/mol| +| sn= 8 | S(rot)= 0.00799724 Eh 5.02 kcal/mol| +| sn= 9 | S(rot)= 0.00788603 Eh 4.95 kcal/mol| +| sn=10 | S(rot)= 0.00778655 Eh 4.89 kcal/mol| +| sn=11 | S(rot)= 0.00769656 Eh 4.83 kcal/mol| +| sn=12 | S(rot)= 0.00761441 Eh 4.78 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.41220378 Eh +Total entropy correction ... -0.02817147 Eh -17.68 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44037525 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00618941 Eh -3.88 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.434185842 Eh +Current gradient norm .... 0.006983249 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + -0.030831171 0.091539448 0.162915951 0.466256401 0.498038795 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999893836 +Lowest eigenvalues of augmented Hessian: + -0.000047762 0.090739851 0.162917480 0.465797512 0.498048138 +Length of the computed step .... 0.014572636 +The final length of the internal step .... 0.014572636 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0059492537 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0037910124 RMS(Int)= 0.0059473722 + Iter 1: RMS(Cart)= 0.0000191204 RMS(Int)= 0.0000255099 + Iter 2: RMS(Cart)= 0.0000001098 RMS(Int)= 0.0000001501 + Iter 3: RMS(Cart)= 0.0000000009 RMS(Int)= 0.0000000010 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000002 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0017658814 0.0001000000 NO + MAX gradient 0.0029421541 0.0003000000 NO + RMS step 0.0059492537 0.0020000000 NO + MAX step 0.0084946417 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0045 Max(Angles) 0.46 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.5082 0.000748 -0.0045 1.5037 + 2. B(O 2,N 1) 1.1666 0.001912 -0.0009 1.1657 + 3. B(H 3,O 0) 0.9724 0.002287 -0.0025 0.9699 + 4. A(N 1,O 0,H 3) 102.84 -0.000780 0.46 103.30 + 5. A(O 0,N 1,O 2) 110.89 -0.002942 0.41 111.30 + 6. D(O 2,N 1,O 0,H 3) -81.82 -0.002713 0.00 -81.82 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.790940 -0.279014 0.295543 + N 0.632560 -0.465824 -0.151634 + O 0.899065 0.254797 -1.028258 + H -0.740684 0.490041 0.884350 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.494660 -0.527260 0.558496 + 1 N 7.0000 0 14.007 1.195365 -0.880279 -0.286548 + 2 O 8.0000 0 15.999 1.698987 0.481497 -1.943127 + 3 H 1.0000 0 1.008 -1.399690 0.926043 1.671179 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.503734395260 0.00000000 0.00000000 + O 2 1 0 1.165671018475 111.30105330 0.00000000 + H 1 2 3 0.969878422926 103.29657009 278.18181822 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.841646185200 0.00000000 0.00000000 + O 2 1 0 2.202798987166 111.30105330 0.00000000 + H 1 2 3 1.832804602530 103.29657009 278.18181822 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2229 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2697 + la=0 lb=0: 549 shell pairs + la=1 lb=0: 535 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.359235750255 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.824e-04 +Time for diagonalization ... 0.004 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.003 sec +Total time needed ... 0.007 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7050897701 0.000000000000 0.00018365 0.00000612 0.0011271 0.7000 + 1 -204.7050981794 -0.000008409301 0.00014411 0.00000504 0.0009236 0.7000 + ***Turning on DIIS*** + 2 -204.7051051566 -0.000006977170 0.00034654 0.00001326 0.0007429 0.0000 + 3 -204.7047684871 0.000336669445 0.00013129 0.00000551 0.0002442 0.0000 + 4 -204.7052112486 -0.000442761486 0.00004160 0.00000195 0.0000713 0.0000 + 5 -204.7053266077 -0.000115359111 0.00002528 0.00000103 0.0000589 0.0000 + 6 -204.7050005996 0.000326008133 0.00002360 0.00000101 0.0000349 0.0000 + 7 -204.7051510644 -0.000150464773 0.00001560 0.00000072 0.0000169 0.0000 + 8 -204.7051180257 0.000033038661 0.00001264 0.00000051 0.0000095 0.0000 + 9 -204.7051081497 0.000009876050 0.00000627 0.00000025 0.0000052 0.0000 + 10 -204.7051411673 -0.000033017609 0.00000311 0.00000011 0.0000023 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + +Total Energy : -204.70512510 Eh -5570.30964 eV + Last Energy change ... 1.6069e-05 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.1726e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.277 sec +Reference energy ... -204.705128630 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.758 sec +AO-integral generation ... 0.159 sec +Half transformation ... 0.087 sec +K-integral sorting ... 5.596 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.029 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.031 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.034 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.044 s ( 0.000 ms/b) + 159120 b 0 skpd 0.020 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.039 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.035 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.027 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.046 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.026 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.401 sec +AO-integral generation ... 0.284 sec +Half transformation ... 0.048 sec +J-integral sorting ... 0.052 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.161 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.266 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090011403 +EMP2(bb)= -0.090011403 +EMP2(ab)= -0.517382050 + +Initial guess performed in 0.139 sec +E(0) ... -204.705128630 +E(MP2) ... -0.697404857 +Initial E(tot) ... -205.402533488 + ... 0.189537013 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.402533488 -0.697404857 -0.000000000 0.019035440 3.09 0.000001351 + *** Turning on DIIS *** + 1 -205.374215856 -0.669087226 0.028317632 0.010716019 3.86 0.055521817 + 2 -205.393756005 -0.688627374 -0.019540149 0.003785967 4.53 0.058239428 + 3 -205.397579707 -0.692451076 -0.003823702 0.002049391 4.32 0.071147623 + 4 -205.399115868 -0.693987238 -0.001536161 0.000941580 3.84 0.076865199 + 5 -205.399598534 -0.694469904 -0.000482667 0.000444611 3.88 0.081095405 + 6 -205.399674619 -0.694545989 -0.000076085 0.000332769 3.79 0.083010833 + 7 -205.399704868 -0.694576237 -0.000030248 0.000247713 3.35 0.083850266 + 8 -205.399711546 -0.694582915 -0.000006678 0.000176896 3.27 0.084223239 + 9 -205.399708545 -0.694579914 0.000003001 0.000116371 3.35 0.084380529 + 10 -205.399713277 -0.694584646 -0.000004732 0.000058825 4.70 0.084468073 + 11 -205.399709764 -0.694581133 0.000003513 0.000025520 4.54 0.084498049 + 12 -205.399712328 -0.694583698 -0.000002565 0.000012800 4.34 0.084514867 + 13 -205.399712439 -0.694583808 -0.000000111 0.000008924 3.87 0.084518311 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.705128630 +E(CORR) ... -0.694583808 +E(TOT) ... -205.399712439 +Singles norm **1/2 ... 0.084518311 ( 0.042259155, 0.042259155) +T1 diagnostic ... 0.019921157 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.060810 + 8a-> 13a 8b-> 13b 0.055954 + 8a-> 13a 9b-> 13b 0.046489 + 9a-> 13a 8b-> 13b 0.046489 + 5a-> 13a 5b-> 13b 0.030074 + 11a-> 13a 11b-> 13b 0.028362 + 8a-> 13a -1a-> -1a 0.028031 + 8b-> 13b -1b-> -1b 0.028031 + 11a-> 24a 11b-> 24b 0.024143 + 9a-> 13a 9b-> 22b 0.023475 + 9a-> 22a 9b-> 13b 0.023475 + 11a-> 25a 11b-> 25b 0.022655 + 11a-> 25a 11b-> 24b 0.022215 + 11a-> 24a 11b-> 25b 0.022215 + 11a-> 24a -1a-> -1a 0.020264 + 11b-> 24b -1b-> -1b 0.020264 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034497252 + alpha-alpha-alpha ... -0.000860992 ( 2.5%) + alpha-alpha-beta ... -0.016387634 ( 47.5%) + alpha-beta -beta ... -0.016387634 ( 47.5%) + beta -beta -beta ... -0.000860992 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034497252 + +Final correlation energy ... -0.729081061 +E(CCSD) ... -205.399712439 +E(CCSD(T)) ... -205.434209691 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210208049 sqrt= 1.100094563 +W(HF) = 0.826304205 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 71.819 sec + +Fock Matrix Formation ... 0.277 sec ( 0.4%) +Initial Guess ... 0.139 sec ( 0.2%) +DIIS Solver ... 3.175 sec ( 4.4%) +State Vector Update ... 0.164 sec ( 0.2%) +Sigma-vector construction ... 51.377 sec ( 71.5%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (0-ext) ... 0.078 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.028 sec ( 0.1% of sigma) + (2-ext) ... 1.041 sec ( 2.0% of sigma) + (4-ext) ... 30.595 sec ( 59.5% of sigma) + ... 2.094 sec ( 4.1% of sigma) + ... 0.003 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.138 sec ( 0.3% of sigma) + Fock-dressing ... 2.811 sec ( 5.5% of sigma) + (ik|jl)-dressing ... 0.082 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 11.481 sec ( 22.3% of sigma) + Pair energies ... 0.015 sec ( 0.0% of sigma) +Total Time for computing (T) ... 8.179 sec ( 11.4% of ALL) + I/O of integral and amplitudes ... 0.864 sec ( 10.6% of (T)) + External N**7 contributions ... 4.246 sec ( 51.9% of (T)) + Internal N**7 contributions ... 0.342 sec ( 4.2% of (T)) + N**6 triples energy contributions ... 1.845 sec ( 22.6% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.434209691330 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.000417871 0.000864036 -0.001703258 + 2 N : 0.000561981 0.001131313 0.001360375 + 3 O : -0.000421500 -0.000993331 -0.000903726 + 4 H : 0.000277390 -0.001002018 0.001246608 + +Norm of the cartesian gradient ... 0.003447417 +RMS gradient ... 0.000995183 +MAX gradient ... 0.001703258 + +------- +TIMINGS +------- + +Total numerical gradient time ... 464.218 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.434209691 Eh +Current gradient norm .... 0.003447417 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999986 +Lowest eigenvalues of augmented Hessian: + -0.000000006 0.090852111 0.162409115 0.465890595 0.500364552 +Length of the computed step .... 0.000166281 +The final length of the internal step .... 0.000166281 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0000678839 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0000631289 RMS(Int)= 0.0000678841 + Iter 1: RMS(Cart)= 0.0000000013 RMS(Int)= 0.0000000026 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000238495 0.0000050000 NO + RMS gradient 0.0000197475 0.0001000000 YES + MAX gradient 0.0000305863 0.0003000000 YES + RMS step 0.0000678839 0.0020000000 YES + MAX step 0.0001192583 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.5037 -0.000020 0.0001 1.5038 + 2. B(O 2,N 1) 1.1657 -0.000031 0.0000 1.1657 + 3. B(H 3,O 0) 0.9699 -0.000023 0.0000 0.9699 + 4. A(N 1,O 0,H 3) 103.30 -0.000020 0.01 103.30 + 5. A(O 0,N 1,O 2) 111.30 0.000008 -0.00 111.30 + 6. D(O 2,N 1,O 0,H 3) -81.82 -0.002892 -0.00 -81.82 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.790943 -0.278999 0.295554 + N 0.632605 -0.465852 -0.151666 + O 0.899092 0.254792 -1.028290 + H -0.740752 0.490058 0.884401 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.494666 -0.527232 0.558516 + 1 N 7.0000 0 14.007 1.195449 -0.880332 -0.286607 + 2 O 8.0000 0 15.999 1.699037 0.481488 -1.943186 + 3 H 1.0000 0 1.008 -1.399818 0.926076 1.671276 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.503797504027 0.00000000 0.00000000 + O 2 1 0 1.165681146687 111.29949237 0.00000000 + H 1 2 3 0.969902010152 103.30239386 278.18181822 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.841765443484 0.00000000 0.00000000 + O 2 1 0 2.202818126714 111.29949237 0.00000000 + H 1 2 3 1.832849175926 103.30239386 278.18181822 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2229 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2697 + la=0 lb=0: 549 shell pairs + la=1 lb=0: 535 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.357564847673 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.3575648477 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.824e-04 +Time for diagonalization ... 0.004 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.003 sec +Total time needed ... 0.007 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7051206206 0.000000000000 0.00000306 0.00000007 0.0000136 0.7000 + 1 -204.7051206218 -0.000000001252 0.00000234 0.00000006 0.0000101 0.7000 + ***Turning on DIIS*** + 2 -204.7051206231 -0.000000001319 0.00000602 0.00000015 0.0000074 0.0000 + 3 -204.7051263996 -0.000005776407 0.00000176 0.00000006 0.0000015 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 4 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70512069 Eh -5570.30952 eV + +Components: +Nuclear Repulsion : 68.35756485 Eh 1860.10391 eV +Electronic Energy : -273.06268554 Eh -7430.41343 eV +One Electron Energy: -416.41245863 Eh -11331.15906 eV +Two Electron Energy: 143.34977309 Eh 3900.74564 eV + +Virial components: +Potential Energy : -408.93199161 Eh -11127.60521 eV +Kinetic Energy : 204.22687092 Eh 5557.29569 eV +Virial Ratio : 2.00234176 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 5.7090e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.9502e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.8801e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.4241e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.692583 -563.0738 + 1 1.0000 -20.616629 -561.0070 + 2 1.0000 -15.805931 -430.1012 + 3 1.0000 -1.618289 -44.0359 + 4 1.0000 -1.371594 -37.3230 + 5 1.0000 -0.956217 -26.0200 + 6 1.0000 -0.767527 -20.8855 + 7 1.0000 -0.734110 -19.9761 + 8 1.0000 -0.699782 -19.0420 + 9 1.0000 -0.604917 -16.4606 + 10 1.0000 -0.529517 -14.4089 + 11 1.0000 -0.459351 -12.4996 + 12 0.0000 0.031008 0.8438 + 13 0.0000 0.065971 1.7952 + 14 0.0000 0.091806 2.4982 + 15 0.0000 0.104271 2.8374 + 16 0.0000 0.113057 3.0764 + 17 0.0000 0.155512 4.2317 + 18 0.0000 0.157299 4.2803 + 19 0.0000 0.174476 4.7477 + 20 0.0000 0.178955 4.8696 + 21 0.0000 0.189860 5.1663 + 22 0.0000 0.201092 5.4720 + 23 0.0000 0.235279 6.4023 + 24 0.0000 0.269084 7.3221 + 25 0.0000 0.290476 7.9043 + 26 0.0000 0.301645 8.2082 + 27 0.0000 0.331823 9.0294 + 28 0.0000 0.334096 9.0912 + 29 0.0000 0.352097 9.5811 + 30 0.0000 0.424771 11.5586 + 31 0.0000 0.506481 13.7820 + 32 0.0000 0.529994 14.4219 + 33 0.0000 0.543528 14.7902 + 34 0.0000 0.565802 15.3963 + 35 0.0000 0.599591 16.3157 + 36 0.0000 0.630970 17.1696 + 37 0.0000 0.646412 17.5898 + 38 0.0000 0.709180 19.2978 + 39 0.0000 0.716603 19.4998 + 40 0.0000 0.736242 20.0342 + 41 0.0000 0.755513 20.5586 + 42 0.0000 0.761243 20.7145 + 43 0.0000 0.788960 21.4687 + 44 0.0000 0.807280 21.9672 + 45 0.0000 0.817480 22.2448 + 46 0.0000 0.860241 23.4083 + 47 0.0000 0.873204 23.7611 + 48 0.0000 0.893045 24.3010 + 49 0.0000 0.953737 25.9525 + 50 0.0000 0.961947 26.1759 + 51 0.0000 0.975830 26.5537 + 52 0.0000 0.991170 26.9711 + 53 0.0000 1.028556 27.9884 + 54 0.0000 1.044133 28.4123 + 55 0.0000 1.099836 29.9280 + 56 0.0000 1.154534 31.4165 + 57 0.0000 1.221490 33.2384 + 58 0.0000 1.246857 33.9287 + 59 0.0000 1.264136 34.3989 + 60 0.0000 1.315148 35.7870 + 61 0.0000 1.409193 38.3461 + 62 0.0000 1.460003 39.7287 + 63 0.0000 1.515788 41.2467 + 64 0.0000 1.530512 41.6474 + 65 0.0000 1.572477 42.7893 + 66 0.0000 1.589211 43.2446 + 67 0.0000 1.631033 44.3827 + 68 0.0000 1.649876 44.8954 + 69 0.0000 1.723364 46.8951 + 70 0.0000 1.761389 47.9298 + 71 0.0000 1.779730 48.4289 + 72 0.0000 1.902307 51.7644 + 73 0.0000 1.924371 52.3648 + 74 0.0000 1.979952 53.8772 + 75 0.0000 2.010151 54.6990 + 76 0.0000 2.042185 55.5707 + 77 0.0000 2.095511 57.0218 + 78 0.0000 2.135623 58.1132 + 79 0.0000 2.195477 59.7420 + 80 0.0000 2.273901 61.8760 + 81 0.0000 2.290468 62.3268 + 82 0.0000 2.332661 63.4749 + 83 0.0000 2.352861 64.0246 + 84 0.0000 2.406339 65.4798 + 85 0.0000 2.452484 66.7355 + 86 0.0000 2.465585 67.0920 + 87 0.0000 2.476697 67.3944 + 88 0.0000 2.509775 68.2945 + 89 0.0000 2.563606 69.7593 + 90 0.0000 2.584788 70.3356 + 91 0.0000 2.600663 70.7676 + 92 0.0000 2.664771 72.5121 + 93 0.0000 2.721371 74.0523 + 94 0.0000 2.749839 74.8269 + 95 0.0000 2.764300 75.2204 + 96 0.0000 2.842358 77.3445 + 97 0.0000 2.908252 79.1376 + 98 0.0000 2.958018 80.4918 + 99 0.0000 2.982376 81.1546 + 100 0.0000 3.066312 83.4386 + 101 0.0000 3.167406 86.1895 + 102 0.0000 3.223079 87.7044 + 103 0.0000 3.485763 94.8524 + 104 0.0000 3.718656 101.1898 + 105 0.0000 3.815131 103.8150 + 106 0.0000 4.045005 110.0702 + 107 0.0000 4.170780 113.4927 + 108 0.0000 4.202077 114.3443 + 109 0.0000 4.282807 116.5411 + 110 0.0000 4.364996 118.7776 + 111 0.0000 4.392959 119.5385 + 112 0.0000 4.523786 123.0985 + 113 0.0000 4.611055 125.4732 + 114 0.0000 4.662277 126.8670 + 115 0.0000 4.718668 128.4015 + 116 0.0000 4.838610 131.6653 + 117 0.0000 4.895219 133.2057 + 118 0.0000 4.928658 134.1156 + 119 0.0000 4.953718 134.7975 + 120 0.0000 5.048736 137.3831 + 121 0.0000 5.105321 138.9228 + 122 0.0000 5.184372 141.0739 + 123 0.0000 5.194938 141.3615 + 124 0.0000 5.232648 142.3876 + 125 0.0000 5.309355 144.4749 + 126 0.0000 5.387224 146.5938 + 127 0.0000 5.487138 149.3126 + 128 0.0000 5.548453 150.9811 + 129 0.0000 5.696057 154.9976 + 130 0.0000 5.740189 156.1985 + 131 0.0000 5.935894 161.5239 + 132 0.0000 6.173563 167.9912 + 133 0.0000 6.418199 174.6481 + 134 0.0000 6.479239 176.3091 + 135 0.0000 6.506106 177.0402 + 136 0.0000 6.696214 182.2132 + 137 0.0000 6.720458 182.8729 + 138 0.0000 6.772777 184.2966 + 139 0.0000 6.817132 185.5036 + 140 0.0000 6.830083 185.8560 + 141 0.0000 7.069347 192.3667 + 142 0.0000 7.102272 193.2626 + 143 0.0000 7.117308 193.6718 + 144 0.0000 7.200407 195.9330 + 145 0.0000 7.255890 197.4428 + 146 0.0000 7.281531 198.1405 + 147 0.0000 7.338815 199.6993 + 148 0.0000 7.383812 200.9238 + 149 0.0000 7.454441 202.8457 + 150 0.0000 7.464962 203.1319 + 151 0.0000 7.567172 205.9132 + 152 0.0000 7.570522 206.0044 + 153 0.0000 7.635406 207.7700 + 154 0.0000 7.700033 209.5285 + 155 0.0000 7.893648 214.7971 + 156 0.0000 7.930810 215.8083 + 157 0.0000 8.395725 228.4593 + 158 0.0000 14.051567 382.3626 + 159 0.0000 14.867913 404.5765 + 160 0.0000 16.079103 437.5346 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.692583 -563.0738 + 1 1.0000 -20.616629 -561.0070 + 2 1.0000 -15.805931 -430.1012 + 3 1.0000 -1.618289 -44.0359 + 4 1.0000 -1.371594 -37.3230 + 5 1.0000 -0.956217 -26.0200 + 6 1.0000 -0.767527 -20.8855 + 7 1.0000 -0.734110 -19.9761 + 8 1.0000 -0.699782 -19.0420 + 9 1.0000 -0.604917 -16.4606 + 10 1.0000 -0.529517 -14.4089 + 11 1.0000 -0.459351 -12.4996 + 12 0.0000 0.031008 0.8438 + 13 0.0000 0.065971 1.7952 + 14 0.0000 0.091806 2.4982 + 15 0.0000 0.104271 2.8374 + 16 0.0000 0.113057 3.0764 + 17 0.0000 0.155512 4.2317 + 18 0.0000 0.157299 4.2803 + 19 0.0000 0.174476 4.7477 + 20 0.0000 0.178955 4.8696 + 21 0.0000 0.189860 5.1663 + 22 0.0000 0.201092 5.4720 + 23 0.0000 0.235279 6.4023 + 24 0.0000 0.269084 7.3221 + 25 0.0000 0.290476 7.9043 + 26 0.0000 0.301645 8.2082 + 27 0.0000 0.331823 9.0294 + 28 0.0000 0.334096 9.0912 + 29 0.0000 0.352097 9.5811 + 30 0.0000 0.424771 11.5586 + 31 0.0000 0.506481 13.7820 + 32 0.0000 0.529994 14.4219 + 33 0.0000 0.543528 14.7902 + 34 0.0000 0.565802 15.3963 + 35 0.0000 0.599591 16.3157 + 36 0.0000 0.630970 17.1696 + 37 0.0000 0.646412 17.5898 + 38 0.0000 0.709180 19.2978 + 39 0.0000 0.716603 19.4998 + 40 0.0000 0.736242 20.0342 + 41 0.0000 0.755513 20.5586 + 42 0.0000 0.761243 20.7145 + 43 0.0000 0.788960 21.4687 + 44 0.0000 0.807280 21.9672 + 45 0.0000 0.817480 22.2448 + 46 0.0000 0.860241 23.4083 + 47 0.0000 0.873204 23.7611 + 48 0.0000 0.893045 24.3010 + 49 0.0000 0.953737 25.9525 + 50 0.0000 0.961947 26.1759 + 51 0.0000 0.975830 26.5537 + 52 0.0000 0.991170 26.9711 + 53 0.0000 1.028556 27.9884 + 54 0.0000 1.044133 28.4123 + 55 0.0000 1.099836 29.9280 + 56 0.0000 1.154534 31.4165 + 57 0.0000 1.221490 33.2384 + 58 0.0000 1.246857 33.9287 + 59 0.0000 1.264136 34.3989 + 60 0.0000 1.315148 35.7870 + 61 0.0000 1.409193 38.3461 + 62 0.0000 1.460003 39.7287 + 63 0.0000 1.515788 41.2467 + 64 0.0000 1.530512 41.6474 + 65 0.0000 1.572477 42.7893 + 66 0.0000 1.589211 43.2446 + 67 0.0000 1.631033 44.3827 + 68 0.0000 1.649876 44.8954 + 69 0.0000 1.723364 46.8951 + 70 0.0000 1.761389 47.9298 + 71 0.0000 1.779730 48.4289 + 72 0.0000 1.902307 51.7644 + 73 0.0000 1.924371 52.3648 + 74 0.0000 1.979952 53.8772 + 75 0.0000 2.010151 54.6990 + 76 0.0000 2.042185 55.5707 + 77 0.0000 2.095511 57.0218 + 78 0.0000 2.135623 58.1132 + 79 0.0000 2.195477 59.7420 + 80 0.0000 2.273901 61.8760 + 81 0.0000 2.290468 62.3268 + 82 0.0000 2.332661 63.4749 + 83 0.0000 2.352861 64.0246 + 84 0.0000 2.406339 65.4798 + 85 0.0000 2.452484 66.7355 + 86 0.0000 2.465585 67.0920 + 87 0.0000 2.476697 67.3944 + 88 0.0000 2.509775 68.2945 + 89 0.0000 2.563606 69.7593 + 90 0.0000 2.584788 70.3356 + 91 0.0000 2.600663 70.7676 + 92 0.0000 2.664771 72.5121 + 93 0.0000 2.721371 74.0523 + 94 0.0000 2.749839 74.8269 + 95 0.0000 2.764300 75.2204 + 96 0.0000 2.842358 77.3445 + 97 0.0000 2.908252 79.1376 + 98 0.0000 2.958018 80.4918 + 99 0.0000 2.982376 81.1546 + 100 0.0000 3.066312 83.4386 + 101 0.0000 3.167406 86.1895 + 102 0.0000 3.223079 87.7044 + 103 0.0000 3.485763 94.8524 + 104 0.0000 3.718656 101.1898 + 105 0.0000 3.815131 103.8150 + 106 0.0000 4.045005 110.0702 + 107 0.0000 4.170780 113.4927 + 108 0.0000 4.202077 114.3443 + 109 0.0000 4.282807 116.5411 + 110 0.0000 4.364996 118.7776 + 111 0.0000 4.392959 119.5385 + 112 0.0000 4.523786 123.0985 + 113 0.0000 4.611055 125.4732 + 114 0.0000 4.662277 126.8670 + 115 0.0000 4.718668 128.4015 + 116 0.0000 4.838610 131.6653 + 117 0.0000 4.895219 133.2057 + 118 0.0000 4.928658 134.1156 + 119 0.0000 4.953718 134.7975 + 120 0.0000 5.048736 137.3831 + 121 0.0000 5.105321 138.9228 + 122 0.0000 5.184372 141.0739 + 123 0.0000 5.194938 141.3615 + 124 0.0000 5.232648 142.3876 + 125 0.0000 5.309355 144.4749 + 126 0.0000 5.387224 146.5938 + 127 0.0000 5.487138 149.3126 + 128 0.0000 5.548453 150.9811 + 129 0.0000 5.696057 154.9976 + 130 0.0000 5.740189 156.1985 + 131 0.0000 5.935894 161.5239 + 132 0.0000 6.173563 167.9912 + 133 0.0000 6.418199 174.6481 + 134 0.0000 6.479239 176.3091 + 135 0.0000 6.506106 177.0402 + 136 0.0000 6.696214 182.2132 + 137 0.0000 6.720458 182.8729 + 138 0.0000 6.772777 184.2966 + 139 0.0000 6.817132 185.5036 + 140 0.0000 6.830083 185.8560 + 141 0.0000 7.069347 192.3667 + 142 0.0000 7.102272 193.2626 + 143 0.0000 7.117308 193.6718 + 144 0.0000 7.200407 195.9330 + 145 0.0000 7.255890 197.4428 + 146 0.0000 7.281531 198.1405 + 147 0.0000 7.338815 199.6993 + 148 0.0000 7.383812 200.9238 + 149 0.0000 7.454441 202.8457 + 150 0.0000 7.464962 203.1319 + 151 0.0000 7.567172 205.9132 + 152 0.0000 7.570522 206.0044 + 153 0.0000 7.635406 207.7700 + 154 0.0000 7.700033 209.5285 + 155 0.0000 7.893648 214.7971 + 156 0.0000 7.930810 215.8083 + 157 0.0000 8.395725 228.4593 + 158 0.0000 14.051567 382.3626 + 159 0.0000 14.867913 404.5765 + 160 0.0000 16.079103 437.5346 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.375282 0.000000 + 1 N : 0.353464 0.000000 + 2 O : -0.225962 0.000000 + 3 H : 0.247780 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.861065 s : 3.861065 + pz : 1.665790 p : 4.483767 + px : 1.263431 + py : 1.554545 + dz2 : 0.002577 d : 0.026246 + dxz : 0.004427 + dyz : 0.002576 + dx2y2 : 0.012778 + dxy : 0.003888 + f0 : 0.000660 f : 0.004205 + f+1 : 0.000773 + f-1 : 0.000271 + f+2 : 0.000526 + f-2 : 0.000084 + f+3 : 0.001064 + f-3 : 0.000828 + 1 N s : 3.823306 s : 3.823306 + pz : 0.864279 p : 2.654022 + px : 0.818015 + py : 0.971728 + dz2 : 0.035736 d : 0.138290 + dxz : 0.031459 + dyz : 0.014416 + dx2y2 : 0.035346 + dxy : 0.021333 + f0 : 0.004045 f : 0.030917 + f+1 : 0.005199 + f-1 : 0.003165 + f+2 : 0.003962 + f-2 : 0.004243 + f+3 : 0.004512 + f-3 : 0.005791 + 2 O s : 3.875329 s : 3.875329 + pz : 1.190503 p : 4.280555 + px : 1.775876 + py : 1.314176 + dz2 : 0.025271 d : 0.062595 + dxz : 0.008613 + dyz : 0.010896 + dx2y2 : 0.007356 + dxy : 0.010459 + f0 : 0.001761 f : 0.007482 + f+1 : 0.000660 + f-1 : 0.001422 + f+2 : 0.001131 + f-2 : 0.001265 + f+3 : 0.000682 + f-3 : 0.000561 + 3 H s : 0.643802 s : 0.643802 + pz : 0.037757 p : 0.088229 + px : 0.022968 + py : 0.027504 + dz2 : 0.006978 d : 0.020189 + dxz : 0.003332 + dyz : 0.000692 + dx2y2 : 0.002983 + dxy : 0.006205 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.574115 0.000000 + 1 N : -0.232409 0.000000 + 2 O : 0.249838 0.000000 + 3 H : -0.591544 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.136667 s : 3.136667 + pz : 1.396848 p : 3.960160 + px : 1.182841 + py : 1.380472 + dz2 : 0.033852 d : 0.255023 + dxz : 0.056647 + dyz : 0.029458 + dx2y2 : 0.081617 + dxy : 0.053450 + f0 : 0.006161 f : 0.074035 + f+1 : 0.016040 + f-1 : 0.001996 + f+2 : 0.013947 + f-2 : 0.004491 + f+3 : 0.012959 + f-3 : 0.018442 + 1 N s : 3.038665 s : 3.038665 + pz : 0.960448 p : 2.837845 + px : 0.867105 + py : 1.010292 + dz2 : 0.163179 d : 0.918077 + dxz : 0.240384 + dyz : 0.170337 + dx2y2 : 0.194913 + dxy : 0.149264 + f0 : 0.048377 f : 0.437822 + f+1 : 0.067487 + f-1 : 0.055431 + f+2 : 0.076887 + f-2 : 0.070073 + f+3 : 0.054881 + f-3 : 0.064687 + 2 O s : 3.314037 s : 3.314037 + pz : 1.247757 p : 3.987576 + px : 1.461465 + py : 1.278354 + dz2 : 0.054562 d : 0.330911 + dxz : 0.069701 + dyz : 0.113996 + dx2y2 : 0.060014 + dxy : 0.032638 + f0 : 0.013954 f : 0.117639 + f+1 : 0.012043 + f-1 : 0.026213 + f+2 : 0.030833 + f-2 : 0.019551 + f+3 : 0.004573 + f-3 : 0.010471 + 3 H s : 0.627148 s : 0.627148 + pz : 0.200413 p : 0.574496 + px : 0.139094 + py : 0.234989 + dz2 : 0.086513 d : 0.389900 + dxz : 0.054558 + dyz : 0.098234 + dx2y2 : 0.074257 + dxy : 0.076338 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3753 8.0000 -0.3753 1.8166 1.8166 -0.0000 + 1 N 6.6465 7.0000 0.3535 2.5943 2.5943 0.0000 + 2 O 8.2260 8.0000 -0.2260 1.8099 1.8099 -0.0000 + 3 H 0.7522 1.0000 0.2478 0.9971 0.9971 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8028 B( 0-O , 3-H ) : 0.9565 B( 1-N , 2-O ) : 1.7518 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.937 sec +Sum of individual times .... 0.713 sec ( 76.1%) + +Fock matrix formation .... 0.567 sec ( 60.5%) +Diagonalization .... 0.060 sec ( 6.4%) +Density matrix formation .... 0.005 sec ( 0.6%) +Population analysis .... 0.028 sec ( 3.0%) +Initial guess .... 0.010 sec ( 1.1%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.006 sec ( 0.6%) +DIIS solution .... 0.042 sec ( 4.4%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.274 sec +Reference energy ... -204.705120624 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 7.056 sec +AO-integral generation ... 0.169 sec +Half transformation ... 0.095 sec +K-integral sorting ... 5.873 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.029 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.031 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.034 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.041 s ( 0.000 ms/b) + 159120 b 0 skpd 0.020 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.041 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.033 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.025 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.046 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.026 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.393 sec +AO-integral generation ... 0.281 sec +Half transformation ... 0.046 sec +J-integral sorting ... 0.051 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.159 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.259 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090012329 +EMP2(bb)= -0.090012329 +EMP2(ab)= -0.517388286 + +Initial guess performed in 0.137 sec +E(0) ... -204.705120624 +E(MP2) ... -0.697412944 +Initial E(tot) ... -205.402533568 + ... 0.189544955 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.402533568 -0.697412944 -0.000000000 0.019035811 3.66 0.000003656 + *** Turning on DIIS *** + 1 -205.374212266 -0.669091642 0.028321302 0.010715012 4.32 0.055525739 + 2 -205.393753737 -0.688633113 -0.019541471 0.003785926 3.82 0.058242948 + 3 -205.397577698 -0.692457074 -0.003823961 0.002049255 4.52 0.071152282 + 4 -205.399114024 -0.693993400 -0.001536326 0.000942121 4.00 0.076870470 + 5 -205.399596776 -0.694476152 -0.000482752 0.000445022 3.33 0.081101446 + 6 -205.399672878 -0.694552254 -0.000076102 0.000333085 3.31 0.083017417 + 7 -205.399703138 -0.694582515 -0.000030260 0.000247945 3.64 0.083857298 + 8 -205.399709823 -0.694589199 -0.000006685 0.000177053 3.44 0.084230598 + 9 -205.399706822 -0.694586198 0.000003001 0.000116458 4.33 0.084388098 + 10 -205.399711559 -0.694590936 -0.000004738 0.000058850 4.69 0.084475796 + 11 -205.399708044 -0.694587420 0.000003515 0.000025520 3.37 0.084505832 + 12 -205.399710611 -0.694589987 -0.000002567 0.000012810 3.96 0.084522672 + 13 -205.399710722 -0.694590098 -0.000000111 0.000008929 4.69 0.084526121 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.705120624 +E(CORR) ... -0.694590098 +E(TOT) ... -205.399710722 +Singles norm **1/2 ... 0.084526121 ( 0.042263061, 0.042263061) +T1 diagnostic ... 0.019922998 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.060801 + 8a-> 13a 8b-> 13b 0.055968 + 9a-> 13a 8b-> 13b 0.046493 + 8a-> 13a 9b-> 13b 0.046493 + 5a-> 13a 5b-> 13b 0.030076 + 11a-> 13a 11b-> 13b 0.028359 + 8a-> 13a -1a-> -1a 0.028031 + 8b-> 13b -1b-> -1b 0.028031 + 11a-> 24a 11b-> 24b 0.024174 + 9a-> 22a 9b-> 13b 0.023470 + 9a-> 13a 9b-> 22b 0.023470 + 11a-> 25a 11b-> 25b 0.022647 + 11a-> 25a 11b-> 24b 0.022226 + 11a-> 24a 11b-> 25b 0.022226 + 11b-> 24b -1b-> -1b 0.020276 + 11a-> 24a -1a-> -1a 0.020276 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034498967 + alpha-alpha-alpha ... -0.000861010 ( 2.5%) + alpha-alpha-beta ... -0.016388474 ( 47.5%) + alpha-beta -beta ... -0.016388474 ( 47.5%) + beta -beta -beta ... -0.000861010 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034498967 + +Final correlation energy ... -0.729089065 +E(CCSD) ... -205.399710722 +E(CCSD(T)) ... -205.434209689 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210218332 sqrt= 1.100099237 +W(HF) = 0.826297184 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.318344 -0.000000 + 1 N : 0.181782 -0.000000 + 2 O : -0.099536 0.000000 + 3 H : 0.236099 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.840158 s : 3.840158 + pz : 1.638324 p : 4.413188 + px : 1.248342 + py : 1.526522 + dz2 : 0.009517 d : 0.057060 + dxz : 0.010865 + dyz : 0.008847 + dx2y2 : 0.016670 + dxy : 0.011162 + f0 : 0.001181 f : 0.007938 + f+1 : 0.001268 + f-1 : 0.000920 + f+2 : 0.001064 + f-2 : 0.000762 + f+3 : 0.001396 + f-3 : 0.001348 + 1 N s : 3.877546 s : 3.877546 + pz : 0.891617 p : 2.743457 + px : 0.867360 + py : 0.984480 + dz2 : 0.036419 d : 0.167380 + dxz : 0.041887 + dyz : 0.019267 + dx2y2 : 0.041289 + dxy : 0.028519 + f0 : 0.003424 f : 0.029834 + f+1 : 0.005278 + f-1 : 0.002909 + f+2 : 0.003794 + f-2 : 0.004116 + f+3 : 0.004515 + f-3 : 0.005799 + 2 O s : 3.862298 s : 3.862298 + pz : 1.168378 p : 4.143866 + px : 1.691970 + py : 1.283518 + dz2 : 0.025326 d : 0.083533 + dxz : 0.015410 + dyz : 0.014167 + dx2y2 : 0.013087 + dxy : 0.015542 + f0 : 0.001789 f : 0.009840 + f+1 : 0.001205 + f-1 : 0.001512 + f+2 : 0.001460 + f-2 : 0.001619 + f+3 : 0.001185 + f-3 : 0.001070 + 3 H s : 0.651116 s : 0.651116 + pz : 0.041251 p : 0.095502 + px : 0.026210 + py : 0.028041 + dz2 : 0.006261 d : 0.017283 + dxz : 0.003109 + dyz : -0.000014 + dx2y2 : 0.002378 + dxy : 0.005548 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.579004 -0.000000 + 1 N : -0.275822 -0.000000 + 2 O : 0.293230 0.000000 + 3 H : -0.596411 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.140912 s : 3.140912 + pz : 1.374113 p : 3.913178 + px : 1.182287 + py : 1.356778 + dz2 : 0.039594 d : 0.285950 + dxz : 0.062934 + dyz : 0.036644 + dx2y2 : 0.088140 + dxy : 0.058638 + f0 : 0.007295 f : 0.080956 + f+1 : 0.016496 + f-1 : 0.002683 + f+2 : 0.015430 + f-2 : 0.005401 + f+3 : 0.014620 + f-3 : 0.019032 + 1 N s : 3.043592 s : 3.043592 + pz : 0.974011 p : 2.878399 + px : 0.889744 + py : 1.014644 + dz2 : 0.161104 d : 0.925301 + dxz : 0.241677 + dyz : 0.176158 + dx2y2 : 0.198889 + dxy : 0.147473 + f0 : 0.048030 f : 0.428530 + f+1 : 0.065225 + f-1 : 0.055727 + f+2 : 0.074114 + f-2 : 0.066925 + f+3 : 0.055814 + f-3 : 0.062696 + 2 O s : 3.316837 s : 3.316837 + pz : 1.235160 p : 3.904981 + px : 1.408219 + py : 1.261602 + dz2 : 0.063263 d : 0.358962 + dxz : 0.073574 + dyz : 0.118587 + dx2y2 : 0.065237 + dxy : 0.038301 + f0 : 0.017064 f : 0.125991 + f+1 : 0.012907 + f-1 : 0.027719 + f+2 : 0.030818 + f-2 : 0.020830 + f+3 : 0.005849 + f-3 : 0.010804 + 3 H s : 0.627465 s : 0.627465 + pz : 0.208223 p : 0.589192 + px : 0.138722 + py : 0.242248 + dz2 : 0.083690 d : 0.379754 + dxz : 0.052332 + dyz : 0.096966 + dx2y2 : 0.073015 + dxy : 0.073752 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3183 8.0000 -0.3183 2.1589 1.6962 0.4627 + 1 N 6.8182 7.0000 0.1818 2.8558 2.3612 0.4946 + 2 O 8.0995 8.0000 -0.0995 2.1937 1.6956 0.4982 + 3 H 0.7639 1.0000 0.2361 1.0176 0.9429 0.0747 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7142 B( 0-O , 3-H ) : 0.8939 B( 1-N , 2-O ) : 1.6027 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 72.829 sec + +Fock Matrix Formation ... 0.274 sec ( 0.4%) +Initial Guess ... 0.137 sec ( 0.2%) +DIIS Solver ... 3.027 sec ( 4.2%) +State Vector Update ... 0.125 sec ( 0.2%) +Sigma-vector construction ... 51.930 sec ( 71.3%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.028 sec ( 0.1% of sigma) + (0-ext) ... 0.080 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.030 sec ( 0.1% of sigma) + (2-ext) ... 1.087 sec ( 2.1% of sigma) + (4-ext) ... 31.596 sec ( 60.8% of sigma) + ... 2.195 sec ( 4.2% of sigma) + ... 0.003 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.141 sec ( 0.3% of sigma) + Fock-dressing ... 2.396 sec ( 4.6% of sigma) + (ik|jl)-dressing ... 0.086 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 11.477 sec ( 22.1% of sigma) + Pair energies ... 0.012 sec ( 0.0% of sigma) +Total Time for computing (T) ... 8.460 sec ( 11.6% of ALL) + I/O of integral and amplitudes ... 0.901 sec ( 10.7% of (T)) + External N**7 contributions ... 4.620 sec ( 54.6% of (T)) + Internal N**7 contributions ... 0.370 sec ( 4.4% of (T)) + N**6 triples energy contributions ... 1.934 sec ( 22.9% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.434209688798 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.013.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.013.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.395707, -0.257996 -0.520775) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 1.04124 -0.15210 -0.65542 +Nuclear contribution : -0.89367 0.58971 1.08627 + ----------------------------------------- +Total Dipole Moment : 0.14757 0.43762 0.43085 + ----------------------------------------- +Magnitude (a.u.) : 0.63160 +Magnitude (Debye) : 1.60540 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.710731 0.399824 0.360321 +Rotational constants in MHz : 81265.671383 11986.416352 10802.150872 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.059321 0.062100 0.625734 +x,y,z [Debye]: -0.150783 0.157845 1.590489 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.395707, -0.257996 -0.520775) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 1.09057 -0.09823 -0.81166 +Nuclear contribution : -0.89367 0.58971 1.08627 + ----------------------------------------- +Total Dipole Moment : 0.19690 0.49148 0.27461 + ----------------------------------------- +Magnitude (a.u.) : 0.59644 +Magnitude (Debye) : 1.51602 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.710731 0.399824 0.360321 +Rotational constants in MHz : 81265.671383 11986.416352 10802.150872 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.081530 0.146184 0.572467 +x,y,z [Debye]: 0.207232 0.371569 1.455095 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 14 * + * * + * Dihedral ( 2, 1, 0, 3) : -73.63636364 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0385366763 RMS(Int)= 0.0006582361 + Iter 1: RMS(Cart)= 0.0001776351 RMS(Int)= 0.0000074568 + Iter 2: RMS(Cart)= 0.0000020123 RMS(Int)= 0.0000000848 + Iter 3: RMS(Cart)= 0.0000000229 RMS(Int)= 0.0000000010 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.5044 0.000000 + 2. B(O 2,N 1) 1.1675 0.000000 + 3. B(H 3,O 0) 0.9725 0.000000 + 4. A(N 1,O 0,H 3) 103.1866 0.000000 + 5. A(O 0,N 1,O 2) 111.1894 0.000000 + 6. D(O 2,N 1,O 0,H 3) -73.6364 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.786582 -0.299801 0.318372 + N 0.624182 -0.491684 -0.167438 + O 0.891714 0.279713 -1.002022 + H -0.729313 0.511773 0.851088 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.486424 -0.566542 0.601635 + 1 N 7.0000 0 14.007 1.179533 -0.929148 -0.316411 + 2 O 8.0000 0 15.999 1.685095 0.528580 -1.893547 + 3 H 1.0000 0 1.008 -1.378203 0.967110 1.608323 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.503797504027 0.00000000 0.00000000 + O 2 1 0 1.165681146687 111.29949237 0.00000000 + H 1 2 3 0.969902010152 103.30239386 278.18181822 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.841765443484 0.00000000 0.00000000 + O 2 1 0 2.202818126714 111.29949237 0.00000000 + H 1 2 3 1.832849175926 103.30239386 278.18181822 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2231 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2701 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.332758732233 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.3327587322 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.788e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7005555856 0.000000000000 0.00162908 0.00005053 0.0190042 0.7000 + 1 -204.7014296796 -0.000874094024 0.00154448 0.00004654 0.0157733 0.7000 + ***Turning on DIIS*** + 2 -204.7021828402 -0.000753160602 0.00433864 0.00012839 0.0128611 0.0000 + 3 -204.7065694355 -0.004386595289 0.00203937 0.00005944 0.0050026 0.0000 + 4 -204.7037901498 0.002779285729 0.00095708 0.00003129 0.0019489 0.0000 + 5 -204.7059173115 -0.002127161738 0.00088409 0.00002714 0.0011456 0.0000 + 6 -204.7047738389 0.001143472623 0.00097684 0.00003183 0.0006684 0.0000 + 7 -204.7047088685 0.000064970399 0.00035096 0.00001403 0.0002678 0.0000 + 8 -204.7053869128 -0.000678044327 0.00019541 0.00000851 0.0001714 0.0000 + 9 -204.7048792106 0.000507702215 0.00015485 0.00000644 0.0001134 0.0000 + 10 -204.7051487687 -0.000269558062 0.00005726 0.00000234 0.0000454 0.0000 + 11 -204.7051179509 0.000030817771 0.00001633 0.00000044 0.0000260 0.0000 + 12 -204.7050792520 0.000038698871 0.00000656 0.00000024 0.0000130 0.0000 + 13 -204.7051078145 -0.000028562482 0.00000235 0.00000009 0.0000032 0.0000 + 14 -204.7051014518 0.000006362704 0.00000120 0.00000004 0.0000027 0.0000 + 15 -204.7051029025 -0.000001450666 0.00000089 0.00000003 0.0000016 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 16 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70510482 Eh -5570.30909 eV + +Components: +Nuclear Repulsion : 68.33275873 Eh 1859.42890 eV +Electronic Energy : -273.03786355 Eh -7429.73799 eV +One Electron Energy: -416.35973224 Eh -11329.72431 eV +Two Electron Energy: 143.32186869 Eh 3899.98632 eV + +Virial components: +Potential Energy : -408.91814365 Eh -11127.22839 eV +Kinetic Energy : 204.21303883 Eh 5556.91930 eV +Virial Ratio : 2.00240957 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.9148e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.9795e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.0886e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.9089e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.692310 -563.0664 + 1 1.0000 -20.618081 -561.0465 + 2 1.0000 -15.807046 -430.1316 + 3 1.0000 -1.617296 -44.0089 + 4 1.0000 -1.371190 -37.3120 + 5 1.0000 -0.957070 -26.0432 + 6 1.0000 -0.766120 -20.8472 + 7 1.0000 -0.734822 -19.9955 + 8 1.0000 -0.698787 -19.0150 + 9 1.0000 -0.605072 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2.5027 + 15 0.0000 0.105119 2.8604 + 16 0.0000 0.113283 3.0826 + 17 0.0000 0.155484 4.2309 + 18 0.0000 0.157419 4.2836 + 19 0.0000 0.174042 4.7359 + 20 0.0000 0.178474 4.8565 + 21 0.0000 0.189958 5.1690 + 22 0.0000 0.201177 5.4743 + 23 0.0000 0.234601 6.3838 + 24 0.0000 0.268596 7.3089 + 25 0.0000 0.285786 7.7766 + 26 0.0000 0.304597 8.2885 + 27 0.0000 0.331907 9.0316 + 28 0.0000 0.336308 9.1514 + 29 0.0000 0.353482 9.6187 + 30 0.0000 0.423824 11.5328 + 31 0.0000 0.508070 13.8253 + 32 0.0000 0.530842 14.4450 + 33 0.0000 0.542200 14.7540 + 34 0.0000 0.562101 15.2955 + 35 0.0000 0.600021 16.3274 + 36 0.0000 0.631678 17.1888 + 37 0.0000 0.644808 17.5461 + 38 0.0000 0.707195 19.2437 + 39 0.0000 0.717701 19.5296 + 40 0.0000 0.733557 19.9611 + 41 0.0000 0.752398 20.4738 + 42 0.0000 0.763891 20.7865 + 43 0.0000 0.787413 21.4266 + 44 0.0000 0.808330 21.9958 + 45 0.0000 0.819886 22.3102 + 46 0.0000 0.856728 23.3127 + 47 0.0000 0.878535 23.9062 + 48 0.0000 0.894897 24.3514 + 49 0.0000 0.958475 26.0814 + 50 0.0000 0.963443 26.2166 + 51 0.0000 0.974502 26.5176 + 52 0.0000 0.989204 26.9176 + 53 0.0000 1.025032 27.8925 + 54 0.0000 1.044494 28.4221 + 55 0.0000 1.094701 29.7883 + 56 0.0000 1.155235 31.4355 + 57 0.0000 1.217503 33.1299 + 58 0.0000 1.234248 33.5856 + 59 0.0000 1.272416 34.6242 + 60 0.0000 1.320681 35.9376 + 61 0.0000 1.409412 38.3521 + 62 0.0000 1.466734 39.9118 + 63 0.0000 1.510781 41.1105 + 64 0.0000 1.528229 41.5852 + 65 0.0000 1.579364 42.9767 + 66 0.0000 1.590753 43.2866 + 67 0.0000 1.630863 44.3780 + 68 0.0000 1.651138 44.9297 + 69 0.0000 1.729489 47.0618 + 70 0.0000 1.748552 47.5805 + 71 0.0000 1.777442 48.3666 + 72 0.0000 1.910608 51.9903 + 73 0.0000 1.925624 52.3989 + 74 0.0000 1.969380 53.5896 + 75 0.0000 2.007470 54.6260 + 76 0.0000 2.041337 55.5476 + 77 0.0000 2.089820 56.8669 + 78 0.0000 2.139347 58.2146 + 79 0.0000 2.189034 59.5666 + 80 0.0000 2.269991 61.7696 + 81 0.0000 2.299403 62.5699 + 82 0.0000 2.331465 63.4424 + 83 0.0000 2.358036 64.1654 + 84 0.0000 2.410080 65.5816 + 85 0.0000 2.452616 66.7391 + 86 0.0000 2.467389 67.1411 + 87 0.0000 2.476218 67.3813 + 88 0.0000 2.512423 68.3665 + 89 0.0000 2.559315 69.6425 + 90 0.0000 2.595196 70.6189 + 91 0.0000 2.598864 70.7187 + 92 0.0000 2.661081 72.4117 + 93 0.0000 2.699756 73.4641 + 94 0.0000 2.743908 74.6655 + 95 0.0000 2.772733 75.4499 + 96 0.0000 2.835128 77.1478 + 97 0.0000 2.914903 79.3186 + 98 0.0000 2.958446 80.5034 + 99 0.0000 2.973785 80.9208 + 100 0.0000 3.073935 83.6460 + 101 0.0000 3.169423 86.2444 + 102 0.0000 3.222026 87.6758 + 103 0.0000 3.482553 94.7651 + 104 0.0000 3.706913 100.8702 + 105 0.0000 3.823304 104.0374 + 106 0.0000 4.039346 109.9162 + 107 0.0000 4.164919 113.3332 + 108 0.0000 4.206149 114.4551 + 109 0.0000 4.280657 116.4826 + 110 0.0000 4.366047 118.8062 + 111 0.0000 4.389278 119.4383 + 112 0.0000 4.533552 123.3642 + 113 0.0000 4.613721 125.5457 + 114 0.0000 4.659003 126.7779 + 115 0.0000 4.719557 128.4257 + 116 0.0000 4.831991 131.4852 + 117 0.0000 4.887696 133.0010 + 118 0.0000 4.927650 134.0882 + 119 0.0000 4.957850 134.9100 + 120 0.0000 5.049316 137.3989 + 121 0.0000 5.104028 138.8877 + 122 0.0000 5.179794 140.9494 + 123 0.0000 5.197364 141.4275 + 124 0.0000 5.238591 142.5493 + 125 0.0000 5.295350 144.0938 + 126 0.0000 5.388072 146.6169 + 127 0.0000 5.488041 149.3372 + 128 0.0000 5.517799 150.1469 + 129 0.0000 5.696164 155.0005 + 130 0.0000 5.741995 156.2476 + 131 0.0000 5.938434 161.5930 + 132 0.0000 6.169634 167.8843 + 133 0.0000 6.409193 174.4030 + 134 0.0000 6.479290 176.3104 + 135 0.0000 6.508428 177.1033 + 136 0.0000 6.692720 182.1182 + 137 0.0000 6.715255 182.7314 + 138 0.0000 6.776711 184.4037 + 139 0.0000 6.816297 185.4809 + 140 0.0000 6.837329 186.0532 + 141 0.0000 7.061437 192.1515 + 142 0.0000 7.105005 193.3370 + 143 0.0000 7.114788 193.6032 + 144 0.0000 7.202186 195.9815 + 145 0.0000 7.255125 197.4220 + 146 0.0000 7.275269 197.9701 + 147 0.0000 7.332489 199.5272 + 148 0.0000 7.380182 200.8250 + 149 0.0000 7.452697 202.7982 + 150 0.0000 7.467817 203.2096 + 151 0.0000 7.554042 205.5559 + 152 0.0000 7.574181 206.1040 + 153 0.0000 7.637464 207.8260 + 154 0.0000 7.683018 209.0655 + 155 0.0000 7.893078 214.7816 + 156 0.0000 7.935912 215.9471 + 157 0.0000 8.385764 228.1883 + 158 0.0000 14.028566 381.7367 + 159 0.0000 14.825215 403.4146 + 160 0.0000 16.049455 436.7279 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.376258 0.000000 + 1 N : 0.354572 0.000000 + 2 O : -0.228921 0.000000 + 3 H : 0.250606 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.859143 s : 3.859143 + pz : 1.691805 p : 4.485558 + px : 1.272341 + py : 1.521412 + dz2 : 0.002456 d : 0.027367 + dxz : 0.005009 + dyz : 0.002401 + dx2y2 : 0.013379 + dxy : 0.004122 + f0 : 0.000718 f : 0.004191 + f+1 : 0.000782 + f-1 : 0.000194 + f+2 : 0.000549 + f-2 : 0.000110 + f+3 : 0.001015 + f-3 : 0.000822 + 1 N s : 3.825716 s : 3.825716 + pz : 0.837471 p : 2.649630 + px : 0.810615 + py : 1.001544 + dz2 : 0.034940 d : 0.139044 + dxz : 0.031380 + dyz : 0.015066 + dx2y2 : 0.036525 + dxy : 0.021133 + f0 : 0.003565 f : 0.031037 + f+1 : 0.004825 + f-1 : 0.003479 + f+2 : 0.003814 + f-2 : 0.004509 + f+3 : 0.004883 + f-3 : 0.005963 + 2 O s : 3.875901 s : 3.875901 + pz : 1.193417 p : 4.283402 + px : 1.764805 + py : 1.325180 + dz2 : 0.024349 d : 0.062131 + dxz : 0.007637 + dyz : 0.010572 + dx2y2 : 0.007866 + dxy : 0.011707 + f0 : 0.001450 f : 0.007486 + f+1 : 0.000506 + f-1 : 0.001598 + f+2 : 0.001192 + f-2 : 0.001271 + f+3 : 0.000814 + f-3 : 0.000655 + 3 H s : 0.642000 s : 0.642000 + pz : 0.038674 p : 0.087482 + px : 0.023094 + py : 0.025713 + dz2 : 0.006071 d : 0.019912 + dxz : 0.002475 + dyz : 0.001613 + dx2y2 : 0.002842 + dxy : 0.006910 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.571499 0.000000 + 1 N : -0.230783 0.000000 + 2 O : 0.248440 0.000000 + 3 H : -0.589156 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.138713 s : 3.138713 + pz : 1.403937 p : 3.960574 + px : 1.188387 + py : 1.368250 + dz2 : 0.032860 d : 0.255213 + dxz : 0.057755 + dyz : 0.028904 + dx2y2 : 0.081011 + dxy : 0.054684 + f0 : 0.006649 f : 0.074002 + f+1 : 0.015553 + f-1 : 0.001245 + f+2 : 0.013712 + f-2 : 0.005204 + f+3 : 0.012464 + f-3 : 0.019175 + 1 N s : 3.040278 s : 3.040278 + pz : 0.922207 p : 2.835899 + px : 0.861172 + py : 1.052520 + dz2 : 0.156283 d : 0.916221 + dxz : 0.231338 + dyz : 0.170879 + dx2y2 : 0.203406 + dxy : 0.154315 + f0 : 0.043999 f : 0.438385 + f+1 : 0.061228 + f-1 : 0.054233 + f+2 : 0.078033 + f-2 : 0.074181 + f+3 : 0.058882 + f-3 : 0.067829 + 2 O s : 3.313246 s : 3.313246 + pz : 1.227758 p : 3.990358 + px : 1.454163 + py : 1.308437 + dz2 : 0.047868 d : 0.330699 + dxz : 0.065271 + dyz : 0.113399 + dx2y2 : 0.067734 + dxy : 0.036426 + f0 : 0.012442 f : 0.117258 + f+1 : 0.009984 + f-1 : 0.024400 + f+2 : 0.031549 + f-2 : 0.020463 + f+3 : 0.005557 + f-3 : 0.012863 + 3 H s : 0.625913 s : 0.625913 + pz : 0.191951 p : 0.572580 + px : 0.139495 + py : 0.241133 + dz2 : 0.078077 d : 0.390664 + dxz : 0.048008 + dyz : 0.100530 + dx2y2 : 0.079727 + dxy : 0.084322 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3763 8.0000 -0.3763 1.8168 1.8168 -0.0000 + 1 N 6.6454 7.0000 0.3546 2.5917 2.5917 0.0000 + 2 O 8.2289 8.0000 -0.2289 1.8038 1.8038 -0.0000 + 3 H 0.7494 1.0000 0.2506 0.9970 0.9970 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8049 B( 0-O , 3-H ) : 0.9533 B( 1-N , 2-O ) : 1.7441 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.899 sec +Sum of individual times .... 2.673 sec ( 92.2%) + +Fock matrix formation .... 2.237 sec ( 77.2%) +Diagonalization .... 0.208 sec ( 7.2%) +Density matrix formation .... 0.015 sec ( 0.5%) +Population analysis .... 0.032 sec ( 1.1%) +Initial guess .... 0.011 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.006 sec ( 0.2%) +DIIS solution .... 0.171 sec ( 5.9%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.246 sec +Reference energy ... -204.705104136 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 7.401 sec +AO-integral generation ... 0.163 sec +Half transformation ... 0.090 sec +K-integral sorting ... 6.073 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.035 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.034 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.035 s ( 0.000 ms/b) + 151164 b 0 skpd 0.039 s ( 0.000 ms/b) +: 159120 b 0 skpd 0.023 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.040 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.035 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.047 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.030 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.424 sec +AO-integral generation ... 0.300 sec +Half transformation ... 0.050 sec +J-integral sorting ... 0.058 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.221 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.310 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090139056 +EMP2(bb)= -0.090139056 +EMP2(ab)= -0.517865092 + +Initial guess performed in 0.138 sec +E(0) ... -204.705104136 +E(MP2) ... -0.698143204 +Initial E(tot) ... -205.403247340 + ... 0.190119948 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.403247340 -0.698143204 -0.000000000 0.019565110 3.54 0.000002602 + *** Turning on DIIS *** + 1 -205.374546324 -0.669442188 0.028701016 0.010198276 3.45 0.056057012 + 2 -205.394205899 -0.689101763 -0.019659576 0.003945031 3.51 0.058792371 + 3 -205.398048406 -0.692944270 -0.003842507 0.001927906 3.32 0.071988326 + 4 -205.399604014 -0.694499878 -0.001555608 0.000951194 3.32 0.077927484 + 5 -205.400105709 -0.695001573 -0.000501695 0.000554575 3.35 0.082465184 + 6 -205.400190027 -0.695085891 -0.000084318 0.000351715 3.47 0.084638042 + 7 -205.400225758 -0.695121622 -0.000035731 0.000241566 3.57 0.085668001 + 8 -205.400234681 -0.695130545 -0.000008923 0.000164730 4.32 0.086150851 + 9 -205.400231531 -0.695127395 0.000003150 0.000102886 4.53 0.086348774 + 10 -205.400236943 -0.695132808 -0.000005413 0.000054023 3.95 0.086441508 + 11 -205.400233283 -0.695129147 0.000003660 0.000029839 3.66 0.086460465 + 12 -205.400235960 -0.695131824 -0.000002677 0.000017149 3.58 0.086476930 + 13 -205.400235824 -0.695131688 0.000000136 0.000009526 3.84 0.086478977 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.705104136 +E(CORR) ... -0.695131688 +E(TOT) ... -205.400235824 +Singles norm **1/2 ... 0.086478977 ( 0.043239488, 0.043239488) +T1 diagnostic ... 0.020383290 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.058044 + 8a-> 13a 8b-> 13b 0.057167 + 9a-> 13a 8b-> 13b 0.045314 + 8a-> 13a 9b-> 13b 0.045314 + 5a-> 13a 5b-> 13b 0.030041 + 8a-> 13a -1a-> -1a 0.029288 + 8b-> 13b -1b-> -1b 0.029288 + 11a-> 13a 11b-> 13b 0.028339 + 11a-> 24a 11b-> 24b 0.023286 + 9a-> 13a 9b-> 22b 0.022290 + 9a-> 22a 9b-> 13b 0.022290 + 11a-> 25a 11b-> 24b 0.021076 + 11a-> 24a 11b-> 25b 0.021076 + 11a-> 25a 11b-> 25b 0.021030 + 11a-> 24a -1a-> -1a 0.020445 + 11b-> 24b -1b-> -1b 0.020445 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034690172 + alpha-alpha-alpha ... -0.000867229 ( 2.5%) + alpha-alpha-beta ... -0.016477857 ( 47.5%) + alpha-beta -beta ... -0.016477857 ( 47.5%) + beta -beta -beta ... -0.000867229 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034690172 + +Final correlation energy ... -0.729821860 +E(CCSD) ... -205.400235824 +E(CCSD(T)) ... -205.434925996 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.211344289 sqrt= 1.100610871 +W(HF) = 0.825529133 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.316801 -0.000000 + 1 N : 0.181002 0.000000 + 2 O : -0.102580 -0.000000 + 3 H : 0.238380 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.839383 s : 3.839383 + pz : 1.659933 p : 4.411378 + px : 1.256707 + py : 1.494737 + dz2 : 0.009476 d : 0.058108 + dxz : 0.011331 + dyz : 0.008746 + dx2y2 : 0.017198 + dxy : 0.011356 + f0 : 0.001230 f : 0.007933 + f+1 : 0.001299 + f-1 : 0.000843 + f+2 : 0.001068 + f-2 : 0.000779 + f+3 : 0.001368 + f-3 : 0.001346 + 1 N s : 3.879326 s : 3.879326 + pz : 0.875941 p : 2.741762 + px : 0.859615 + py : 1.006206 + dz2 : 0.036177 d : 0.167938 + dxz : 0.041456 + dyz : 0.019844 + dx2y2 : 0.042434 + dxy : 0.028028 + f0 : 0.003184 f : 0.029973 + f+1 : 0.004945 + f-1 : 0.003058 + f+2 : 0.003651 + f-2 : 0.004376 + f+3 : 0.004818 + f-3 : 0.005942 + 2 O s : 3.862683 s : 3.862683 + pz : 1.169673 p : 4.146808 + px : 1.682207 + py : 1.294928 + dz2 : 0.024776 d : 0.083236 + dxz : 0.014444 + dyz : 0.013778 + dx2y2 : 0.013618 + dxy : 0.016620 + f0 : 0.001582 f : 0.009854 + f+1 : 0.001063 + f-1 : 0.001620 + f+2 : 0.001519 + f-2 : 0.001626 + f+3 : 0.001294 + f-3 : 0.001150 + 3 H s : 0.650097 s : 0.650097 + pz : 0.042959 p : 0.094436 + px : 0.026461 + py : 0.025017 + dz2 : 0.005491 d : 0.017087 + dxz : 0.002377 + dyz : 0.000887 + dx2y2 : 0.002145 + dxy : 0.006187 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.577540 0.000000 + 1 N : -0.275167 -0.000000 + 2 O : 0.291366 -0.000000 + 3 H : -0.593739 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.143250 s : 3.143250 + pz : 1.378299 p : 3.911907 + px : 1.187166 + py : 1.346443 + dz2 : 0.038639 d : 0.286331 + dxz : 0.064157 + dyz : 0.036073 + dx2y2 : 0.087567 + dxy : 0.059894 + f0 : 0.007816 f : 0.080971 + f+1 : 0.016044 + f-1 : 0.001876 + f+2 : 0.015260 + f-2 : 0.006147 + f+3 : 0.014107 + f-3 : 0.019722 + 1 N s : 3.045159 s : 3.045159 + pz : 0.943076 p : 2.877901 + px : 0.883584 + py : 1.051241 + dz2 : 0.154578 d : 0.923024 + dxz : 0.232949 + dyz : 0.177158 + dx2y2 : 0.206974 + dxy : 0.151365 + f0 : 0.044052 f : 0.429083 + f+1 : 0.058712 + f-1 : 0.054511 + f+2 : 0.075469 + f-2 : 0.070925 + f+3 : 0.059658 + f-3 : 0.065756 + 2 O s : 3.315928 s : 3.315928 + pz : 1.214224 p : 3.907768 + px : 1.401968 + py : 1.291576 + dz2 : 0.057264 d : 0.359249 + dxz : 0.069257 + dyz : 0.117915 + dx2y2 : 0.072741 + dxy : 0.042072 + f0 : 0.015214 f : 0.125690 + f+1 : 0.010802 + f-1 : 0.026578 + f+2 : 0.031400 + f-2 : 0.021637 + f+3 : 0.006946 + f-3 : 0.013112 + 3 H s : 0.626555 s : 0.626555 + pz : 0.199703 p : 0.586903 + px : 0.139139 + py : 0.248060 + dz2 : 0.075658 d : 0.380282 + dxz : 0.046078 + dyz : 0.098745 + dx2y2 : 0.078343 + dxy : 0.081458 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3168 8.0000 -0.3168 2.1654 1.7010 0.4644 + 1 N 6.8190 7.0000 0.1810 2.8558 2.3607 0.4951 + 2 O 8.1026 8.0000 -0.1026 2.1894 1.6906 0.4989 + 3 H 0.7616 1.0000 0.2384 1.0172 0.9422 0.0750 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7198 B( 0-O , 3-H ) : 0.8902 B( 1-N , 2-O ) : 1.5942 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 70.872 sec + +Fock Matrix Formation ... 0.246 sec ( 0.3%) +Initial Guess ... 0.138 sec ( 0.2%) +DIIS Solver ... 2.540 sec ( 3.6%) +State Vector Update ... 0.121 sec ( 0.2%) +Sigma-vector construction ... 48.757 sec ( 68.8%) + <0|H|D> ... 0.005 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (0-ext) ... 0.087 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.031 sec ( 0.1% of sigma) + (2-ext) ... 1.143 sec ( 2.3% of sigma) + (4-ext) ... 27.988 sec ( 57.4% of sigma) + ... 1.962 sec ( 4.0% of sigma) + ... 0.003 sec ( 0.0% of sigma) + (1-ext) ... 0.010 sec ( 0.0% of sigma) + (1-ext) ... 0.131 sec ( 0.3% of sigma) + Fock-dressing ... 2.552 sec ( 5.2% of sigma) + (ik|jl)-dressing ... 0.089 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 11.933 sec ( 24.5% of sigma) + Pair energies ... 0.008 sec ( 0.0% of sigma) +Total Time for computing (T) ... 9.717 sec ( 13.7% of ALL) + I/O of integral and amplitudes ... 1.016 sec ( 10.5% of (T)) + External N**7 contributions ... 4.633 sec ( 47.7% of (T)) + Internal N**7 contributions ... 0.377 sec ( 3.9% of (T)) + N**6 triples energy contributions ... 1.914 sec ( 19.7% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.434925995848 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.003493070 0.000950487 -0.005831424 + 2 N : 0.004269975 0.000046978 0.004961891 + 3 O : -0.002072796 -0.000604815 -0.003513689 + 4 H : 0.001295891 -0.000392651 0.004383222 + +Norm of the cartesian gradient ... 0.011314599 +RMS gradient ... 0.003266244 +MAX gradient ... 0.005831424 + +------- +TIMINGS +------- + +Total numerical gradient time ... 417.243 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: -508.03 cm**-1 ***imaginary mode*** + 7: 544.74 cm**-1 + 8: 764.27 cm**-1 + 9: 1151.59 cm**-1 + 10: 1701.02 cm**-1 + 11: 3707.67 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 -0.045469 0.544619 0.168763 -0.050350 -0.066542 -0.002928 + 1 0.031545 0.100614 -0.151023 -0.051058 0.027650 -0.052101 + 2 -0.056854 -0.381849 0.086693 -0.000601 0.016004 -0.034659 + 3 0.054903 -0.257274 -0.495856 -0.039924 -0.060879 0.000098 + 4 0.047328 -0.097757 0.245043 0.047024 -0.526062 -0.000121 + 5 0.048183 0.254287 0.022772 0.036755 0.503570 -0.000409 + 6 -0.014425 -0.350277 0.295431 0.024566 0.131456 -0.000484 + 7 -0.038408 -0.008076 -0.042517 0.007150 0.433018 -0.000270 + 8 -0.035999 0.163598 -0.134007 -0.016464 -0.462465 0.000536 + 9 0.187721 0.490436 -0.477370 0.964023 -0.184359 0.052782 + 10 -0.548742 -0.110350 -0.333200 0.043479 -0.001669 0.832919 + 11 0.804234 -0.069448 0.434521 -0.239886 0.088720 0.547298 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 7: 544.74 0.023969 121.13 0.013731 (-0.088606 -0.017414 0.074680) + 8: 764.27 0.032180 162.63 0.013140 (-0.097777 0.005680 0.059557) + 9: 1151.59 0.005327 26.92 0.001443 ( 0.031527 -0.014487 -0.015478) + 10: 1701.02 0.034509 174.40 0.006331 (-0.059239 -0.015980 0.050659) + 11: 3707.67 0.010478 52.95 0.000882 (-0.011825 0.017798 0.020624) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 7 +The total number of vibrations considered is 5 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 544.74 E(vib) ... 0.12 +freq. 764.27 E(vib) ... 0.06 +freq. 1151.59 E(vib) ... 0.01 +freq. 1701.02 E(vib) ... 0.00 +freq. 3707.67 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.43492600 Eh +Zero point energy ... 0.01792758 Eh 11.25 kcal/mol +Thermal vibrational correction ... 0.00030488 Eh 0.19 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.41386099 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00313743 Eh 1.97 kcal/mol +Non-thermal (ZPE) correction 0.01792758 Eh 11.25 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02106500 Eh 13.22 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.41386099 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.41291678 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.673551 0.401708 0.360311 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00040386 Eh 0.25 kcal/mol +Rotational entropy ... 0.00995902 Eh 6.25 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02816520 Eh 17.67 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00995902 Eh 6.25 kcal/mol| +| sn= 2 | S(rot)= 0.00930456 Eh 5.84 kcal/mol| +| sn= 3 | S(rot)= 0.00892173 Eh 5.60 kcal/mol| +| sn= 4 | S(rot)= 0.00865010 Eh 5.43 kcal/mol| +| sn= 5 | S(rot)= 0.00843942 Eh 5.30 kcal/mol| +| sn= 6 | S(rot)= 0.00826727 Eh 5.19 kcal/mol| +| sn= 7 | S(rot)= 0.00812173 Eh 5.10 kcal/mol| +| sn= 8 | S(rot)= 0.00799565 Eh 5.02 kcal/mol| +| sn= 9 | S(rot)= 0.00788444 Eh 4.95 kcal/mol| +| sn=10 | S(rot)= 0.00778496 Eh 4.89 kcal/mol| +| sn=11 | S(rot)= 0.00769497 Eh 4.83 kcal/mol| +| sn=12 | S(rot)= 0.00761282 Eh 4.78 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.41291678 Eh +Total entropy correction ... -0.02816520 Eh -17.67 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44108198 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00615599 Eh -3.86 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.434925995 Eh +Current gradient norm .... 0.011314768 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + -0.028176648 0.091994067 0.166223446 0.468017941 0.498435825 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999756403 +Lowest eigenvalues of augmented Hessian: + -0.000071130 0.089937347 0.166186408 0.467504052 0.498422226 +Length of the computed step .... 0.022076508 +The final length of the internal step .... 0.022076508 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0090126965 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0046938071 RMS(Int)= 0.0090116070 + Iter 1: RMS(Cart)= 0.0000263920 RMS(Int)= 0.0000382262 + Iter 2: RMS(Cart)= 0.0000001839 RMS(Int)= 0.0000002310 + Iter 3: RMS(Cart)= 0.0000000017 RMS(Int)= 0.0000000020 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000003 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0018395966 0.0001000000 NO + MAX gradient 0.0031342490 0.0003000000 NO + RMS step 0.0090126965 0.0020000000 NO + MAX step 0.0175969352 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0093 Max(Angles) 0.54 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.5044 0.001664 -0.0093 1.4950 + 2. B(O 2,N 1) 1.1675 0.001637 -0.0001 1.1674 + 3. B(H 3,O 0) 0.9725 0.002150 -0.0023 0.9702 + 4. A(N 1,O 0,H 3) 103.19 -0.000641 0.54 103.73 + 5. A(O 0,N 1,O 2) 111.19 -0.003134 0.48 111.67 + 6. D(O 2,N 1,O 0,H 3) -73.64 -0.007222 0.00 -73.64 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.781491 -0.298674 0.318614 + N 0.619338 -0.489587 -0.167582 + O 0.893980 0.278127 -1.003112 + H -0.731826 0.510133 0.852081 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.476804 -0.564411 0.602093 + 1 N 7.0000 0 14.007 1.170379 -0.925184 -0.316684 + 2 O 8.0000 0 15.999 1.689377 0.525584 -1.895608 + 3 H 1.0000 0 1.008 -1.382950 0.964012 1.610199 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.495043391629 0.00000000 0.00000000 + O 2 1 0 1.167443035339 111.66620708 0.00000000 + H 1 2 3 0.970165906639 103.72803202 286.36363663 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.825222568507 0.00000000 0.00000000 + O 2 1 0 2.206147613745 111.66620708 0.00000000 + H 1 2 3 1.833347868016 103.72803202 286.36363663 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2230 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2699 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 535 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.481795569085 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.771e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7060391140 0.000000000000 0.00027441 0.00000853 0.0014212 0.7000 + 1 -204.7060566011 -0.000017487052 0.00021507 0.00000705 0.0011650 0.7000 + ***Turning on DIIS*** + 2 -204.7060711121 -0.000014511050 0.00055231 0.00001855 0.0009377 0.0000 + 3 -204.7057932425 0.000277869640 0.00019471 0.00000759 0.0003119 0.0000 + 4 -204.7062331492 -0.000439906689 0.00004353 0.00000230 0.0000759 0.0000 + 5 -204.7062404381 -0.000007288948 0.00002924 0.00000107 0.0000575 0.0000 + 6 -204.7059832823 0.000257155874 0.00002151 0.00000086 0.0000435 0.0000 + 7 -204.7061451838 -0.000161901518 0.00001518 0.00000070 0.0000172 0.0000 + 8 -204.7060951421 0.000050041657 0.00001409 0.00000059 0.0000105 0.0000 + 9 -204.7061129700 -0.000017827866 0.00000760 0.00000030 0.0000045 0.0000 + 10 -204.7061284525 -0.000015482513 0.00000237 0.00000009 0.0000022 0.0000 + 11 -204.7061124034 0.000016049094 0.00000092 0.00000003 0.0000013 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + +Total Energy : -204.70611890 Eh -5570.33669 eV + Last Energy change ... -6.4996e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.2203e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.211 sec +Reference energy ... -204.706118624 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.367 sec +AO-integral generation ... 0.143 sec +Half transformation ... 0.080 sec +K-integral sorting ... 5.366 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.027 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.027 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.351 sec +AO-integral generation ... 0.246 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.051 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.155 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.253 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090021612 +EMP2(bb)= -0.090021612 +EMP2(ab)= -0.517072148 + +Initial guess performed in 0.134 sec +E(0) ... -204.706118624 +E(MP2) ... -0.697115372 +Initial E(tot) ... -205.403233996 + ... 0.189174446 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.403233996 -0.697115372 -0.000000000 0.019610358 2.90 0.000000674 + *** Turning on DIIS *** + 1 -205.374977788 -0.668859165 0.028256207 0.010313212 2.92 0.055732766 + 2 -205.394486956 -0.688368333 -0.019509168 0.003973490 2.91 0.058540603 + 3 -205.398302357 -0.692183733 -0.003815400 0.001949900 2.90 0.071663308 + 4 -205.399843613 -0.693724989 -0.001541256 0.000859395 2.98 0.077577954 + 5 -205.400339115 -0.694220491 -0.000495502 0.000540183 3.18 0.082079256 + 6 -205.400422767 -0.694304144 -0.000083653 0.000342339 3.03 0.084226409 + 7 -205.400457804 -0.694339181 -0.000035037 0.000245309 3.18 0.085227808 + 8 -205.400466345 -0.694347721 -0.000008541 0.000167263 3.10 0.085695602 + 9 -205.400463340 -0.694344717 0.000003005 0.000103888 3.06 0.085891220 + 10 -205.400468588 -0.694349965 -0.000005248 0.000054098 3.06 0.085982848 + 11 -205.400465033 -0.694346409 0.000003556 0.000029505 3.06 0.086002733 + 12 -205.400467644 -0.694349020 -0.000002611 0.000016770 3.08 0.086018923 + 13 -205.400467522 -0.694348899 0.000000122 0.000009599 3.02 0.086021461 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.706118624 +E(CORR) ... -0.694348899 +E(TOT) ... -205.400467522 +Singles norm **1/2 ... 0.086021461 ( 0.043010731, 0.043010731) +T1 diagnostic ... 0.020275453 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.058936 + 8a-> 13a 8b-> 13b 0.056082 + 8a-> 13a 9b-> 13b 0.044986 + 9a-> 13a 8b-> 13b 0.044986 + 5a-> 13a 5b-> 13b 0.029690 + 8b-> 13b -1b-> -1b 0.029501 + 8a-> 13a -1a-> -1a 0.029501 + 11a-> 13a 11b-> 13b 0.028951 + 9a-> 22a 9b-> 13b 0.022783 + 9a-> 13a 9b-> 22b 0.022783 + 11a-> 25a 11b-> 25b 0.022094 + 8a-> 22a 8b-> 13b 0.019997 + 8a-> 13a 8b-> 22b 0.019997 + 11a-> 25a 11b-> 24b 0.019151 + 11a-> 24a 11b-> 25b 0.019151 + 11b-> 24b -1b-> -1b 0.018470 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034493588 + alpha-alpha-alpha ... -0.000865471 ( 2.5%) + alpha-alpha-beta ... -0.016381323 ( 47.5%) + alpha-beta -beta ... -0.016381323 ( 47.5%) + beta -beta -beta ... -0.000865471 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034493588 + +Final correlation energy ... -0.728842487 +E(CCSD) ... -205.400467522 +E(CCSD(T)) ... -205.434961111 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210307194 sqrt= 1.100139625 +W(HF) = 0.826236517 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 57.702 sec + +Fock Matrix Formation ... 0.211 sec ( 0.4%) +Initial Guess ... 0.134 sec ( 0.2%) +DIIS Solver ... 1.852 sec ( 3.2%) +State Vector Update ... 0.091 sec ( 0.2%) +Sigma-vector construction ... 40.429 sec ( 70.1%) + <0|H|D> ... 0.005 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.029 sec ( 0.1% of sigma) + (0-ext) ... 0.076 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (2-ext) ... 0.947 sec ( 2.3% of sigma) + (4-ext) ... 23.229 sec ( 57.5% of sigma) + ... 1.434 sec ( 3.5% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.106 sec ( 0.3% of sigma) + Fock-dressing ... 2.127 sec ( 5.3% of sigma) + (ik|jl)-dressing ... 0.080 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.768 sec ( 24.2% of sigma) + Pair energies ... 0.006 sec ( 0.0% of sigma) +Total Time for computing (T) ... 7.098 sec ( 12.3% of ALL) + I/O of integral and amplitudes ... 0.883 sec ( 12.4% of (T)) + External N**7 contributions ... 3.970 sec ( 55.9% of (T)) + Internal N**7 contributions ... 0.326 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.831 sec ( 25.8% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.434961110659 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.001318450 0.002013029 -0.004721948 + 2 N : 0.001634287 0.002737289 0.003836531 + 3 O : -0.001201572 -0.002392478 -0.002553177 + 4 H : 0.000885735 -0.002357840 0.003438594 + +Norm of the cartesian gradient ... 0.009210011 +RMS gradient ... 0.002658701 +MAX gradient ... 0.004721948 + +------- +TIMINGS +------- + +Total numerical gradient time ... 364.931 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.434961111 Eh +Current gradient norm .... 0.009210011 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999859 +Lowest eigenvalues of augmented Hessian: + -0.000000035 0.091294645 0.166184210 0.468416826 0.499522244 +Length of the computed step .... 0.000531775 +The final length of the internal step .... 0.000531775 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0002170963 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001119010 RMS(Int)= 0.0002170962 + Iter 1: RMS(Cart)= 0.0000000042 RMS(Int)= 0.0000000070 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000351153 0.0000050000 NO + RMS gradient 0.0000344486 0.0001000000 YES + MAX gradient 0.0000559988 0.0003000000 YES + RMS step 0.0002170963 0.0020000000 YES + MAX step 0.0005059700 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0003 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4950 -0.000056 0.0003 1.4953 + 2. B(O 2,N 1) 1.1674 -0.000028 -0.0000 1.1674 + 3. B(H 3,O 0) 0.9702 -0.000030 0.0000 0.9702 + 4. A(N 1,O 0,H 3) 103.73 -0.000010 -0.00 103.72 + 5. A(O 0,N 1,O 2) 111.67 0.000047 -0.01 111.66 + 6. D(O 2,N 1,O 0,H 3) -73.64 -0.007588 -0.00 -73.64 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.781603 -0.298667 0.318643 + N 0.619477 -0.489633 -0.167631 + O 0.893990 0.278135 -1.003133 + H -0.731863 0.510165 0.852121 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.477015 -0.564398 0.602149 + 1 N 7.0000 0 14.007 1.170642 -0.925273 -0.316777 + 2 O 8.0000 0 15.999 1.689396 0.525598 -1.895646 + 3 H 1.0000 0 1.008 -1.383022 0.964073 1.610275 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.495311139415 0.00000000 0.00000000 + O 2 1 0 1.167427909941 111.65847270 0.00000000 + H 1 2 3 0.970196546284 103.72423695 286.36363663 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.825728538497 0.00000000 0.00000000 + O 2 1 0 2.206119030884 111.65847270 0.00000000 + H 1 2 3 1.833405768552 103.72423695 286.36363663 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2230 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2699 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 535 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.477334950628 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.4773349506 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.772e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7060952096 0.000000000000 0.00000818 0.00000020 0.0000433 0.7000 + 1 -204.7060952189 -0.000000009355 0.00000592 0.00000017 0.0000336 0.7000 + ***Turning on DIIS*** + 2 -204.7060952267 -0.000000007733 0.00001532 0.00000044 0.0000258 0.0000 + 3 -204.7061016675 -0.000006440829 0.00000505 0.00000018 0.0000067 0.0000 + 4 -204.7060923438 0.000009323728 0.00000154 0.00000005 0.0000018 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70609581 Eh -5570.33606 eV + +Components: +Nuclear Repulsion : 68.47733495 Eh 1863.36302 eV +Electronic Energy : -273.18343076 Eh -7433.69907 eV +One Electron Energy: -416.64222037 Eh -11337.41120 eV +Two Electron Energy: 143.45878960 Eh 3903.71213 eV + +Virial components: +Potential Energy : -408.93420449 Eh -11127.66542 eV +Kinetic Energy : 204.22810868 Eh 5557.32937 eV +Virial Ratio : 2.00234046 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -3.4696e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.5808e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.0167e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.1450e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.690851 -563.0267 + 1 1.0000 -20.618985 -561.0711 + 2 1.0000 -15.805701 -430.0950 + 3 1.0000 -1.616987 -44.0005 + 4 1.0000 -1.374602 -37.4048 + 5 1.0000 -0.957076 -26.0434 + 6 1.0000 -0.768127 -20.9018 + 7 1.0000 -0.734911 -19.9979 + 8 1.0000 -0.699239 -19.0273 + 9 1.0000 -0.604366 -16.4456 + 10 1.0000 -0.530619 -14.4389 + 11 1.0000 -0.460862 -12.5407 + 12 0.0000 0.031017 0.8440 + 13 0.0000 0.066101 1.7987 + 14 0.0000 0.092156 2.5077 + 15 0.0000 0.105497 2.8707 + 16 0.0000 0.113214 3.0807 + 17 0.0000 0.155445 4.2299 + 18 0.0000 0.157226 4.2783 + 19 0.0000 0.174273 4.7422 + 20 0.0000 0.178484 4.8568 + 21 0.0000 0.190176 5.1749 + 22 0.0000 0.201488 5.4828 + 23 0.0000 0.235046 6.3959 + 24 0.0000 0.270456 7.3595 + 25 0.0000 0.287464 7.8223 + 26 0.0000 0.305045 8.3007 + 27 0.0000 0.332337 9.0434 + 28 0.0000 0.336546 9.1579 + 29 0.0000 0.353489 9.6189 + 30 0.0000 0.424115 11.5408 + 31 0.0000 0.508248 13.8301 + 32 0.0000 0.531122 14.4526 + 33 0.0000 0.542354 14.7582 + 34 0.0000 0.562909 15.3175 + 35 0.0000 0.600534 16.3414 + 36 0.0000 0.631942 17.1960 + 37 0.0000 0.645426 17.5629 + 38 0.0000 0.707814 19.2606 + 39 0.0000 0.717816 19.5328 + 40 0.0000 0.734014 19.9735 + 41 0.0000 0.750798 20.4302 + 42 0.0000 0.764170 20.7941 + 43 0.0000 0.786656 21.4060 + 44 0.0000 0.808339 21.9960 + 45 0.0000 0.819423 22.2976 + 46 0.0000 0.857130 23.3237 + 47 0.0000 0.878372 23.9017 + 48 0.0000 0.895084 24.3565 + 49 0.0000 0.958617 26.0853 + 50 0.0000 0.964470 26.2446 + 51 0.0000 0.974643 26.5214 + 52 0.0000 0.988450 26.8971 + 53 0.0000 1.025363 27.9015 + 54 0.0000 1.044825 28.4311 + 55 0.0000 1.094574 29.7849 + 56 0.0000 1.155440 31.4411 + 57 0.0000 1.218297 33.1515 + 58 0.0000 1.235709 33.6253 + 59 0.0000 1.273915 34.6650 + 60 0.0000 1.318480 35.8777 + 61 0.0000 1.409956 38.3669 + 62 0.0000 1.465298 39.8728 + 63 0.0000 1.512115 41.1467 + 64 0.0000 1.530546 41.6483 + 65 0.0000 1.580129 42.9975 + 66 0.0000 1.591788 43.3148 + 67 0.0000 1.632294 44.4170 + 68 0.0000 1.651257 44.9330 + 69 0.0000 1.730139 47.0795 + 70 0.0000 1.751236 47.6535 + 71 0.0000 1.779438 48.4210 + 72 0.0000 1.915059 52.1114 + 73 0.0000 1.926646 52.4267 + 74 0.0000 1.972212 53.6666 + 75 0.0000 2.008083 54.6427 + 76 0.0000 2.041966 55.5647 + 77 0.0000 2.091801 56.9208 + 78 0.0000 2.139949 58.2310 + 79 0.0000 2.189574 59.5813 + 80 0.0000 2.271521 61.8112 + 81 0.0000 2.299070 62.5609 + 82 0.0000 2.331826 63.4522 + 83 0.0000 2.359059 64.1932 + 84 0.0000 2.412050 65.6352 + 85 0.0000 2.453556 66.7647 + 86 0.0000 2.467045 67.1317 + 87 0.0000 2.477139 67.4064 + 88 0.0000 2.512626 68.3720 + 89 0.0000 2.557563 69.5948 + 90 0.0000 2.594718 70.6059 + 91 0.0000 2.597698 70.6870 + 92 0.0000 2.661380 72.4198 + 93 0.0000 2.704244 73.5862 + 94 0.0000 2.749110 74.8071 + 95 0.0000 2.778930 75.6185 + 96 0.0000 2.838505 77.2396 + 97 0.0000 2.919975 79.4566 + 98 0.0000 2.960325 80.5545 + 99 0.0000 2.977653 81.0261 + 100 0.0000 3.083200 83.8981 + 101 0.0000 3.168630 86.2228 + 102 0.0000 3.223726 87.7220 + 103 0.0000 3.487877 94.9100 + 104 0.0000 3.709975 100.9535 + 105 0.0000 3.827004 104.1381 + 106 0.0000 4.038451 109.8918 + 107 0.0000 4.167985 113.4166 + 108 0.0000 4.208489 114.5188 + 109 0.0000 4.282511 116.5330 + 110 0.0000 4.369306 118.8949 + 111 0.0000 4.392698 119.5314 + 112 0.0000 4.533745 123.3695 + 113 0.0000 4.617934 125.6604 + 114 0.0000 4.665786 126.9625 + 115 0.0000 4.721731 128.4848 + 116 0.0000 4.836402 131.6052 + 117 0.0000 4.888622 133.0262 + 118 0.0000 4.930330 134.1611 + 119 0.0000 4.962331 135.0319 + 120 0.0000 5.051430 137.4564 + 121 0.0000 5.107236 138.9750 + 122 0.0000 5.183361 141.0464 + 123 0.0000 5.199076 141.4740 + 124 0.0000 5.240538 142.6023 + 125 0.0000 5.298571 144.1815 + 126 0.0000 5.391938 146.7221 + 127 0.0000 5.494976 149.5259 + 128 0.0000 5.527080 150.3995 + 129 0.0000 5.697062 155.0249 + 130 0.0000 5.743472 156.2878 + 131 0.0000 5.945272 161.7791 + 132 0.0000 6.168026 167.8405 + 133 0.0000 6.415110 174.5640 + 134 0.0000 6.479953 176.3285 + 135 0.0000 6.509809 177.1409 + 136 0.0000 6.691822 182.0937 + 137 0.0000 6.714653 182.7150 + 138 0.0000 6.776854 184.4076 + 139 0.0000 6.816284 185.4805 + 140 0.0000 6.839028 186.0994 + 141 0.0000 7.072819 192.4612 + 142 0.0000 7.107136 193.3950 + 143 0.0000 7.122170 193.8041 + 144 0.0000 7.206108 196.0882 + 145 0.0000 7.254614 197.4081 + 146 0.0000 7.279418 198.0830 + 147 0.0000 7.334288 199.5761 + 148 0.0000 7.384745 200.9491 + 149 0.0000 7.454290 202.8415 + 150 0.0000 7.470307 203.2774 + 151 0.0000 7.557912 205.6612 + 152 0.0000 7.577132 206.1843 + 153 0.0000 7.644161 208.0082 + 154 0.0000 7.690088 209.2579 + 155 0.0000 7.899968 214.9690 + 156 0.0000 7.952507 216.3987 + 157 0.0000 8.391571 228.3463 + 158 0.0000 14.042169 382.1068 + 159 0.0000 14.902678 405.5225 + 160 0.0000 16.060003 437.0149 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.690851 -563.0267 + 1 1.0000 -20.618985 -561.0711 + 2 1.0000 -15.805701 -430.0950 + 3 1.0000 -1.616987 -44.0005 + 4 1.0000 -1.374602 -37.4048 + 5 1.0000 -0.957076 -26.0434 + 6 1.0000 -0.768127 -20.9018 + 7 1.0000 -0.734911 -19.9979 + 8 1.0000 -0.699239 -19.0273 + 9 1.0000 -0.604366 -16.4456 + 10 1.0000 -0.530619 -14.4389 + 11 1.0000 -0.460862 -12.5407 + 12 0.0000 0.031017 0.8440 + 13 0.0000 0.066101 1.7987 + 14 0.0000 0.092156 2.5077 + 15 0.0000 0.105497 2.8707 + 16 0.0000 0.113214 3.0807 + 17 0.0000 0.155445 4.2299 + 18 0.0000 0.157226 4.2783 + 19 0.0000 0.174273 4.7422 + 20 0.0000 0.178484 4.8568 + 21 0.0000 0.190176 5.1749 + 22 0.0000 0.201488 5.4828 + 23 0.0000 0.235046 6.3959 + 24 0.0000 0.270456 7.3595 + 25 0.0000 0.287464 7.8223 + 26 0.0000 0.305045 8.3007 + 27 0.0000 0.332337 9.0434 + 28 0.0000 0.336546 9.1579 + 29 0.0000 0.353489 9.6189 + 30 0.0000 0.424115 11.5408 + 31 0.0000 0.508248 13.8301 + 32 0.0000 0.531122 14.4526 + 33 0.0000 0.542354 14.7582 + 34 0.0000 0.562909 15.3175 + 35 0.0000 0.600534 16.3414 + 36 0.0000 0.631942 17.1960 + 37 0.0000 0.645426 17.5629 + 38 0.0000 0.707814 19.2606 + 39 0.0000 0.717816 19.5328 + 40 0.0000 0.734014 19.9735 + 41 0.0000 0.750798 20.4302 + 42 0.0000 0.764170 20.7941 + 43 0.0000 0.786656 21.4060 + 44 0.0000 0.808339 21.9960 + 45 0.0000 0.819423 22.2976 + 46 0.0000 0.857130 23.3237 + 47 0.0000 0.878372 23.9017 + 48 0.0000 0.895084 24.3565 + 49 0.0000 0.958617 26.0853 + 50 0.0000 0.964470 26.2446 + 51 0.0000 0.974643 26.5214 + 52 0.0000 0.988450 26.8971 + 53 0.0000 1.025363 27.9015 + 54 0.0000 1.044825 28.4311 + 55 0.0000 1.094574 29.7849 + 56 0.0000 1.155440 31.4411 + 57 0.0000 1.218297 33.1515 + 58 0.0000 1.235709 33.6253 + 59 0.0000 1.273915 34.6650 + 60 0.0000 1.318480 35.8777 + 61 0.0000 1.409956 38.3669 + 62 0.0000 1.465298 39.8728 + 63 0.0000 1.512115 41.1467 + 64 0.0000 1.530546 41.6483 + 65 0.0000 1.580129 42.9975 + 66 0.0000 1.591788 43.3148 + 67 0.0000 1.632294 44.4170 + 68 0.0000 1.651257 44.9330 + 69 0.0000 1.730139 47.0795 + 70 0.0000 1.751236 47.6535 + 71 0.0000 1.779438 48.4210 + 72 0.0000 1.915059 52.1114 + 73 0.0000 1.926646 52.4267 + 74 0.0000 1.972212 53.6666 + 75 0.0000 2.008083 54.6427 + 76 0.0000 2.041966 55.5647 + 77 0.0000 2.091801 56.9208 + 78 0.0000 2.139949 58.2310 + 79 0.0000 2.189574 59.5813 + 80 0.0000 2.271521 61.8112 + 81 0.0000 2.299070 62.5609 + 82 0.0000 2.331826 63.4522 + 83 0.0000 2.359059 64.1932 + 84 0.0000 2.412050 65.6352 + 85 0.0000 2.453556 66.7647 + 86 0.0000 2.467045 67.1317 + 87 0.0000 2.477139 67.4064 + 88 0.0000 2.512626 68.3720 + 89 0.0000 2.557563 69.5948 + 90 0.0000 2.594718 70.6059 + 91 0.0000 2.597698 70.6870 + 92 0.0000 2.661380 72.4198 + 93 0.0000 2.704244 73.5862 + 94 0.0000 2.749110 74.8071 + 95 0.0000 2.778930 75.6185 + 96 0.0000 2.838505 77.2396 + 97 0.0000 2.919975 79.4566 + 98 0.0000 2.960325 80.5545 + 99 0.0000 2.977653 81.0261 + 100 0.0000 3.083200 83.8981 + 101 0.0000 3.168630 86.2228 + 102 0.0000 3.223726 87.7220 + 103 0.0000 3.487877 94.9100 + 104 0.0000 3.709975 100.9535 + 105 0.0000 3.827004 104.1381 + 106 0.0000 4.038451 109.8918 + 107 0.0000 4.167985 113.4166 + 108 0.0000 4.208489 114.5188 + 109 0.0000 4.282511 116.5330 + 110 0.0000 4.369306 118.8949 + 111 0.0000 4.392698 119.5314 + 112 0.0000 4.533745 123.3695 + 113 0.0000 4.617934 125.6604 + 114 0.0000 4.665786 126.9625 + 115 0.0000 4.721731 128.4848 + 116 0.0000 4.836402 131.6052 + 117 0.0000 4.888622 133.0262 + 118 0.0000 4.930330 134.1611 + 119 0.0000 4.962331 135.0319 + 120 0.0000 5.051430 137.4564 + 121 0.0000 5.107236 138.9750 + 122 0.0000 5.183361 141.0464 + 123 0.0000 5.199076 141.4740 + 124 0.0000 5.240538 142.6023 + 125 0.0000 5.298571 144.1815 + 126 0.0000 5.391938 146.7221 + 127 0.0000 5.494976 149.5259 + 128 0.0000 5.527080 150.3995 + 129 0.0000 5.697062 155.0249 + 130 0.0000 5.743472 156.2878 + 131 0.0000 5.945272 161.7791 + 132 0.0000 6.168026 167.8405 + 133 0.0000 6.415110 174.5640 + 134 0.0000 6.479953 176.3285 + 135 0.0000 6.509809 177.1409 + 136 0.0000 6.691822 182.0937 + 137 0.0000 6.714653 182.7150 + 138 0.0000 6.776854 184.4076 + 139 0.0000 6.816284 185.4805 + 140 0.0000 6.839028 186.0994 + 141 0.0000 7.072819 192.4612 + 142 0.0000 7.107136 193.3950 + 143 0.0000 7.122170 193.8041 + 144 0.0000 7.206108 196.0882 + 145 0.0000 7.254614 197.4081 + 146 0.0000 7.279418 198.0830 + 147 0.0000 7.334288 199.5761 + 148 0.0000 7.384745 200.9491 + 149 0.0000 7.454290 202.8415 + 150 0.0000 7.470307 203.2774 + 151 0.0000 7.557912 205.6612 + 152 0.0000 7.577132 206.1843 + 153 0.0000 7.644161 208.0082 + 154 0.0000 7.690088 209.2579 + 155 0.0000 7.899968 214.9690 + 156 0.0000 7.952507 216.3987 + 157 0.0000 8.391571 228.3463 + 158 0.0000 14.042169 382.1068 + 159 0.0000 14.902678 405.5225 + 160 0.0000 16.060003 437.0149 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.369476 0.000000 + 1 N : 0.353164 0.000000 + 2 O : -0.231752 0.000000 + 3 H : 0.248065 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.855893 s : 3.855893 + pz : 1.688367 p : 4.481903 + px : 1.271898 + py : 1.521639 + dz2 : 0.002505 d : 0.027449 + dxz : 0.005080 + dyz : 0.002311 + dx2y2 : 0.013277 + dxy : 0.004277 + f0 : 0.000711 f : 0.004231 + f+1 : 0.000800 + f-1 : 0.000191 + f+2 : 0.000549 + f-2 : 0.000110 + f+3 : 0.001022 + f-3 : 0.000848 + 1 N s : 3.825394 s : 3.825394 + pz : 0.837274 p : 2.650924 + px : 0.808844 + py : 1.004806 + dz2 : 0.035069 d : 0.139322 + dxz : 0.031348 + dyz : 0.015202 + dx2y2 : 0.036509 + dxy : 0.021196 + f0 : 0.003564 f : 0.031197 + f+1 : 0.004908 + f-1 : 0.003471 + f+2 : 0.003884 + f-2 : 0.004494 + f+3 : 0.004842 + f-3 : 0.006034 + 2 O s : 3.875550 s : 3.875550 + pz : 1.193336 p : 4.286500 + px : 1.763649 + py : 1.329516 + dz2 : 0.024385 d : 0.062231 + dxz : 0.007755 + dyz : 0.010521 + dx2y2 : 0.007848 + dxy : 0.011723 + f0 : 0.001454 f : 0.007471 + f+1 : 0.000514 + f-1 : 0.001587 + f+2 : 0.001192 + f-2 : 0.001265 + f+3 : 0.000805 + f-3 : 0.000654 + 3 H s : 0.643001 s : 0.643001 + pz : 0.039062 p : 0.088613 + px : 0.023670 + py : 0.025882 + dz2 : 0.006179 d : 0.020321 + dxz : 0.002564 + dyz : 0.001659 + dx2y2 : 0.002870 + dxy : 0.007050 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.576364 0.000000 + 1 N : -0.237038 0.000000 + 2 O : 0.249023 0.000000 + 3 H : -0.588349 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.133911 s : 3.133911 + pz : 1.399796 p : 3.955957 + px : 1.189295 + py : 1.366866 + dz2 : 0.033470 d : 0.258407 + dxz : 0.058484 + dyz : 0.029193 + dx2y2 : 0.081503 + dxy : 0.055758 + f0 : 0.006707 f : 0.075361 + f+1 : 0.015960 + f-1 : 0.001275 + f+2 : 0.013900 + f-2 : 0.005372 + f+3 : 0.012517 + f-3 : 0.019629 + 1 N s : 3.035975 s : 3.035975 + pz : 0.921390 p : 2.837237 + px : 0.863344 + py : 1.052503 + dz2 : 0.158044 d : 0.922989 + dxz : 0.233900 + dyz : 0.170981 + dx2y2 : 0.204732 + dxy : 0.155332 + f0 : 0.044184 f : 0.440836 + f+1 : 0.062170 + f-1 : 0.054152 + f+2 : 0.078865 + f-2 : 0.074141 + f+3 : 0.058791 + f-3 : 0.068533 + 2 O s : 3.313046 s : 3.313046 + pz : 1.227670 p : 3.990655 + px : 1.453130 + py : 1.309855 + dz2 : 0.047934 d : 0.329904 + dxz : 0.065253 + dyz : 0.113014 + dx2y2 : 0.067665 + dxy : 0.036038 + f0 : 0.012472 f : 0.117372 + f+1 : 0.010150 + f-1 : 0.024292 + f+2 : 0.031720 + f-2 : 0.020348 + f+3 : 0.005523 + f-3 : 0.012866 + 3 H s : 0.625834 s : 0.625834 + pz : 0.192240 p : 0.572462 + px : 0.138965 + py : 0.241258 + dz2 : 0.078360 d : 0.390052 + dxz : 0.047948 + dyz : 0.100334 + dx2y2 : 0.079678 + dxy : 0.083732 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3695 8.0000 -0.3695 1.8164 1.8164 0.0000 + 1 N 6.6468 7.0000 0.3532 2.5866 2.5866 -0.0000 + 2 O 8.2318 8.0000 -0.2318 1.7995 1.7995 -0.0000 + 3 H 0.7519 1.0000 0.2481 1.0003 1.0003 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8030 B( 0-O , 3-H ) : 0.9550 B( 1-N , 2-O ) : 1.7397 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.950 sec +Sum of individual times .... 0.765 sec ( 80.5%) + +Fock matrix formation .... 0.611 sec ( 64.3%) +Diagonalization .... 0.066 sec ( 6.9%) +Density matrix formation .... 0.005 sec ( 0.5%) +Population analysis .... 0.028 sec ( 2.9%) +Initial guess .... 0.010 sec ( 1.0%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.5%) +DIIS solution .... 0.046 sec ( 4.8%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.210 sec +Reference energy ... -204.706095251 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.374 sec +AO-integral generation ... 0.143 sec +Half transformation ... 0.080 sec +K-integral sorting ... 5.379 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.027 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.027 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.351 sec +AO-integral generation ... 0.246 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.149 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.252 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090024350 +EMP2(bb)= -0.090024350 +EMP2(ab)= -0.517091059 + +Initial guess performed in 0.133 sec +E(0) ... -204.706095251 +E(MP2) ... -0.697139758 +Initial E(tot) ... -205.403235009 + ... 0.189197587 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.403235009 -0.697139758 -0.000000000 0.019609964 2.74 0.000001280 + *** Turning on DIIS *** + 1 -205.374967696 -0.668872445 0.028267313 0.010308440 2.77 0.055742389 + 2 -205.394480649 -0.688385398 -0.019512953 0.003972871 2.88 0.058548252 + 3 -205.398296706 -0.692201456 -0.003816057 0.001948984 2.88 0.071673193 + 4 -205.399838348 -0.693743097 -0.001541642 0.000862287 2.89 0.077588707 + 5 -205.400334030 -0.694238779 -0.000495682 0.000540484 2.93 0.082091295 + 6 -205.400417707 -0.694322456 -0.000083677 0.000342306 2.87 0.084239376 + 7 -205.400452767 -0.694357516 -0.000035060 0.000245278 2.96 0.085241650 + 8 -205.400461318 -0.694366067 -0.000008551 0.000167245 2.96 0.085709874 + 9 -205.400458310 -0.694363059 0.000003008 0.000103892 2.87 0.085905575 + 10 -205.400463563 -0.694368312 -0.000005253 0.000054106 2.86 0.085997264 + 11 -205.400460004 -0.694364753 0.000003559 0.000029515 2.91 0.086017133 + 12 -205.400462618 -0.694367367 -0.000002614 0.000016777 2.96 0.086033339 + 13 -205.400462496 -0.694367245 0.000000122 0.000009600 2.89 0.086035864 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.706095251 +E(CORR) ... -0.694367245 +E(TOT) ... -205.400462496 +Singles norm **1/2 ... 0.086035864 ( 0.043017932, 0.043017932) +T1 diagnostic ... 0.020278848 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.058897 + 8a-> 13a 8b-> 13b 0.056125 + 9a-> 13a 8b-> 13b 0.044994 + 8a-> 13a 9b-> 13b 0.044994 + 5a-> 13a 5b-> 13b 0.029699 + 8a-> 13a -1a-> -1a 0.029497 + 8b-> 13b -1b-> -1b 0.029497 + 11a-> 13a 11b-> 13b 0.028936 + 9a-> 13a 9b-> 22b 0.022764 + 9a-> 22a 9b-> 13b 0.022764 + 11a-> 25a 11b-> 25b 0.022077 + 8a-> 13a 8b-> 22b 0.020011 + 8a-> 22a 8b-> 13b 0.020011 + 11a-> 25a 11b-> 24b 0.019220 + 11a-> 24a 11b-> 25b 0.019220 + 11a-> 24a 11b-> 24b 0.018583 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034498627 + alpha-alpha-alpha ... -0.000865515 ( 2.5%) + alpha-alpha-beta ... -0.016383799 ( 47.5%) + alpha-beta -beta ... -0.016383799 ( 47.5%) + beta -beta -beta ... -0.000865515 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034498627 + +Final correlation energy ... -0.728865872 +E(CCSD) ... -205.400462496 +E(CCSD(T)) ... -205.434961123 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210333546 sqrt= 1.100151601 +W(HF) = 0.826218528 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.310206 -0.000000 + 1 N : 0.179542 0.000000 + 2 O : -0.105850 -0.000000 + 3 H : 0.236513 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.836081 s : 3.836081 + pz : 1.656533 p : 4.407995 + px : 1.256448 + py : 1.495014 + dz2 : 0.009531 d : 0.058170 + dxz : 0.011374 + dyz : 0.008662 + dx2y2 : 0.017079 + dxy : 0.011524 + f0 : 0.001224 f : 0.007960 + f+1 : 0.001311 + f-1 : 0.000841 + f+2 : 0.001066 + f-2 : 0.000777 + f+3 : 0.001377 + f-3 : 0.001364 + 1 N s : 3.879600 s : 3.879600 + pz : 0.875997 p : 2.742315 + px : 0.856730 + py : 1.009588 + dz2 : 0.036307 d : 0.168437 + dxz : 0.041498 + dyz : 0.020013 + dx2y2 : 0.042573 + dxy : 0.028046 + f0 : 0.003179 f : 0.030106 + f+1 : 0.005016 + f-1 : 0.003058 + f+2 : 0.003709 + f-2 : 0.004358 + f+3 : 0.004775 + f-3 : 0.006009 + 2 O s : 3.862298 s : 3.862298 + pz : 1.169425 p : 4.150371 + px : 1.681998 + py : 1.298948 + dz2 : 0.024816 d : 0.083332 + dxz : 0.014512 + dyz : 0.013772 + dx2y2 : 0.013647 + dxy : 0.016585 + f0 : 0.001586 f : 0.009849 + f+1 : 0.001069 + f-1 : 0.001616 + f+2 : 0.001522 + f-2 : 0.001620 + f+3 : 0.001284 + f-3 : 0.001152 + 3 H s : 0.650731 s : 0.650731 + pz : 0.043179 p : 0.095294 + px : 0.026983 + py : 0.025133 + dz2 : 0.005585 d : 0.017462 + dxz : 0.002459 + dyz : 0.000925 + dx2y2 : 0.002171 + dxy : 0.006323 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.582306 -0.000000 + 1 N : -0.280892 0.000000 + 2 O : 0.291638 -0.000000 + 3 H : -0.593053 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.138589 s : 3.138589 + pz : 1.374322 p : 3.907341 + px : 1.187892 + py : 1.345127 + dz2 : 0.039215 d : 0.289431 + dxz : 0.064889 + dyz : 0.036374 + dx2y2 : 0.087991 + dxy : 0.060963 + f0 : 0.007871 f : 0.082333 + f+1 : 0.016449 + f-1 : 0.001906 + f+2 : 0.015451 + f-2 : 0.006325 + f+3 : 0.014166 + f-3 : 0.020165 + 1 N s : 3.041034 s : 3.041034 + pz : 0.942373 p : 2.878412 + px : 0.884680 + py : 1.051360 + dz2 : 0.156253 d : 0.930042 + dxz : 0.235723 + dyz : 0.177217 + dx2y2 : 0.208434 + dxy : 0.152415 + f0 : 0.044232 f : 0.431404 + f+1 : 0.059583 + f-1 : 0.054422 + f+2 : 0.076169 + f-2 : 0.070988 + f+3 : 0.059574 + f-3 : 0.066435 + 2 O s : 3.315740 s : 3.315740 + pz : 1.213993 p : 3.908383 + px : 1.401603 + py : 1.292787 + dz2 : 0.057344 d : 0.358494 + dxz : 0.069252 + dyz : 0.117526 + dx2y2 : 0.072664 + dxy : 0.041707 + f0 : 0.015262 f : 0.125745 + f+1 : 0.010973 + f-1 : 0.026447 + f+2 : 0.031543 + f-2 : 0.021510 + f+3 : 0.006907 + f-3 : 0.013103 + 3 H s : 0.626525 s : 0.626525 + pz : 0.199798 p : 0.586715 + px : 0.138775 + py : 0.248141 + dz2 : 0.075930 d : 0.379812 + dxz : 0.046053 + dyz : 0.098580 + dx2y2 : 0.078304 + dxy : 0.080945 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3102 8.0000 -0.3102 2.1634 1.7021 0.4613 + 1 N 6.8205 7.0000 0.1795 2.8506 2.3578 0.4928 + 2 O 8.1058 8.0000 -0.1058 2.1842 1.6860 0.4982 + 3 H 0.7635 1.0000 0.2365 1.0197 0.9451 0.0746 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7201 B( 0-O , 3-H ) : 0.8915 B( 1-N , 2-O ) : 1.5899 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 55.494 sec + +Fock Matrix Formation ... 0.210 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 1.878 sec ( 3.4%) +State Vector Update ... 0.088 sec ( 0.2%) +Sigma-vector construction ... 38.404 sec ( 69.2%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.022 sec ( 0.1% of sigma) + (0-ext) ... 0.070 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (2-ext) ... 0.943 sec ( 2.5% of sigma) + (4-ext) ... 21.323 sec ( 55.5% of sigma) + ... 1.416 sec ( 3.7% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.106 sec ( 0.3% of sigma) + Fock-dressing ... 2.177 sec ( 5.7% of sigma) + (ik|jl)-dressing ... 0.076 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.587 sec ( 25.0% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.883 sec ( 12.4% of ALL) + I/O of integral and amplitudes ... 0.770 sec ( 11.2% of (T)) + External N**7 contributions ... 4.011 sec ( 58.3% of (T)) + Internal N**7 contributions ... 0.334 sec ( 4.9% of (T)) + N**6 triples energy contributions ... 1.627 sec ( 23.6% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.434961122883 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.014.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.014.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.391402, -0.268208 -0.500045) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 1.00692 -0.15709 -0.64418 +Nuclear contribution : -0.88313 0.61376 1.04593 + ----------------------------------------- +Total Dipole Moment : 0.12380 0.45667 0.40175 + ----------------------------------------- +Magnitude (a.u.) : 0.62071 +Magnitude (Debye) : 1.57771 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.712216 0.402591 0.361591 +Rotational constants in MHz : 81310.186262 12069.378435 10840.235242 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.050268 -0.155019 0.598933 +x,y,z [Debye]: 0.127772 -0.394028 1.522367 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.391402, -0.268208 -0.500045) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 1.05209 -0.09822 -0.79066 +Nuclear contribution : -0.88313 0.61376 1.04593 + ----------------------------------------- +Total Dipole Moment : 0.16896 0.51554 0.25528 + ----------------------------------------- +Magnitude (a.u.) : 0.59958 +Magnitude (Debye) : 1.52401 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.712216 0.402591 0.361591 +Rotational constants in MHz : 81310.186262 12069.378435 10840.235242 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.083493 -0.233967 0.545696 +x,y,z [Debye]: -0.212223 -0.594697 1.387049 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 15 * + * * + * Dihedral ( 2, 1, 0, 3) : -65.45454545 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0378411475 RMS(Int)= 0.0007296955 + Iter 1: RMS(Cart)= 0.0001933654 RMS(Int)= 0.0000090544 + Iter 2: RMS(Cart)= 0.0000023994 RMS(Int)= 0.0000001128 + Iter 3: RMS(Cart)= 0.0000000299 RMS(Int)= 0.0000000014 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4960 0.000000 + 2. B(O 2,N 1) 1.1692 0.000000 + 3. B(H 3,O 0) 0.9727 0.000000 + 4. A(N 1,O 0,H 3) 103.5945 0.000000 + 5. A(O 0,N 1,O 2) 111.5386 0.000000 + 6. D(O 2,N 1,O 0,H 3) -65.4545 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.775791 -0.317335 0.343024 + N 0.610090 -0.513548 -0.184980 + O 0.887301 0.301277 -0.976353 + H -0.721598 0.529606 0.818308 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.466033 -0.599675 0.648222 + 1 N 7.0000 0 14.007 1.152903 -0.970465 -0.349562 + 2 O 8.0000 0 15.999 1.676755 0.569331 -1.845040 + 3 H 1.0000 0 1.008 -1.363622 1.000810 1.546379 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.495311139415 0.00000000 0.00000000 + O 2 1 0 1.167427909941 111.65847270 0.00000000 + H 1 2 3 0.970196546284 103.72423695 286.36363663 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.825728538497 0.00000000 0.00000000 + O 2 1 0 2.206119030884 111.65847270 0.00000000 + H 1 2 3 1.833405768552 103.72423695 286.36363663 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2233 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2703 + la=0 lb=0: 552 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.454920472239 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.4549204722 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.737e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7020646413 0.000000000000 0.00162790 0.00005014 0.0184969 0.7000 + 1 -204.7029186168 -0.000853975516 0.00153749 0.00004627 0.0153605 0.7000 + ***Turning on DIIS*** + 2 -204.7036555922 -0.000736975359 0.00425520 0.00012788 0.0125315 0.0000 + 3 -204.7079313189 -0.004275726722 0.00198471 0.00005973 0.0049674 0.0000 + 4 -204.7052272533 0.002704065595 0.00092638 0.00003153 0.0019577 0.0000 + 5 -204.7073494910 -0.002122237660 0.00085490 0.00002727 0.0011331 0.0000 + 6 -204.7062977585 0.001051732484 0.00092808 0.00003201 0.0006942 0.0000 + 7 -204.7060913683 0.000206390183 0.00036439 0.00001474 0.0002777 0.0000 + 8 -204.7068322215 -0.000740853141 0.00020384 0.00000887 0.0001811 0.0000 + 9 -204.7063165260 0.000515695419 0.00016345 0.00000621 0.0001162 0.0000 + 10 -204.7065327493 -0.000216223235 0.00004916 0.00000213 0.0000667 0.0000 + 11 -204.7065837569 -0.000051007633 0.00002598 0.00000074 0.0000367 0.0000 + 12 -204.7065117316 0.000072025340 0.00000768 0.00000028 0.0000099 0.0000 + 13 -204.7065354080 -0.000023676478 0.00000217 0.00000009 0.0000027 0.0000 + 14 -204.7065310080 0.000004400085 0.00000106 0.00000004 0.0000025 0.0000 + 15 -204.7065318336 -0.000000825636 0.00000088 0.00000003 0.0000018 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 16 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70653353 Eh -5570.34797 eV + +Components: +Nuclear Repulsion : 68.45492047 Eh 1862.75309 eV +Electronic Energy : -273.16145400 Eh -7433.10105 eV +One Electron Energy: -416.59286726 Eh -11336.06823 eV +Two Electron Energy: 143.43141326 Eh 3902.96718 eV + +Virial components: +Potential Energy : -408.91956398 Eh -11127.26704 eV +Kinetic Energy : 204.21303046 Eh 5556.91907 eV +Virial Ratio : 2.00241661 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.6916e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.6462e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.2698e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.5271e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.690357 -563.0132 + 1 1.0000 -20.620811 -561.1208 + 2 1.0000 -15.807048 -430.1317 + 3 1.0000 -1.616073 -43.9756 + 4 1.0000 -1.374333 -37.3975 + 5 1.0000 -0.957963 -26.0675 + 6 1.0000 -0.766906 -20.8686 + 7 1.0000 -0.735675 -20.0187 + 8 1.0000 -0.697756 -18.9869 + 9 1.0000 -0.605335 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2.5123 + 15 0.0000 0.106408 2.8955 + 16 0.0000 0.113768 3.0958 + 17 0.0000 0.155172 4.2224 + 18 0.0000 0.157528 4.2866 + 19 0.0000 0.173040 4.7086 + 20 0.0000 0.178854 4.8669 + 21 0.0000 0.190441 5.1822 + 22 0.0000 0.201536 5.4841 + 23 0.0000 0.234356 6.3772 + 24 0.0000 0.269560 7.3351 + 25 0.0000 0.282706 7.6928 + 26 0.0000 0.306964 8.3529 + 27 0.0000 0.332622 9.0511 + 28 0.0000 0.338853 9.2207 + 29 0.0000 0.356616 9.7040 + 30 0.0000 0.423243 11.5170 + 31 0.0000 0.510086 13.8801 + 32 0.0000 0.531594 14.4654 + 33 0.0000 0.539852 14.6901 + 34 0.0000 0.560363 15.2482 + 35 0.0000 0.601735 16.3740 + 36 0.0000 0.632846 17.2206 + 37 0.0000 0.644585 17.5401 + 38 0.0000 0.703515 19.1436 + 39 0.0000 0.717573 19.5262 + 40 0.0000 0.732473 19.9316 + 41 0.0000 0.748088 20.3565 + 42 0.0000 0.765986 20.8435 + 43 0.0000 0.785151 21.3650 + 44 0.0000 0.811546 22.0833 + 45 0.0000 0.821591 22.3566 + 46 0.0000 0.853942 23.2369 + 47 0.0000 0.881570 23.9887 + 48 0.0000 0.900148 24.4943 + 49 0.0000 0.952664 25.9233 + 50 0.0000 0.970706 26.4142 + 51 0.0000 0.981152 26.6985 + 52 0.0000 0.985981 26.8299 + 53 0.0000 1.021765 27.8036 + 54 0.0000 1.046636 28.4804 + 55 0.0000 1.091208 29.6933 + 56 0.0000 1.155351 31.4387 + 57 0.0000 1.214107 33.0375 + 58 0.0000 1.226795 33.3828 + 59 0.0000 1.278602 34.7925 + 60 0.0000 1.327987 36.1364 + 61 0.0000 1.411193 38.4005 + 62 0.0000 1.467576 39.9348 + 63 0.0000 1.508310 41.0432 + 64 0.0000 1.528820 41.6013 + 65 0.0000 1.580753 43.0145 + 66 0.0000 1.593948 43.3735 + 67 0.0000 1.631785 44.4031 + 68 0.0000 1.652850 44.9763 + 69 0.0000 1.732815 47.1523 + 70 0.0000 1.743037 47.4305 + 71 0.0000 1.779465 48.4217 + 72 0.0000 1.922931 52.3256 + 73 0.0000 1.927177 52.4411 + 74 0.0000 1.964584 53.4591 + 75 0.0000 2.004229 54.5378 + 76 0.0000 2.043612 55.6095 + 77 0.0000 2.081705 56.6461 + 78 0.0000 2.146415 58.4069 + 79 0.0000 2.183130 59.4060 + 80 0.0000 2.261088 61.5273 + 81 0.0000 2.307655 62.7945 + 82 0.0000 2.328593 63.3642 + 83 0.0000 2.369145 64.4677 + 84 0.0000 2.418059 65.7987 + 85 0.0000 2.452683 66.7409 + 86 0.0000 2.465047 67.0773 + 87 0.0000 2.482629 67.5558 + 88 0.0000 2.512375 68.3652 + 89 0.0000 2.555371 69.5352 + 90 0.0000 2.590883 70.5015 + 91 0.0000 2.601904 70.8014 + 92 0.0000 2.665986 72.5452 + 93 0.0000 2.681165 72.9582 + 94 0.0000 2.746942 74.7481 + 95 0.0000 2.791033 75.9479 + 96 0.0000 2.829577 76.9967 + 97 0.0000 2.917061 79.3773 + 98 0.0000 2.962248 80.6069 + 99 0.0000 2.968275 80.7709 + 100 0.0000 3.089661 84.0740 + 101 0.0000 3.169680 86.2514 + 102 0.0000 3.224840 87.7523 + 103 0.0000 3.485227 94.8378 + 104 0.0000 3.698369 100.6377 + 105 0.0000 3.837421 104.4215 + 106 0.0000 4.032838 109.7391 + 107 0.0000 4.161642 113.2440 + 108 0.0000 4.205713 114.4433 + 109 0.0000 4.294734 116.8657 + 110 0.0000 4.364733 118.7704 + 111 0.0000 4.388022 119.4041 + 112 0.0000 4.542513 123.6081 + 113 0.0000 4.615929 125.6058 + 114 0.0000 4.661650 126.8499 + 115 0.0000 4.728194 128.6607 + 116 0.0000 4.823262 131.2476 + 117 0.0000 4.880312 132.8000 + 118 0.0000 4.934122 134.2643 + 119 0.0000 4.967063 135.1607 + 120 0.0000 5.053652 137.5169 + 121 0.0000 5.104640 138.9043 + 122 0.0000 5.179257 140.9347 + 123 0.0000 5.204841 141.6309 + 124 0.0000 5.242701 142.6612 + 125 0.0000 5.288332 143.9028 + 126 0.0000 5.388396 146.6257 + 127 0.0000 5.483215 149.2059 + 128 0.0000 5.502781 149.7383 + 129 0.0000 5.699448 155.0899 + 130 0.0000 5.748146 156.4150 + 131 0.0000 5.944831 161.7671 + 132 0.0000 6.164709 167.7503 + 133 0.0000 6.402911 174.2321 + 134 0.0000 6.481064 176.3587 + 135 0.0000 6.511637 177.1907 + 136 0.0000 6.689069 182.0188 + 137 0.0000 6.712571 182.6583 + 138 0.0000 6.779348 184.4754 + 139 0.0000 6.814067 185.4202 + 140 0.0000 6.846738 186.3092 + 141 0.0000 7.065507 192.2622 + 142 0.0000 7.108819 193.4408 + 143 0.0000 7.123498 193.8402 + 144 0.0000 7.207142 196.1163 + 145 0.0000 7.252932 197.3623 + 146 0.0000 7.271865 197.8775 + 147 0.0000 7.328690 199.4238 + 148 0.0000 7.382501 200.8881 + 149 0.0000 7.455574 202.8765 + 150 0.0000 7.469033 203.2427 + 151 0.0000 7.542140 205.2321 + 152 0.0000 7.576728 206.1732 + 153 0.0000 7.646198 208.0636 + 154 0.0000 7.676590 208.8906 + 155 0.0000 7.903108 215.0545 + 156 0.0000 7.959361 216.5852 + 157 0.0000 8.377989 227.9767 + 158 0.0000 14.016411 381.4059 + 159 0.0000 14.857060 404.2811 + 160 0.0000 16.022869 436.0044 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.369756 0.000000 + 1 N : 0.355642 0.000000 + 2 O : -0.236731 0.000000 + 3 H : 0.250845 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.853602 s : 3.853602 + pz : 1.708486 p : 4.483354 + px : 1.284107 + py : 1.490761 + dz2 : 0.002686 d : 0.028545 + dxz : 0.005658 + dyz : 0.001995 + dx2y2 : 0.013798 + dxy : 0.004407 + f0 : 0.000741 f : 0.004256 + f+1 : 0.000820 + f-1 : 0.000148 + f+2 : 0.000562 + f-2 : 0.000166 + f+3 : 0.000971 + f-3 : 0.000846 + 1 N s : 3.828767 s : 3.828767 + pz : 0.811934 p : 2.644576 + px : 0.799313 + py : 1.033330 + dz2 : 0.033915 d : 0.139735 + dxz : 0.031080 + dyz : 0.016418 + dx2y2 : 0.037348 + dxy : 0.020975 + f0 : 0.003032 f : 0.031279 + f+1 : 0.004621 + f-1 : 0.003849 + f+2 : 0.003689 + f-2 : 0.004693 + f+3 : 0.005201 + f-3 : 0.006194 + 2 O s : 3.875371 s : 3.875371 + pz : 1.201288 p : 4.291829 + px : 1.750734 + py : 1.339807 + dz2 : 0.023155 d : 0.062031 + dxz : 0.006890 + dyz : 0.010732 + dx2y2 : 0.008278 + dxy : 0.012977 + f0 : 0.001155 f : 0.007499 + f+1 : 0.000385 + f-1 : 0.001770 + f+2 : 0.001249 + f-2 : 0.001250 + f+3 : 0.000936 + f-3 : 0.000755 + 3 H s : 0.641364 s : 0.641364 + pz : 0.039585 p : 0.087699 + px : 0.023886 + py : 0.024227 + dz2 : 0.005124 d : 0.020093 + dxz : 0.001753 + dyz : 0.002843 + dx2y2 : 0.002605 + dxy : 0.007768 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.574231 0.000000 + 1 N : -0.234891 0.000000 + 2 O : 0.247528 0.000000 + 3 H : -0.586868 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.136056 s : 3.136056 + pz : 1.404558 p : 3.955687 + px : 1.196104 + py : 1.355025 + dz2 : 0.033015 d : 0.258672 + dxz : 0.060013 + dyz : 0.028412 + dx2y2 : 0.080611 + dxy : 0.056622 + f0 : 0.007126 f : 0.075355 + f+1 : 0.015338 + f-1 : 0.000761 + f+2 : 0.013648 + f-2 : 0.006290 + f+3 : 0.011955 + f-3 : 0.020236 + 1 N s : 3.037614 s : 3.037614 + pz : 0.885506 p : 2.834691 + px : 0.855963 + py : 1.093222 + dz2 : 0.153287 d : 0.921262 + dxz : 0.225059 + dyz : 0.170130 + dx2y2 : 0.212975 + dxy : 0.159810 + f0 : 0.040066 f : 0.441325 + f+1 : 0.057010 + f-1 : 0.053483 + f+2 : 0.079068 + f-2 : 0.077125 + f+3 : 0.062686 + f-3 : 0.071887 + 2 O s : 3.311865 s : 3.311865 + pz : 1.211576 p : 3.993913 + px : 1.444013 + py : 1.338324 + dz2 : 0.043146 d : 0.329728 + dxz : 0.060982 + dyz : 0.110325 + dx2y2 : 0.075658 + dxy : 0.039618 + f0 : 0.011400 f : 0.116966 + f+1 : 0.008346 + f-1 : 0.022540 + f+2 : 0.031746 + f-2 : 0.020879 + f+3 : 0.006625 + f-3 : 0.015429 + 3 H s : 0.624712 s : 0.624712 + pz : 0.184135 p : 0.570472 + px : 0.139356 + py : 0.246981 + dz2 : 0.070135 d : 0.391684 + dxz : 0.042134 + dyz : 0.103402 + dx2y2 : 0.084735 + dxy : 0.091279 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3698 8.0000 -0.3698 1.8184 1.8184 0.0000 + 1 N 6.6444 7.0000 0.3556 2.5829 2.5829 -0.0000 + 2 O 8.2367 8.0000 -0.2367 1.7917 1.7917 -0.0000 + 3 H 0.7492 1.0000 0.2508 1.0000 1.0000 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8066 B( 0-O , 3-H ) : 0.9517 B( 1-N , 2-O ) : 1.7298 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.406 sec +Sum of individual times .... 2.196 sec ( 91.3%) + +Fock matrix formation .... 1.793 sec ( 74.5%) +Diagonalization .... 0.194 sec ( 8.1%) +Density matrix formation .... 0.014 sec ( 0.6%) +Population analysis .... 0.029 sec ( 1.2%) +Initial guess .... 0.009 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.2%) +DIIS solution .... 0.157 sec ( 6.5%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.212 sec +Reference energy ... -204.706533152 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.364 sec +AO-integral generation ... 0.142 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.376 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.030 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.025 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.032 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.042 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.023 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.365 sec +AO-integral generation ... 0.257 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.051 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.151 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.251 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090195115 +EMP2(bb)= -0.090195115 +EMP2(ab)= -0.517665003 + +Initial guess performed in 0.132 sec +E(0) ... -204.706533152 +E(MP2) ... -0.698055233 +Initial E(tot) ... -205.404588385 + ... 0.189890607 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.404588385 -0.698055233 -0.000000000 0.020409662 2.76 0.000002790 + *** Turning on DIIS *** + 1 -205.375812690 -0.669279538 0.028775695 0.009701291 2.74 0.056494533 + 2 -205.395476321 -0.688943169 -0.019663630 0.004200474 2.92 0.059314765 + 3 -205.399312628 -0.692779476 -0.003836307 0.001752355 2.88 0.072834530 + 4 -205.400879761 -0.694346609 -0.001567133 0.001213419 3.01 0.079047268 + 5 -205.401401515 -0.694868363 -0.000521754 0.000764998 3.10 0.083968115 + 6 -205.401496296 -0.694963144 -0.000094781 0.000481584 2.93 0.086452205 + 7 -205.401538398 -0.695005246 -0.000042102 0.000257804 2.87 0.087692328 + 8 -205.401549557 -0.695016405 -0.000011159 0.000146041 2.97 0.088273995 + 9 -205.401546226 -0.695013074 0.000003331 0.000087577 2.89 0.088493636 + 10 -205.401551996 -0.695018844 -0.000005770 0.000047977 2.84 0.088587486 + 11 -205.401548216 -0.695015064 0.000003780 0.000030478 2.92 0.088592087 + 12 -205.401551020 -0.695017868 -0.000002804 0.000018193 2.89 0.088611965 + 13 -205.401550591 -0.695017438 0.000000430 0.000010497 2.95 0.088609071 + 14 -205.401551156 -0.695018004 -0.000000566 0.000004821 2.97 0.088616769 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.706533152 +E(CORR) ... -0.695018004 +E(TOT) ... -205.401551156 +Singles norm **1/2 ... 0.088616769 ( 0.044308384, 0.044308384) +T1 diagnostic ... 0.020887173 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.057839 + 9a-> 13a 9b-> 13b 0.054169 + 8a-> 13a 9b-> 13b 0.043176 + 9a-> 13a 8b-> 13b 0.043176 + 8a-> 13a -1a-> -1a 0.031261 + 8b-> 13b -1b-> -1b 0.031261 + 5a-> 13a 5b-> 13b 0.029617 + 11a-> 13a 11b-> 13b 0.028759 + 11a-> 25a 11b-> 25b 0.025549 + 10a-> 13a -1a-> -1a 0.024928 + 10b-> 13b -1b-> -1b 0.024928 + 8a-> 22a 8b-> 13b 0.020855 + 8a-> 13a 8b-> 22b 0.020855 + 9a-> 13a 9b-> 22b 0.020796 + 9a-> 22a 9b-> 13b 0.020796 + 11a-> 25a -1a-> -1a 0.020661 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034749855 + alpha-alpha-alpha ... -0.000874229 ( 2.5%) + alpha-alpha-beta ... -0.016500698 ( 47.5%) + alpha-beta -beta ... -0.016500698 ( 47.5%) + beta -beta -beta ... -0.000874229 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034749855 + +Final correlation energy ... -0.729767859 +E(CCSD) ... -205.401551156 +E(CCSD(T)) ... -205.436301011 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.211727496 sqrt= 1.100784946 +W(HF) = 0.825268060 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.306579 0.000000 + 1 N : 0.178959 -0.000000 + 2 O : -0.111010 -0.000000 + 3 H : 0.238630 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.835058 s : 3.835058 + pz : 1.671490 p : 4.404314 + px : 1.268005 + py : 1.464819 + dz2 : 0.009743 d : 0.059213 + dxz : 0.011826 + dyz : 0.008452 + dx2y2 : 0.017547 + dxy : 0.011645 + f0 : 0.001247 f : 0.007994 + f+1 : 0.001357 + f-1 : 0.000798 + f+2 : 0.001053 + f-2 : 0.000819 + f+3 : 0.001349 + f-3 : 0.001372 + 1 N s : 3.882152 s : 3.882152 + pz : 0.862240 p : 2.740013 + px : 0.847775 + py : 1.029998 + dz2 : 0.035901 d : 0.168649 + dxz : 0.040806 + dyz : 0.021012 + dx2y2 : 0.043397 + dxy : 0.027534 + f0 : 0.002871 f : 0.030227 + f+1 : 0.004756 + f-1 : 0.003294 + f+2 : 0.003526 + f-2 : 0.004570 + f+3 : 0.005055 + f-3 : 0.006154 + 2 O s : 3.862054 s : 3.862054 + pz : 1.175668 p : 4.155748 + px : 1.670439 + py : 1.309642 + dz2 : 0.024085 d : 0.083318 + dxz : 0.013661 + dyz : 0.013785 + dx2y2 : 0.014138 + dxy : 0.017649 + f0 : 0.001387 f : 0.009890 + f+1 : 0.000949 + f-1 : 0.001739 + f+2 : 0.001576 + f-2 : 0.001612 + f+3 : 0.001388 + f-3 : 0.001239 + 3 H s : 0.650149 s : 0.650149 + pz : 0.044297 p : 0.093890 + px : 0.027326 + py : 0.022266 + dz2 : 0.004652 d : 0.017332 + dxz : 0.001774 + dyz : 0.002073 + dx2y2 : 0.001848 + dxy : 0.006985 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.581846 0.000000 + 1 N : -0.280186 0.000000 + 2 O : 0.289316 -0.000000 + 3 H : -0.590976 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.141143 s : 3.141143 + pz : 1.375973 p : 3.904680 + px : 1.194020 + py : 1.334687 + dz2 : 0.038841 d : 0.289945 + dxz : 0.066565 + dyz : 0.035545 + dx2y2 : 0.087172 + dxy : 0.061822 + f0 : 0.008291 f : 0.082387 + f+1 : 0.015910 + f-1 : 0.001369 + f+2 : 0.015246 + f-2 : 0.007254 + f+3 : 0.013577 + f-3 : 0.020740 + 1 N s : 3.042606 s : 3.042606 + pz : 0.914071 p : 2.877913 + px : 0.877639 + py : 1.086204 + dz2 : 0.151972 d : 0.927860 + dxz : 0.227199 + dyz : 0.176587 + dx2y2 : 0.216243 + dxy : 0.155858 + f0 : 0.040451 f : 0.431808 + f+1 : 0.054033 + f-1 : 0.053656 + f+2 : 0.076754 + f-2 : 0.073941 + f+3 : 0.063306 + f-3 : 0.069667 + 2 O s : 3.314400 s : 3.314400 + pz : 1.197057 p : 3.911845 + px : 1.393662 + py : 1.321126 + dz2 : 0.053223 d : 0.358980 + dxz : 0.065093 + dyz : 0.114872 + dx2y2 : 0.080420 + dxy : 0.045372 + f0 : 0.013773 f : 0.125458 + f+1 : 0.009150 + f-1 : 0.025405 + f+2 : 0.031503 + f-2 : 0.021934 + f+3 : 0.008137 + f-3 : 0.015556 + 3 H s : 0.625810 s : 0.625810 + pz : 0.191392 p : 0.584040 + px : 0.139198 + py : 0.253451 + dz2 : 0.068098 d : 0.381125 + dxz : 0.040534 + dyz : 0.100965 + dx2y2 : 0.083308 + dxy : 0.088221 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3066 8.0000 -0.3066 2.1740 1.7103 0.4636 + 1 N 6.8210 7.0000 0.1790 2.8506 2.3578 0.4928 + 2 O 8.1110 8.0000 -0.1110 2.1792 1.6802 0.4989 + 3 H 0.7614 1.0000 0.2386 1.0191 0.9442 0.0749 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7283 B( 0-O , 3-H ) : 0.8874 B( 1-N , 2-O ) : 1.5792 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 58.878 sec + +Fock Matrix Formation ... 0.212 sec ( 0.4%) +Initial Guess ... 0.132 sec ( 0.2%) +DIIS Solver ... 1.966 sec ( 3.3%) +State Vector Update ... 0.094 sec ( 0.2%) +Sigma-vector construction ... 41.562 sec ( 70.6%) + <0|H|D> ... 0.005 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (0-ext) ... 0.076 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (2-ext) ... 1.007 sec ( 2.4% of sigma) + (4-ext) ... 23.139 sec ( 55.7% of sigma) + ... 1.583 sec ( 3.8% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.114 sec ( 0.3% of sigma) + Fock-dressing ... 2.292 sec ( 5.5% of sigma) + (ik|jl)-dressing ... 0.079 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.417 sec ( 25.1% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 7.020 sec ( 11.9% of ALL) + I/O of integral and amplitudes ... 0.856 sec ( 12.2% of (T)) + External N**7 contributions ... 4.076 sec ( 58.1% of (T)) + Internal N**7 contributions ... 0.314 sec ( 4.5% of (T)) + N**6 triples energy contributions ... 1.721 sec ( 24.5% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.436301011332 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.005223504 0.001960338 -0.007925776 + 2 N : 0.006232084 0.000958728 0.006526959 + 3 O : -0.002924334 -0.001605035 -0.004750013 + 4 H : 0.001915753 -0.001314031 0.006148830 + +Norm of the cartesian gradient ... 0.015912274 +RMS gradient ... 0.004593478 +MAX gradient ... 0.007925776 + +------- +TIMINGS +------- + +Total numerical gradient time ... 375.093 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: -463.85 cm**-1 ***imaginary mode*** + 7: 555.25 cm**-1 + 8: 765.15 cm**-1 + 9: 1177.77 cm**-1 + 10: 1695.68 cm**-1 + 11: 3702.42 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 -0.061452 -0.482777 0.164922 0.050477 -0.061631 -0.002934 + 1 0.028401 -0.108165 -0.134039 0.057103 0.032940 -0.054393 + 2 -0.053308 0.373969 0.047421 -0.005647 0.017397 -0.030893 + 3 0.069753 0.208229 -0.437340 0.047588 -0.062247 0.000237 + 4 0.042784 0.101339 0.227314 -0.048653 -0.548241 -0.000210 + 5 0.045814 -0.244674 0.050864 -0.041286 0.459906 -0.000384 + 6 -0.014047 0.337416 0.249705 -0.032049 0.131990 -0.000488 + 7 -0.035299 0.010977 -0.043240 -0.011857 0.447436 -0.000200 + 8 -0.039253 -0.157540 -0.123752 0.024585 -0.427723 0.000519 + 9 0.229042 -0.586337 -0.503758 -0.953775 -0.251766 0.051031 + 10 -0.485040 0.134385 -0.344951 -0.042070 -0.006273 0.869424 + 11 0.832510 -0.035216 0.504738 0.273119 0.121922 0.487417 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 7: 555.25 0.021030 106.28 0.011819 ( 0.076371 0.021000 -0.074471) + 8: 765.15 0.036016 182.01 0.014689 (-0.100569 0.004700 0.067475) + 9: 1177.77 0.003734 18.87 0.000989 (-0.025063 0.014548 0.012232) + 10: 1695.68 0.034323 173.45 0.006317 (-0.058758 -0.017048 0.050729) + 11: 3702.42 0.010209 51.59 0.000860 (-0.011484 0.018192 0.019941) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 7 +The total number of vibrations considered is 5 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 555.25 E(vib) ... 0.12 +freq. 765.15 E(vib) ... 0.06 +freq. 1177.77 E(vib) ... 0.01 +freq. 1695.68 E(vib) ... 0.00 +freq. 3702.42 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.43630101 Eh +Zero point energy ... 0.01798903 Eh 11.29 kcal/mol +Thermal vibrational correction ... 0.00029591 Eh 0.19 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.41518353 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00312845 Eh 1.96 kcal/mol +Non-thermal (ZPE) correction 0.01798903 Eh 11.29 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02111748 Eh 13.25 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.41518353 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.41423932 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.677920 0.404681 0.361354 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00039071 Eh 0.25 kcal/mol +Rotational entropy ... 0.00995340 Eh 6.25 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02814642 Eh 17.66 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00995340 Eh 6.25 kcal/mol| +| sn= 2 | S(rot)= 0.00929894 Eh 5.84 kcal/mol| +| sn= 3 | S(rot)= 0.00891611 Eh 5.59 kcal/mol| +| sn= 4 | S(rot)= 0.00864449 Eh 5.42 kcal/mol| +| sn= 5 | S(rot)= 0.00843380 Eh 5.29 kcal/mol| +| sn= 6 | S(rot)= 0.00826166 Eh 5.18 kcal/mol| +| sn= 7 | S(rot)= 0.00811611 Eh 5.09 kcal/mol| +| sn= 8 | S(rot)= 0.00799003 Eh 5.01 kcal/mol| +| sn= 9 | S(rot)= 0.00787882 Eh 4.94 kcal/mol| +| sn=10 | S(rot)= 0.00777934 Eh 4.88 kcal/mol| +| sn=11 | S(rot)= 0.00768935 Eh 4.83 kcal/mol| +| sn=12 | S(rot)= 0.00760720 Eh 4.77 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.41423932 Eh +Total entropy correction ... -0.02814642 Eh -17.66 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44238575 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00608474 Eh -3.82 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.436301010 Eh +Current gradient norm .... 0.015912276 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + -0.023487213 0.094640526 0.170495716 0.472014322 0.499320512 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999578095 +Lowest eigenvalues of augmented Hessian: + -0.000102966 0.091006189 0.170345269 0.471518957 0.499257777 +Length of the computed step .... 0.029057598 +The final length of the internal step .... 0.029057598 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0118627148 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0057640631 RMS(Int)= 0.0118627164 + Iter 1: RMS(Cart)= 0.0000301772 RMS(Int)= 0.0000473081 + Iter 2: RMS(Cart)= 0.0000002489 RMS(Int)= 0.0000002728 + Iter 3: RMS(Cart)= 0.0000000023 RMS(Int)= 0.0000000031 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000004 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0019365296 0.0001000000 NO + MAX gradient 0.0031779763 0.0003000000 NO + RMS step 0.0118627148 0.0020000000 NO + MAX step 0.0253510587 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0134 Max(Angles) 0.59 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4960 0.002522 -0.0134 1.4826 + 2. B(O 2,N 1) 1.1692 0.001403 0.0006 1.1698 + 3. B(H 3,O 0) 0.9727 0.001967 -0.0021 0.9706 + 4. A(N 1,O 0,H 3) 103.59 -0.000451 0.59 104.18 + 5. A(O 0,N 1,O 2) 111.54 -0.003178 0.51 112.05 + 6. D(O 2,N 1,O 0,H 3) -65.45 -0.011195 0.00 -65.45 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.768991 -0.316437 0.342042 + N 0.603437 -0.511164 -0.183810 + O 0.888972 0.299830 -0.977080 + H -0.723418 0.527771 0.818848 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.453182 -0.597979 0.646366 + 1 N 7.0000 0 14.007 1.140331 -0.965961 -0.347351 + 2 O 8.0000 0 15.999 1.679914 0.566597 -1.846413 + 3 H 1.0000 0 1.008 -1.367061 0.997343 1.547398 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.482564515172 0.00000000 0.00000000 + O 2 1 0 1.169837200868 112.04966907 0.00000000 + H 1 2 3 0.970622182197 104.18251596 294.54545446 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.801640909545 0.00000000 0.00000000 + O 2 1 0 2.210671930914 112.04966907 0.00000000 + H 1 2 3 1.834210103862 104.18251596 294.54545446 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2233 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2703 + la=0 lb=0: 552 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.665574536177 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.715e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7076748154 0.000000000000 0.00038192 0.00001098 0.0020225 0.7000 + 1 -204.7077041640 -0.000029348594 0.00030923 0.00000912 0.0015806 0.7000 + ***Turning on DIIS*** + 2 -204.7077285301 -0.000024366116 0.00078700 0.00002356 0.0012188 0.0000 + 3 -204.7074645199 0.000264010197 0.00028532 0.00001044 0.0003653 0.0000 + 4 -204.7079779841 -0.000513464215 0.00009337 0.00000313 0.0000872 0.0000 + 5 -204.7077674015 0.000210582601 0.00003781 0.00000135 0.0000493 0.0000 + 6 -204.7076462679 0.000121133607 0.00001777 0.00000069 0.0000412 0.0000 + 7 -204.7078553107 -0.000209042771 0.00001562 0.00000060 0.0000183 0.0000 + 8 -204.7077779220 0.000077388687 0.00001426 0.00000058 0.0000139 0.0000 + 9 -204.7077924401 -0.000014518069 0.00000841 0.00000036 0.0000047 0.0000 + 10 -204.7078238897 -0.000031449644 0.00000317 0.00000012 0.0000032 0.0000 + 11 -204.7078025172 0.000021372499 0.00000158 0.00000005 0.0000016 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + +Total Energy : -204.70780845 Eh -5570.38266 eV + Last Energy change ... -5.9302e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.1708e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.203 sec +Reference energy ... -204.707807692 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.401 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.079 sec +K-integral sorting ... 5.407 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.028 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.030 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.345 sec +AO-integral generation ... 0.241 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.049 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.146 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.251 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090052735 +EMP2(bb)= -0.090052735 +EMP2(ab)= -0.516674064 + +Initial guess performed in 0.134 sec +E(0) ... -204.707807692 +E(MP2) ... -0.696779534 +Initial E(tot) ... -205.404587225 + ... 0.188700495 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.404587225 -0.696779534 -0.000000000 0.020497059 2.67 0.000000722 + *** Turning on DIIS *** + 1 -205.376374116 -0.668566424 0.028213110 0.009596906 2.67 0.056054296 + 2 -205.395845577 -0.688037885 -0.019471461 0.004247698 2.75 0.058977952 + 3 -205.399648048 -0.691840356 -0.003802471 0.001779474 2.78 0.072393270 + 4 -205.401196715 -0.693389023 -0.001548668 0.001173926 2.77 0.078568423 + 5 -205.401709513 -0.693901821 -0.000512798 0.000739211 2.86 0.083423165 + 6 -205.401802873 -0.693995181 -0.000093359 0.000461685 2.82 0.085853029 + 7 -205.401843536 -0.694035844 -0.000040663 0.000247077 2.85 0.087036806 + 8 -205.401853964 -0.694046272 -0.000010428 0.000149423 2.86 0.087590123 + 9 -205.401850841 -0.694043149 0.000003123 0.000089208 2.78 0.087803884 + 10 -205.401856295 -0.694048604 -0.000005455 0.000048683 2.74 0.087893849 + 11 -205.401852685 -0.694044994 0.000003610 0.000030558 2.74 0.087900381 + 12 -205.401855393 -0.694047701 -0.000002708 0.000018078 2.74 0.087919137 + 13 -205.401854978 -0.694047286 0.000000415 0.000009969 2.77 0.087917576 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.707807692 +E(CORR) ... -0.694047286 +E(TOT) ... -205.401854978 +Singles norm **1/2 ... 0.087917576 ( 0.043958788, 0.043958788) +T1 diagnostic ... 0.020722371 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.056078 + 9a-> 13a 9b-> 13b 0.055451 + 9a-> 13a 8b-> 13b 0.042709 + 8a-> 13a 9b-> 13b 0.042709 + 8a-> 13a -1a-> -1a 0.031619 + 8b-> 13b -1b-> -1b 0.031619 + 11a-> 13a 11b-> 13b 0.029571 + 5a-> 13a 5b-> 13b 0.029116 + 11a-> 25a 11b-> 25b 0.026031 + 10b-> 13b -1b-> -1b 0.023976 + 10a-> 13a -1a-> -1a 0.023976 + 9a-> 13a 9b-> 22b 0.021472 + 9a-> 22a 9b-> 13b 0.021472 + 11a-> 25a -1a-> -1a 0.021184 + 11b-> 25b -1b-> -1b 0.021184 + 8a-> 13a 8b-> 22b 0.020311 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034495510 + alpha-alpha-alpha ... -0.000871951 ( 2.5%) + alpha-alpha-beta ... -0.016375804 ( 47.5%) + alpha-beta -beta ... -0.016375804 ( 47.5%) + beta -beta -beta ... -0.000871951 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034495510 + +Final correlation energy ... -0.728542797 +E(CCSD) ... -205.401854978 +E(CCSD(T)) ... -205.436350489 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210369051 sqrt= 1.100167737 +W(HF) = 0.826194291 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 53.806 sec + +Fock Matrix Formation ... 0.203 sec ( 0.4%) +Initial Guess ... 0.134 sec ( 0.2%) +DIIS Solver ... 1.699 sec ( 3.2%) +State Vector Update ... 0.085 sec ( 0.2%) +Sigma-vector construction ... 37.005 sec ( 68.8%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.024 sec ( 0.1% of sigma) + (0-ext) ... 0.070 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (2-ext) ... 0.931 sec ( 2.5% of sigma) + (4-ext) ... 20.391 sec ( 55.1% of sigma) + ... 1.335 sec ( 3.6% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.106 sec ( 0.3% of sigma) + Fock-dressing ... 2.079 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.074 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.373 sec ( 25.3% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.805 sec ( 12.6% of ALL) + I/O of integral and amplitudes ... 0.808 sec ( 11.9% of (T)) + External N**7 contributions ... 3.901 sec ( 57.3% of (T)) + Internal N**7 contributions ... 0.311 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.711 sec ( 25.1% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.436350488506 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.002286551 0.002741534 -0.007685815 + 2 N : 0.002751289 0.003991663 0.006240008 + 3 O : -0.002132101 -0.003476447 -0.004087277 + 4 H : 0.001667364 -0.003256749 0.005533083 + +Norm of the cartesian gradient ... 0.014546327 +RMS gradient ... 0.004199163 +MAX gradient ... 0.007685815 + +------- +TIMINGS +------- + +Total numerical gradient time ... 360.575 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.436350489 Eh +Current gradient norm .... 0.014546327 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999997719 +Lowest eigenvalues of augmented Hessian: + -0.000000507 0.096904901 0.170915885 0.469963006 0.497398444 +Length of the computed step .... 0.002135663 +The final length of the internal step .... 0.002135663 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0008718807 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0004289241 RMS(Int)= 0.0008718800 + Iter 1: RMS(Cart)= 0.0000000864 RMS(Int)= 0.0000001429 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000494782 0.0000050000 NO + RMS gradient 0.0001240399 0.0001000000 NO + MAX gradient 0.0002419312 0.0003000000 YES + RMS step 0.0008718807 0.0020000000 YES + MAX step 0.0020108212 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0011 Max(Angles) 0.04 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4826 -0.000242 0.0011 1.4836 + 2. B(O 2,N 1) 1.1698 -0.000171 -0.0000 1.1698 + 3. B(H 3,O 0) 0.9706 -0.000046 0.0000 0.9707 + 4. A(N 1,O 0,H 3) 104.18 0.000029 -0.04 104.14 + 5. A(O 0,N 1,O 2) 112.05 0.000039 -0.01 112.03 + 6. D(O 2,N 1,O 0,H 3) -65.45 -0.011759 -0.00 -65.45 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.769546 -0.316475 0.342246 + N 0.603888 -0.511235 -0.183967 + O 0.889084 0.299871 -0.977186 + H -0.723425 0.527838 0.818907 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.454232 -0.598050 0.646751 + 1 N 7.0000 0 14.007 1.141183 -0.966094 -0.347647 + 2 O 8.0000 0 15.999 1.680126 0.566675 -1.846614 + 3 H 1.0000 0 1.008 -1.367075 0.997469 1.547510 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.483628595901 0.00000000 0.00000000 + O 2 1 0 1.169797333946 112.03498514 0.00000000 + H 1 2 3 0.970668239599 104.14456547 294.54545446 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.803651730707 0.00000000 0.00000000 + O 2 1 0 2.210596593350 112.03498514 0.00000000 + H 1 2 3 1.834297139737 104.14456547 294.54545446 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2233 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2703 + la=0 lb=0: 552 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.646343429184 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.716e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7077113077 0.000000000000 0.00003021 0.00000074 0.0001584 0.7000 + 1 -204.7077114399 -0.000000132218 0.00002482 0.00000062 0.0001252 0.7000 + ***Turning on DIIS*** + 2 -204.7077115501 -0.000000110199 0.00006431 0.00000165 0.0000976 0.0000 + 3 -204.7077291530 -0.000017602877 0.00002182 0.00000071 0.0000257 0.0000 + 4 -204.7077020416 0.000027111398 0.00000778 0.00000022 0.0000071 0.0000 + 5 -204.7077079304 -0.000005888884 0.00000282 0.00000009 0.0000033 0.0000 + 6 -204.7077168493 -0.000008918831 0.00000125 0.00000005 0.0000017 0.0000 + 7 -204.7077120616 0.000004787634 0.00000088 0.00000003 0.0000010 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + +Total Energy : -204.70771224 Eh -5570.38004 eV + Last Energy change ... -1.7817e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.7332e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.204 sec +Reference energy ... -204.707711913 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.355 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.363 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.028 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.030 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.344 sec +AO-integral generation ... 0.241 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.049 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.166 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.249 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090063954 +EMP2(bb)= -0.090063954 +EMP2(ab)= -0.516751344 + +Initial guess performed in 0.134 sec +E(0) ... -204.707711913 +E(MP2) ... -0.696879251 +Initial E(tot) ... -205.404591164 + ... 0.188794284 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.404591164 -0.696879251 -0.000000000 0.020496418 2.71 0.000001728 + *** Turning on DIIS *** + 1 -205.376332150 -0.668620237 0.028259014 0.009588290 2.71 0.056093322 + 2 -205.395819395 -0.688107482 -0.019487245 0.004245537 2.76 0.059007991 + 3 -205.399624510 -0.691912597 -0.003805115 0.001777922 2.79 0.072433149 + 4 -205.401174825 -0.693462912 -0.001550315 0.001176935 2.78 0.078612387 + 5 -205.401688483 -0.693976570 -0.000513658 0.000741128 2.89 0.083473660 + 6 -205.401781979 -0.694070066 -0.000093496 0.000463115 2.81 0.085908369 + 7 -205.401822764 -0.694110851 -0.000040785 0.000247840 2.85 0.087096577 + 8 -205.401833249 -0.694121336 -0.000010485 0.000149305 2.85 0.087652030 + 9 -205.401830109 -0.694118196 0.000003139 0.000089184 2.79 0.087866270 + 10 -205.401835591 -0.694123678 -0.000005482 0.000048683 2.76 0.087956586 + 11 -205.401831965 -0.694120052 0.000003626 0.000030581 2.75 0.087962996 + 12 -205.401834683 -0.694122770 -0.000002718 0.000018099 2.73 0.087981855 + 13 -205.401834265 -0.694122352 0.000000417 0.000010011 2.73 0.087980197 + 14 -205.401834831 -0.694122918 -0.000000566 0.000004492 2.77 0.087987665 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.707711913 +E(CORR) ... -0.694122918 +E(TOT) ... -205.401834831 +Singles norm **1/2 ... 0.087987665 ( 0.043993832, 0.043993832) +T1 diagnostic ... 0.020738891 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.056219 + 9a-> 13a 9b-> 13b 0.055365 + 8a-> 13a 9b-> 13b 0.042751 + 9a-> 13a 8b-> 13b 0.042751 + 8a-> 13a -1a-> -1a 0.031600 + 8b-> 13b -1b-> -1b 0.031600 + 11a-> 13a 11b-> 13b 0.029524 + 5a-> 13a 5b-> 13b 0.029157 + 11a-> 25a 11b-> 25b 0.026166 + 10b-> 13b -1b-> -1b 0.024023 + 10a-> 13a -1a-> -1a 0.024023 + 9a-> 22a 9b-> 13b 0.021422 + 9a-> 13a 9b-> 22b 0.021422 + 11b-> 25b -1b-> -1b 0.021227 + 11a-> 25a -1a-> -1a 0.021227 + 8a-> 13a 8b-> 22b 0.020351 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034516441 + alpha-alpha-alpha ... -0.000872160 ( 2.5%) + alpha-alpha-beta ... -0.016386060 ( 47.5%) + alpha-beta -beta ... -0.016386060 ( 47.5%) + beta -beta -beta ... -0.000872160 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034516441 + +Final correlation energy ... -0.728639359 +E(CCSD) ... -205.401834831 +E(CCSD(T)) ... -205.436351272 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210481794 sqrt= 1.100218976 +W(HF) = 0.826117340 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 56.544 sec + +Fock Matrix Formation ... 0.204 sec ( 0.4%) +Initial Guess ... 0.134 sec ( 0.2%) +DIIS Solver ... 1.830 sec ( 3.2%) +State Vector Update ... 0.089 sec ( 0.2%) +Sigma-vector construction ... 39.760 sec ( 70.3%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.024 sec ( 0.1% of sigma) + (0-ext) ... 0.074 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (2-ext) ... 0.998 sec ( 2.5% of sigma) + (4-ext) ... 21.978 sec ( 55.3% of sigma) + ... 1.378 sec ( 3.5% of sigma) + ... 0.005 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.114 sec ( 0.3% of sigma) + Fock-dressing ... 2.239 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.080 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.093 sec ( 25.4% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.719 sec ( 11.9% of ALL) + I/O of integral and amplitudes ... 0.773 sec ( 11.5% of (T)) + External N**7 contributions ... 3.882 sec ( 57.8% of (T)) + Internal N**7 contributions ... 0.310 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.581 sec ( 23.5% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.436351272257 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.002518782 0.002805976 -0.007675773 + 2 N : 0.002943881 0.003822511 0.006247151 + 3 O : -0.002101436 -0.003344341 -0.004180556 + 4 H : 0.001676337 -0.003284146 0.005609179 + +Norm of the cartesian gradient ... 0.014614257 +RMS gradient ... 0.004218772 +MAX gradient ... 0.007675773 + +------- +TIMINGS +------- + +Total numerical gradient time ... 362.745 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.436351272 Eh +Current gradient norm .... 0.014614257 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999822 +Lowest eigenvalues of augmented Hessian: + -0.000000038 0.076253694 0.201866373 0.473888458 0.493185648 +Length of the computed step .... 0.000596428 +The final length of the internal step .... 0.000596428 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0002434906 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001888689 RMS(Int)= 0.0002434922 + Iter 1: RMS(Cart)= 0.0000000431 RMS(Int)= 0.0000000705 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000007838 0.0000050000 YES + RMS gradient 0.0000306334 0.0001000000 YES + MAX gradient 0.0000677525 0.0003000000 YES + RMS step 0.0002434906 0.0020000000 YES + MAX step 0.0005467071 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.03 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4836 0.000003 0.0001 1.4837 + 2. B(O 2,N 1) 1.1698 -0.000017 0.0000 1.1698 + 3. B(H 3,O 0) 0.9707 -0.000027 0.0000 0.9707 + 4. A(N 1,O 0,H 3) 104.14 0.000068 -0.03 104.11 + 5. A(O 0,N 1,O 2) 112.03 -0.000005 -0.00 112.03 + 6. D(O 2,N 1,O 0,H 3) -65.45 -0.011814 -0.00 -65.45 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.769706 -0.316570 0.342250 + N 0.603899 -0.511204 -0.183896 + O 0.889014 0.299930 -0.977125 + H -0.723205 0.527844 0.818771 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.454534 -0.598230 0.646759 + 1 N 7.0000 0 14.007 1.141204 -0.966036 -0.347513 + 2 O 8.0000 0 15.999 1.679992 0.566786 -1.846498 + 3 H 1.0000 0 1.008 -1.366660 0.997480 1.547253 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.483746780543 0.00000000 0.00000000 + O 2 1 0 1.169803698496 112.03249587 0.00000000 + H 1 2 3 0.970705379599 104.11324147 294.54545446 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.803875067313 0.00000000 0.00000000 + O 2 1 0 2.210608620606 112.03249587 0.00000000 + H 1 2 3 1.834367324166 104.11324147 294.54545446 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2233 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2703 + la=0 lb=0: 552 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.644416403783 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.6444164038 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.716e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7076959091 0.000000000000 0.00000434 0.00000017 0.0000534 0.7000 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 1 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70769592 Eh -5570.37960 eV + +Components: +Nuclear Repulsion : 68.64441640 Eh 1867.90953 eV +Electronic Energy : -273.35211232 Eh -7438.28913 eV +One Electron Energy: -416.96469289 Eh -11346.18612 eV +Two Electron Energy: 143.61258057 Eh 3907.89699 eV + +Virial components: +Potential Energy : -408.93682811 Eh -11127.73682 eV +Kinetic Energy : 204.22913219 Eh 5557.35722 eV +Virial Ratio : 2.00234327 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -8.1204e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.6963e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.5206e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 4.2470e-05 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.688224 -562.9552 + 1 1.0000 -20.622401 -561.1641 + 2 1.0000 -15.805319 -430.0846 + 3 1.0000 -1.615124 -43.9498 + 4 1.0000 -1.378788 -37.5187 + 5 1.0000 -0.958030 -26.0693 + 6 1.0000 -0.769129 -20.9291 + 7 1.0000 -0.735621 -20.0173 + 8 1.0000 -0.698341 -19.0028 + 9 1.0000 -0.604185 -16.4407 + 10 1.0000 -0.531840 -14.4721 + 11 1.0000 -0.462767 -12.5925 + 12 0.0000 0.031010 0.8438 + 13 0.0000 0.066642 1.8134 + 14 0.0000 0.092600 2.5198 + 15 0.0000 0.106855 2.9077 + 16 0.0000 0.113614 3.0916 + 17 0.0000 0.155134 4.2214 + 18 0.0000 0.157169 4.2768 + 19 0.0000 0.173426 4.7192 + 20 0.0000 0.178769 4.8646 + 21 0.0000 0.190694 5.1891 + 22 0.0000 0.201935 5.4949 + 23 0.0000 0.234887 6.3916 + 24 0.0000 0.271133 7.3779 + 25 0.0000 0.285577 7.7710 + 26 0.0000 0.307784 8.3752 + 27 0.0000 0.333468 9.0741 + 28 0.0000 0.339086 9.2270 + 29 0.0000 0.356778 9.7084 + 30 0.0000 0.423275 11.5179 + 31 0.0000 0.510325 13.8866 + 32 0.0000 0.531970 14.4756 + 33 0.0000 0.540000 14.6941 + 34 0.0000 0.561295 15.2736 + 35 0.0000 0.602232 16.3876 + 36 0.0000 0.633125 17.2282 + 37 0.0000 0.645047 17.5526 + 38 0.0000 0.704208 19.1625 + 39 0.0000 0.717857 19.5339 + 40 0.0000 0.733018 19.9464 + 41 0.0000 0.746055 20.3012 + 42 0.0000 0.766362 20.8538 + 43 0.0000 0.784509 21.3476 + 44 0.0000 0.811513 22.0824 + 45 0.0000 0.821223 22.3466 + 46 0.0000 0.854533 23.2530 + 47 0.0000 0.881719 23.9928 + 48 0.0000 0.900198 24.4956 + 49 0.0000 0.952888 25.9294 + 50 0.0000 0.971610 26.4389 + 51 0.0000 0.981114 26.6975 + 52 0.0000 0.984884 26.8001 + 53 0.0000 1.021719 27.8024 + 54 0.0000 1.047076 28.4924 + 55 0.0000 1.091086 29.6900 + 56 0.0000 1.155953 31.4551 + 57 0.0000 1.214869 33.0583 + 58 0.0000 1.228630 33.4327 + 59 0.0000 1.280097 34.8332 + 60 0.0000 1.325948 36.0809 + 61 0.0000 1.411109 38.3982 + 62 0.0000 1.465519 39.8788 + 63 0.0000 1.509308 41.0704 + 64 0.0000 1.532230 41.6941 + 65 0.0000 1.581792 43.0428 + 66 0.0000 1.595381 43.4125 + 67 0.0000 1.634015 44.4638 + 68 0.0000 1.652883 44.9772 + 69 0.0000 1.733643 47.1748 + 70 0.0000 1.745890 47.5081 + 71 0.0000 1.782170 48.4953 + 72 0.0000 1.926458 52.4216 + 73 0.0000 1.929654 52.5086 + 74 0.0000 1.968086 53.5543 + 75 0.0000 2.005522 54.5730 + 76 0.0000 2.044555 55.6352 + 77 0.0000 2.084631 56.7257 + 78 0.0000 2.147142 58.4267 + 79 0.0000 2.183658 59.4203 + 80 0.0000 2.263131 61.5829 + 81 0.0000 2.308232 62.8102 + 82 0.0000 2.328639 63.3655 + 83 0.0000 2.370509 64.5048 + 84 0.0000 2.420009 65.8518 + 85 0.0000 2.454160 66.7811 + 86 0.0000 2.464511 67.0628 + 87 0.0000 2.485097 67.6229 + 88 0.0000 2.512066 68.3568 + 89 0.0000 2.553951 69.4965 + 90 0.0000 2.589238 70.4567 + 91 0.0000 2.602071 70.8060 + 92 0.0000 2.666594 72.5617 + 93 0.0000 2.685800 73.0843 + 94 0.0000 2.753852 74.9361 + 95 0.0000 2.798466 76.1501 + 96 0.0000 2.832291 77.0706 + 97 0.0000 2.922957 79.5377 + 98 0.0000 2.965082 80.6840 + 99 0.0000 2.975413 80.9651 + 100 0.0000 3.100855 84.3785 + 101 0.0000 3.169258 86.2399 + 102 0.0000 3.225671 87.7750 + 103 0.0000 3.491861 95.0184 + 104 0.0000 3.701376 100.7196 + 105 0.0000 3.842356 104.5558 + 106 0.0000 4.031715 109.7085 + 107 0.0000 4.164232 113.3145 + 108 0.0000 4.207337 114.4875 + 109 0.0000 4.296168 116.9047 + 110 0.0000 4.367434 118.8439 + 111 0.0000 4.393462 119.5522 + 112 0.0000 4.543007 123.6215 + 113 0.0000 4.620101 125.7193 + 114 0.0000 4.669012 127.0503 + 115 0.0000 4.731374 128.7472 + 116 0.0000 4.826182 131.3271 + 117 0.0000 4.881139 132.8226 + 118 0.0000 4.938100 134.3725 + 119 0.0000 4.972151 135.2991 + 120 0.0000 5.056289 137.5886 + 121 0.0000 5.107732 138.9885 + 122 0.0000 5.182318 141.0181 + 123 0.0000 5.207787 141.7111 + 124 0.0000 5.244797 142.7182 + 125 0.0000 5.290492 143.9616 + 126 0.0000 5.392718 146.7433 + 127 0.0000 5.495238 149.5330 + 128 0.0000 5.510845 149.9577 + 129 0.0000 5.700842 155.1278 + 130 0.0000 5.749930 156.4636 + 131 0.0000 5.953767 162.0102 + 132 0.0000 6.163777 167.7249 + 133 0.0000 6.409545 174.4126 + 134 0.0000 6.482340 176.3934 + 135 0.0000 6.513554 177.2428 + 136 0.0000 6.688037 181.9908 + 137 0.0000 6.711716 182.6351 + 138 0.0000 6.779583 184.4818 + 139 0.0000 6.814130 185.4219 + 140 0.0000 6.849591 186.3868 + 141 0.0000 7.076516 192.5618 + 142 0.0000 7.111602 193.5165 + 143 0.0000 7.133336 194.1079 + 144 0.0000 7.210715 196.2135 + 145 0.0000 7.252516 197.3510 + 146 0.0000 7.276155 197.9943 + 147 0.0000 7.329392 199.4429 + 148 0.0000 7.387610 201.0271 + 149 0.0000 7.457888 202.9394 + 150 0.0000 7.473079 203.3528 + 151 0.0000 7.547122 205.3676 + 152 0.0000 7.579305 206.2434 + 153 0.0000 7.658629 208.4019 + 154 0.0000 7.683790 209.0865 + 155 0.0000 7.907232 215.1667 + 156 0.0000 7.983149 217.2325 + 157 0.0000 8.384663 228.1583 + 158 0.0000 14.028690 381.7401 + 159 0.0000 14.947275 406.7360 + 160 0.0000 16.019945 435.9249 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.688224 -562.9552 + 1 1.0000 -20.622401 -561.1641 + 2 1.0000 -15.805319 -430.0846 + 3 1.0000 -1.615124 -43.9498 + 4 1.0000 -1.378788 -37.5187 + 5 1.0000 -0.958030 -26.0693 + 6 1.0000 -0.769129 -20.9291 + 7 1.0000 -0.735621 -20.0173 + 8 1.0000 -0.698341 -19.0028 + 9 1.0000 -0.604185 -16.4407 + 10 1.0000 -0.531840 -14.4721 + 11 1.0000 -0.462767 -12.5925 + 12 0.0000 0.031010 0.8438 + 13 0.0000 0.066642 1.8134 + 14 0.0000 0.092600 2.5198 + 15 0.0000 0.106855 2.9077 + 16 0.0000 0.113614 3.0916 + 17 0.0000 0.155134 4.2214 + 18 0.0000 0.157169 4.2768 + 19 0.0000 0.173426 4.7192 + 20 0.0000 0.178769 4.8646 + 21 0.0000 0.190694 5.1891 + 22 0.0000 0.201935 5.4949 + 23 0.0000 0.234887 6.3916 + 24 0.0000 0.271133 7.3779 + 25 0.0000 0.285577 7.7710 + 26 0.0000 0.307784 8.3752 + 27 0.0000 0.333468 9.0741 + 28 0.0000 0.339086 9.2270 + 29 0.0000 0.356778 9.7084 + 30 0.0000 0.423275 11.5179 + 31 0.0000 0.510325 13.8866 + 32 0.0000 0.531970 14.4756 + 33 0.0000 0.540000 14.6941 + 34 0.0000 0.561295 15.2736 + 35 0.0000 0.602232 16.3876 + 36 0.0000 0.633125 17.2282 + 37 0.0000 0.645047 17.5526 + 38 0.0000 0.704208 19.1625 + 39 0.0000 0.717857 19.5339 + 40 0.0000 0.733018 19.9464 + 41 0.0000 0.746055 20.3012 + 42 0.0000 0.766362 20.8538 + 43 0.0000 0.784509 21.3476 + 44 0.0000 0.811513 22.0824 + 45 0.0000 0.821223 22.3466 + 46 0.0000 0.854533 23.2530 + 47 0.0000 0.881719 23.9928 + 48 0.0000 0.900198 24.4956 + 49 0.0000 0.952888 25.9294 + 50 0.0000 0.971610 26.4389 + 51 0.0000 0.981114 26.6975 + 52 0.0000 0.984884 26.8001 + 53 0.0000 1.021719 27.8024 + 54 0.0000 1.047076 28.4924 + 55 0.0000 1.091086 29.6900 + 56 0.0000 1.155953 31.4551 + 57 0.0000 1.214869 33.0583 + 58 0.0000 1.228630 33.4327 + 59 0.0000 1.280097 34.8332 + 60 0.0000 1.325948 36.0809 + 61 0.0000 1.411109 38.3982 + 62 0.0000 1.465519 39.8788 + 63 0.0000 1.509308 41.0704 + 64 0.0000 1.532230 41.6941 + 65 0.0000 1.581792 43.0428 + 66 0.0000 1.595381 43.4125 + 67 0.0000 1.634015 44.4638 + 68 0.0000 1.652883 44.9772 + 69 0.0000 1.733643 47.1748 + 70 0.0000 1.745890 47.5081 + 71 0.0000 1.782170 48.4953 + 72 0.0000 1.926458 52.4216 + 73 0.0000 1.929654 52.5086 + 74 0.0000 1.968086 53.5543 + 75 0.0000 2.005522 54.5730 + 76 0.0000 2.044555 55.6352 + 77 0.0000 2.084631 56.7257 + 78 0.0000 2.147142 58.4267 + 79 0.0000 2.183658 59.4203 + 80 0.0000 2.263131 61.5829 + 81 0.0000 2.308232 62.8102 + 82 0.0000 2.328639 63.3655 + 83 0.0000 2.370509 64.5048 + 84 0.0000 2.420009 65.8518 + 85 0.0000 2.454160 66.7811 + 86 0.0000 2.464511 67.0628 + 87 0.0000 2.485097 67.6229 + 88 0.0000 2.512066 68.3568 + 89 0.0000 2.553951 69.4965 + 90 0.0000 2.589238 70.4567 + 91 0.0000 2.602071 70.8060 + 92 0.0000 2.666594 72.5617 + 93 0.0000 2.685800 73.0843 + 94 0.0000 2.753852 74.9361 + 95 0.0000 2.798466 76.1501 + 96 0.0000 2.832291 77.0706 + 97 0.0000 2.922957 79.5377 + 98 0.0000 2.965082 80.6840 + 99 0.0000 2.975413 80.9651 + 100 0.0000 3.100855 84.3785 + 101 0.0000 3.169258 86.2399 + 102 0.0000 3.225671 87.7750 + 103 0.0000 3.491861 95.0184 + 104 0.0000 3.701376 100.7196 + 105 0.0000 3.842356 104.5558 + 106 0.0000 4.031715 109.7085 + 107 0.0000 4.164232 113.3145 + 108 0.0000 4.207337 114.4875 + 109 0.0000 4.296168 116.9047 + 110 0.0000 4.367434 118.8439 + 111 0.0000 4.393462 119.5522 + 112 0.0000 4.543007 123.6215 + 113 0.0000 4.620101 125.7193 + 114 0.0000 4.669012 127.0503 + 115 0.0000 4.731374 128.7472 + 116 0.0000 4.826182 131.3271 + 117 0.0000 4.881139 132.8226 + 118 0.0000 4.938100 134.3725 + 119 0.0000 4.972151 135.2991 + 120 0.0000 5.056289 137.5886 + 121 0.0000 5.107732 138.9885 + 122 0.0000 5.182318 141.0181 + 123 0.0000 5.207787 141.7111 + 124 0.0000 5.244797 142.7182 + 125 0.0000 5.290492 143.9616 + 126 0.0000 5.392718 146.7433 + 127 0.0000 5.495238 149.5330 + 128 0.0000 5.510845 149.9577 + 129 0.0000 5.700842 155.1278 + 130 0.0000 5.749930 156.4636 + 131 0.0000 5.953767 162.0102 + 132 0.0000 6.163777 167.7249 + 133 0.0000 6.409545 174.4126 + 134 0.0000 6.482340 176.3934 + 135 0.0000 6.513554 177.2428 + 136 0.0000 6.688037 181.9908 + 137 0.0000 6.711716 182.6351 + 138 0.0000 6.779583 184.4818 + 139 0.0000 6.814130 185.4219 + 140 0.0000 6.849591 186.3868 + 141 0.0000 7.076516 192.5618 + 142 0.0000 7.111602 193.5165 + 143 0.0000 7.133336 194.1079 + 144 0.0000 7.210715 196.2135 + 145 0.0000 7.252516 197.3510 + 146 0.0000 7.276155 197.9943 + 147 0.0000 7.329392 199.4429 + 148 0.0000 7.387610 201.0271 + 149 0.0000 7.457888 202.9394 + 150 0.0000 7.473079 203.3528 + 151 0.0000 7.547122 205.3676 + 152 0.0000 7.579305 206.2434 + 153 0.0000 7.658629 208.4019 + 154 0.0000 7.683790 209.0865 + 155 0.0000 7.907232 215.1667 + 156 0.0000 7.983149 217.2325 + 157 0.0000 8.384663 228.1583 + 158 0.0000 14.028690 381.7401 + 159 0.0000 14.947275 406.7360 + 160 0.0000 16.019945 435.9249 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.360975 0.000000 + 1 N : 0.353048 0.000000 + 2 O : -0.240664 0.000000 + 3 H : 0.248592 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.849593 s : 3.849593 + pz : 1.704610 p : 4.478295 + px : 1.282614 + py : 1.491071 + dz2 : 0.002779 d : 0.028769 + dxz : 0.005739 + dyz : 0.001928 + dx2y2 : 0.013695 + dxy : 0.004629 + f0 : 0.000734 f : 0.004318 + f+1 : 0.000845 + f-1 : 0.000144 + f+2 : 0.000562 + f-2 : 0.000171 + f+3 : 0.000982 + f-3 : 0.000881 + 1 N s : 3.828459 s : 3.828459 + pz : 0.811534 p : 2.646821 + px : 0.797741 + py : 1.037546 + dz2 : 0.034167 d : 0.140165 + dxz : 0.031033 + dyz : 0.016567 + dx2y2 : 0.037363 + dxy : 0.021034 + f0 : 0.003030 f : 0.031507 + f+1 : 0.004736 + f-1 : 0.003843 + f+2 : 0.003774 + f-2 : 0.004681 + f+3 : 0.005163 + f-3 : 0.006281 + 2 O s : 3.875218 s : 3.875218 + pz : 1.200861 p : 4.296031 + px : 1.750449 + py : 1.344721 + dz2 : 0.023153 d : 0.061942 + dxz : 0.006980 + dyz : 0.010640 + dx2y2 : 0.008229 + dxy : 0.012939 + f0 : 0.001159 f : 0.007472 + f+1 : 0.000394 + f-1 : 0.001755 + f+2 : 0.001251 + f-2 : 0.001239 + f+3 : 0.000922 + f-3 : 0.000752 + 3 H s : 0.642079 s : 0.642079 + pz : 0.039992 p : 0.088803 + px : 0.024409 + py : 0.024401 + dz2 : 0.005227 d : 0.020526 + dxz : 0.001838 + dyz : 0.002897 + dx2y2 : 0.002628 + dxy : 0.007936 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.579564 0.000000 + 1 N : -0.243225 0.000000 + 2 O : 0.247865 0.000000 + 3 H : -0.584204 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.130300 s : 3.130300 + pz : 1.399536 p : 3.949613 + px : 1.197094 + py : 1.352984 + dz2 : 0.033850 d : 0.263213 + dxz : 0.060972 + dyz : 0.028855 + dx2y2 : 0.081309 + dxy : 0.058228 + f0 : 0.007213 f : 0.077310 + f+1 : 0.015893 + f-1 : 0.000785 + f+2 : 0.013906 + f-2 : 0.006548 + f+3 : 0.012064 + f-3 : 0.020901 + 1 N s : 3.032013 s : 3.032013 + pz : 0.884281 p : 2.836484 + px : 0.859339 + py : 1.092864 + dz2 : 0.155656 d : 0.929885 + dxz : 0.228021 + dyz : 0.170301 + dx2y2 : 0.214510 + dxy : 0.161397 + f0 : 0.040322 f : 0.444844 + f+1 : 0.058251 + f-1 : 0.053405 + f+2 : 0.080091 + f-2 : 0.077241 + f+3 : 0.062681 + f-3 : 0.072852 + 2 O s : 3.311832 s : 3.311832 + pz : 1.211132 p : 3.994705 + px : 1.443882 + py : 1.339691 + dz2 : 0.043180 d : 0.328554 + dxz : 0.060975 + dyz : 0.109799 + dx2y2 : 0.075419 + dxy : 0.039181 + f0 : 0.011427 f : 0.117044 + f+1 : 0.008542 + f-1 : 0.022385 + f+2 : 0.031902 + f-2 : 0.020788 + f+3 : 0.006570 + f-3 : 0.015430 + 3 H s : 0.624054 s : 0.624054 + pz : 0.184016 p : 0.569334 + px : 0.138569 + py : 0.246750 + dz2 : 0.070347 d : 0.390816 + dxz : 0.042094 + dyz : 0.103074 + dx2y2 : 0.084618 + dxy : 0.090683 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3610 8.0000 -0.3610 1.8174 1.8174 0.0000 + 1 N 6.6470 7.0000 0.3530 2.5763 2.5763 0.0000 + 2 O 8.2407 8.0000 -0.2407 1.7853 1.7853 0.0000 + 3 H 0.7514 1.0000 0.2486 1.0033 1.0033 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8048 B( 0-O , 3-H ) : 0.9531 B( 1-N , 2-O ) : 1.7236 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.471 sec +Sum of individual times .... 0.295 sec ( 62.6%) + +Fock matrix formation .... 0.220 sec ( 46.6%) +Diagonalization .... 0.022 sec ( 4.6%) +Density matrix formation .... 0.002 sec ( 0.4%) +Population analysis .... 0.030 sec ( 6.3%) +Initial guess .... 0.010 sec ( 2.2%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 1.0%) +DIIS solution .... 0.012 sec ( 2.5%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.211 sec +Reference energy ... -204.707695944 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.400 sec +AO-integral generation ... 0.146 sec +Half transformation ... 0.079 sec +K-integral sorting ... 5.410 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.028 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.030 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.023 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.351 sec +AO-integral generation ... 0.241 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.055 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.152 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.254 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090066070 +EMP2(bb)= -0.090066070 +EMP2(ab)= -0.516764300 + +Initial guess performed in 0.133 sec +E(0) ... -204.707695944 +E(MP2) ... -0.696896441 +Initial E(tot) ... -205.404592385 + ... 0.188808742 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.404592388 -0.696896443 -0.000000003 0.020496776 2.76 0.000040136 + *** Turning on DIIS *** + 1 -205.376326374 -0.668630430 0.028266013 0.009589448 2.70 0.056097085 + 2 -205.395815945 -0.688120001 -0.019489571 0.004245225 2.76 0.059009675 + 3 -205.399621454 -0.691925510 -0.003805509 0.001778069 2.82 0.072434623 + 4 -205.401171963 -0.693476018 -0.001550508 0.001177931 2.81 0.078612740 + 5 -205.401685642 -0.693989698 -0.000513679 0.000741873 2.89 0.083472331 + 6 -205.401779077 -0.694083133 -0.000093435 0.000463779 2.81 0.085904899 + 7 -205.401819823 -0.694123879 -0.000040746 0.000248395 2.86 0.087091355 + 8 -205.401830281 -0.694134337 -0.000010458 0.000148165 2.87 0.087645251 + 9 -205.401827133 -0.694131189 0.000003148 0.000088530 2.78 0.087858427 + 10 -205.401832601 -0.694136657 -0.000005468 0.000048375 2.75 0.087948106 + 11 -205.401828983 -0.694133039 0.000003618 0.000030431 2.75 0.087954270 + 12 -205.401831688 -0.694135743 -0.000002704 0.000018060 2.76 0.087972941 + 13 -205.401831274 -0.694135330 0.000000414 0.000010029 2.77 0.087971214 + 14 -205.401831836 -0.694135892 -0.000000562 0.000004518 2.82 0.087978614 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.707695944 +E(CORR) ... -0.694135892 +E(TOT) ... -205.401831836 +Singles norm **1/2 ... 0.087978614 ( 0.043989307, 0.043989307) +T1 diagnostic ... 0.020736758 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.056214 + 9a-> 13a 9b-> 13b 0.055374 + 8a-> 13a 9b-> 13b 0.042755 + 9a-> 13a 8b-> 13b 0.042755 + 8a-> 13a -1a-> -1a 0.031595 + 8b-> 13b -1b-> -1b 0.031595 + 11a-> 13a 11b-> 13b 0.029520 + 5a-> 13a 5b-> 13b 0.029164 + 11a-> 25a 11b-> 25b 0.026201 + 10a-> 13a -1a-> -1a 0.024046 + 10b-> 13b -1b-> -1b 0.024046 + 9a-> 13a 9b-> 22b 0.021423 + 9a-> 22a 9b-> 13b 0.021423 + 11a-> 25a -1a-> -1a 0.021238 + 11b-> 25b -1b-> -1b 0.021238 + 8a-> 13a 8b-> 22b 0.020348 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034519362 + alpha-alpha-alpha ... -0.000872195 ( 2.5%) + alpha-alpha-beta ... -0.016387486 ( 47.5%) + alpha-beta -beta ... -0.016387486 ( 47.5%) + beta -beta -beta ... -0.000872195 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034519362 + +Final correlation energy ... -0.728655254 +E(CCSD) ... -205.401831836 +E(CCSD(T)) ... -205.436351198 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210491369 sqrt= 1.100223327 +W(HF) = 0.826110806 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.297948 -0.000000 + 1 N : 0.176426 0.000000 + 2 O : -0.115544 -0.000000 + 3 H : 0.237066 -0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.830981 s : 3.830981 + pz : 1.667586 p : 4.399536 + px : 1.266785 + py : 1.465165 + dz2 : 0.009837 d : 0.059392 + dxz : 0.011872 + dyz : 0.008389 + dx2y2 : 0.017415 + dxy : 0.011879 + f0 : 0.001241 f : 0.008039 + f+1 : 0.001373 + f-1 : 0.000794 + f+2 : 0.001053 + f-2 : 0.000821 + f+3 : 0.001361 + f-3 : 0.001396 + 1 N s : 3.882556 s : 3.882556 + pz : 0.862266 p : 2.741256 + px : 0.844693 + py : 1.034296 + dz2 : 0.036116 d : 0.169338 + dxz : 0.040866 + dyz : 0.021211 + dx2y2 : 0.043599 + dxy : 0.027547 + f0 : 0.002865 f : 0.030423 + f+1 : 0.004855 + f-1 : 0.003296 + f+2 : 0.003596 + f-2 : 0.004558 + f+3 : 0.005014 + f-3 : 0.006239 + 2 O s : 3.861825 s : 3.861825 + pz : 1.174963 p : 4.160579 + px : 1.671520 + py : 1.314096 + dz2 : 0.024092 d : 0.083259 + dxz : 0.013704 + dyz : 0.013747 + dx2y2 : 0.014148 + dxy : 0.017568 + f0 : 0.001391 f : 0.009880 + f+1 : 0.000956 + f-1 : 0.001733 + f+2 : 0.001582 + f-2 : 0.001604 + f+3 : 0.001375 + f-3 : 0.001240 + 3 H s : 0.650539 s : 0.650539 + pz : 0.044503 p : 0.094655 + px : 0.027777 + py : 0.022375 + dz2 : 0.004742 d : 0.017741 + dxz : 0.001854 + dyz : 0.002122 + dx2y2 : 0.001872 + dxy : 0.007150 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.587061 0.000000 + 1 N : -0.287846 -0.000000 + 2 O : 0.289311 -0.000000 + 3 H : -0.588526 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.135585 s : 3.135585 + pz : 1.371118 p : 3.898639 + px : 1.194791 + py : 1.332730 + dz2 : 0.039634 d : 0.294369 + dxz : 0.067517 + dyz : 0.036014 + dx2y2 : 0.087794 + dxy : 0.063410 + f0 : 0.008371 f : 0.084346 + f+1 : 0.016476 + f-1 : 0.001393 + f+2 : 0.015500 + f-2 : 0.007526 + f+3 : 0.013696 + f-3 : 0.021383 + 1 N s : 3.037225 s : 3.037225 + pz : 0.913061 p : 2.878692 + px : 0.879632 + py : 1.085998 + dz2 : 0.154128 d : 0.936779 + dxz : 0.230453 + dyz : 0.176728 + dx2y2 : 0.217978 + dxy : 0.157492 + f0 : 0.040688 f : 0.435149 + f+1 : 0.055177 + f-1 : 0.053567 + f+2 : 0.077623 + f-2 : 0.074176 + f+3 : 0.063313 + f-3 : 0.070606 + 2 O s : 3.314383 s : 3.314383 + pz : 1.196366 p : 3.912968 + px : 1.394436 + py : 1.322166 + dz2 : 0.053273 d : 0.357875 + dxz : 0.065107 + dyz : 0.114343 + dx2y2 : 0.080186 + dxy : 0.044967 + f0 : 0.013820 f : 0.125463 + f+1 : 0.009352 + f-1 : 0.025228 + f+2 : 0.031630 + f-2 : 0.021820 + f+3 : 0.008074 + f-3 : 0.015540 + 3 H s : 0.625270 s : 0.625270 + pz : 0.191031 p : 0.582793 + px : 0.138597 + py : 0.253166 + dz2 : 0.068305 d : 0.380462 + dxz : 0.040533 + dyz : 0.100690 + dx2y2 : 0.083210 + dxy : 0.087724 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2979 8.0000 -0.2979 2.1709 1.7113 0.4596 + 1 N 6.8236 7.0000 0.1764 2.8441 2.3539 0.4902 + 2 O 8.1155 8.0000 -0.1155 2.1718 1.6734 0.4984 + 3 H 0.7629 1.0000 0.2371 1.0215 0.9470 0.0746 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7293 B( 0-O , 3-H ) : 0.8883 B( 1-N , 2-O ) : 1.5729 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 57.121 sec + +Fock Matrix Formation ... 0.211 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 1.912 sec ( 3.3%) +State Vector Update ... 0.089 sec ( 0.2%) +Sigma-vector construction ... 39.902 sec ( 69.9%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (0-ext) ... 0.075 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.028 sec ( 0.1% of sigma) + (2-ext) ... 1.014 sec ( 2.5% of sigma) + (4-ext) ... 21.975 sec ( 55.1% of sigma) + ... 1.403 sec ( 3.5% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.115 sec ( 0.3% of sigma) + Fock-dressing ... 2.349 sec ( 5.9% of sigma) + (ik|jl)-dressing ... 0.081 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.049 sec ( 25.2% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.963 sec ( 12.2% of ALL) + I/O of integral and amplitudes ... 0.882 sec ( 12.7% of (T)) + External N**7 contributions ... 3.970 sec ( 57.0% of (T)) + Internal N**7 contributions ... 0.329 sec ( 4.7% of (T)) + N**6 triples energy contributions ... 1.699 sec ( 24.4% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.436351197968 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.015.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.015.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.387432, -0.277134 -0.478647) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.96252 -0.16448 -0.62646 +Nuclear contribution : -0.87294 0.63488 1.00427 + ----------------------------------------- +Total Dipole Moment : 0.08958 0.47040 0.37780 + ----------------------------------------- +Magnitude (a.u.) : 0.60995 +Magnitude (Debye) : 1.55037 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.719257 0.406385 0.363350 +Rotational constants in MHz : 81521.264993 12183.114313 10892.946292 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.052946 0.239305 0.558540 +x,y,z [Debye]: -0.134579 0.608264 1.419697 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.387432, -0.277134 -0.478647) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 1.00099 -0.10129 -0.76111 +Nuclear contribution : -0.87294 0.63488 1.00427 + ----------------------------------------- +Total Dipole Moment : 0.12805 0.53359 0.24315 + ----------------------------------------- +Magnitude (a.u.) : 0.60019 +Magnitude (Debye) : 1.52557 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.719257 0.406385 0.363350 +Rotational constants in MHz : 81521.264993 12183.114313 10892.946292 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.070629 0.314261 0.506444 +x,y,z [Debye]: 0.179525 0.798788 1.287278 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 16 * + * * + * Dihedral ( 2, 1, 0, 3) : -57.27272727 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0370187824 RMS(Int)= 0.0007951726 + Iter 1: RMS(Cart)= 0.0002061372 RMS(Int)= 0.0000106653 + Iter 2: RMS(Cart)= 0.0000027648 RMS(Int)= 0.0000001437 + Iter 3: RMS(Cart)= 0.0000000372 RMS(Int)= 0.0000000019 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4845 0.000000 + 2. B(O 2,N 1) 1.1715 0.000000 + 3. B(H 3,O 0) 0.9731 0.000000 + 4. A(N 1,O 0,H 3) 103.9695 0.000000 + 5. A(O 0,N 1,O 2) 111.9026 0.000000 + 6. D(O 2,N 1,O 0,H 3) -57.2727 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.762303 -0.333022 0.368033 + N 0.593432 -0.533087 -0.202756 + O 0.883326 0.321141 -0.950200 + H -0.714454 0.544968 0.784923 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.440545 -0.629321 0.695482 + 1 N 7.0000 0 14.007 1.121425 -1.007389 -0.383154 + 2 O 8.0000 0 15.999 1.669245 0.606869 -1.795617 + 3 H 1.0000 0 1.008 -1.350123 1.029841 1.483290 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.483746780543 0.00000000 0.00000000 + O 2 1 0 1.169803698496 112.03249587 0.00000000 + H 1 2 3 0.970705379599 104.11324147 294.54545446 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.803875067313 0.00000000 0.00000000 + O 2 1 0 2.210608620606 112.03249587 0.00000000 + H 1 2 3 1.834367324166 104.11324147 294.54545446 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2235 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2705 + la=0 lb=0: 553 shell pairs + la=1 lb=0: 537 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.623658955322 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.6236589553 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.686e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7041763266 0.000000000000 0.00171249 0.00005010 0.0178908 0.7000 + 1 -204.7050081521 -0.000831825541 0.00157236 0.00004631 0.0148664 0.7000 + ***Turning on DIIS*** + 2 -204.7057271850 -0.000719032890 0.00433965 0.00012813 0.0121359 0.0000 + 3 -204.7098582593 -0.004131074316 0.00188301 0.00006003 0.0049048 0.0000 + 4 -204.7072684980 0.002589761270 0.00088621 0.00003163 0.0019518 0.0000 + 5 -204.7093523938 -0.002083895784 0.00080022 0.00002715 0.0011153 0.0000 + 6 -204.7084118019 0.000940591932 0.00085953 0.00003197 0.0007128 0.0000 + 7 -204.7080812982 0.000330503705 0.00036458 0.00001543 0.0002781 0.0000 + 8 -204.7088608986 -0.000779600398 0.00020075 0.00000913 0.0001856 0.0000 + 9 -204.7083529301 0.000507968476 0.00016468 0.00000590 0.0001202 0.0000 + 10 -204.7085106767 -0.000157746618 0.00004943 0.00000209 0.0000746 0.0000 + 11 -204.7086049053 -0.000094228527 0.00003022 0.00000087 0.0000341 0.0000 + 12 -204.7085321692 0.000072736075 0.00000794 0.00000027 0.0000090 0.0000 + 13 -204.7085534138 -0.000021244649 0.00000213 0.00000009 0.0000028 0.0000 + 14 -204.7085498426 0.000003571222 0.00000086 0.00000004 0.0000022 0.0000 + 15 -204.7085503405 -0.000000497858 0.00000085 0.00000003 0.0000019 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 16 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70855175 Eh -5570.40289 eV + +Components: +Nuclear Repulsion : 68.62365896 Eh 1867.34469 eV +Electronic Energy : -273.33221070 Eh -7437.74758 eV +One Electron Energy: -416.91756891 Eh -11344.90381 eV +Two Electron Energy: 143.58535821 Eh 3907.15623 eV + +Virial components: +Potential Energy : -408.92176887 Eh -11127.32703 eV +Kinetic Energy : 204.21321712 Eh 5556.92415 eV +Virial Ratio : 2.00242558 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.4063e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.6204e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.3439e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.2128e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.687572 -562.9374 + 1 1.0000 -20.624516 -561.2216 + 2 1.0000 -15.806839 -430.1260 + 3 1.0000 -1.614307 -43.9275 + 4 1.0000 -1.378610 -37.5139 + 5 1.0000 -0.958954 -26.0945 + 6 1.0000 -0.768072 -20.9003 + 7 1.0000 -0.736424 -20.0391 + 8 1.0000 -0.696387 -18.9497 + 9 1.0000 -0.605951 -16.4888 + 10 1.0000 -0.531475 -14.4622 + 11 1.0000 -0.464321 -12.6348 + 12 0.0000 0.031323 0.8524 + 13 0.0000 0.066416 1.8073 + 14 0.0000 0.092763 2.5242 + 15 0.0000 0.107797 2.9333 + 16 0.0000 0.114520 3.1162 + 17 0.0000 0.154507 4.2044 + 18 0.0000 0.157640 4.2896 + 19 0.0000 0.171833 4.6758 + 20 0.0000 0.179670 4.8891 + 21 0.0000 0.191139 5.2012 + 22 0.0000 0.201918 5.4945 + 23 0.0000 0.234202 6.3730 + 24 0.0000 0.269015 7.3203 + 25 0.0000 0.282069 7.6755 + 26 0.0000 0.308259 8.3881 + 27 0.0000 0.333892 9.0857 + 28 0.0000 0.341351 9.2886 + 29 0.0000 0.361838 9.8461 + 30 0.0000 0.422561 11.4985 + 31 0.0000 0.511976 13.9316 + 32 0.0000 0.531773 14.4703 + 33 0.0000 0.536977 14.6119 + 34 0.0000 0.560064 15.2401 + 35 0.0000 0.604198 16.4411 + 36 0.0000 0.633618 17.2416 + 37 0.0000 0.645336 17.5605 + 38 0.0000 0.699364 19.0307 + 39 0.0000 0.714617 19.4457 + 40 0.0000 0.733650 19.9636 + 41 0.0000 0.744377 20.2555 + 42 0.0000 0.767361 20.8810 + 43 0.0000 0.783439 21.3184 + 44 0.0000 0.814935 22.1755 + 45 0.0000 0.823497 22.4085 + 46 0.0000 0.851618 23.1737 + 47 0.0000 0.882006 24.0006 + 48 0.0000 0.908218 24.7139 + 49 0.0000 0.946398 25.7528 + 50 0.0000 0.973999 26.5039 + 51 0.0000 0.982008 26.7218 + 52 0.0000 0.993903 27.0455 + 53 0.0000 1.019969 27.7548 + 54 0.0000 1.049839 28.5676 + 55 0.0000 1.088979 29.6326 + 56 0.0000 1.156692 31.4752 + 57 0.0000 1.208730 32.8912 + 58 0.0000 1.225690 33.3527 + 59 0.0000 1.280262 34.8377 + 60 0.0000 1.339057 36.4376 + 61 0.0000 1.412269 38.4298 + 62 0.0000 1.461725 39.7756 + 63 0.0000 1.510611 41.1058 + 64 0.0000 1.531613 41.6773 + 65 0.0000 1.568298 42.6756 + 66 0.0000 1.602833 43.6153 + 67 0.0000 1.631680 44.4003 + 68 0.0000 1.653908 45.0051 + 69 0.0000 1.728411 47.0324 + 70 0.0000 1.750041 47.6210 + 71 0.0000 1.784105 48.5480 + 72 0.0000 1.921541 52.2878 + 73 0.0000 1.938649 52.7533 + 74 0.0000 1.964810 53.4652 + 75 0.0000 2.002173 54.4819 + 76 0.0000 2.046347 55.6839 + 77 0.0000 2.074741 56.4566 + 78 0.0000 2.153905 58.6107 + 79 0.0000 2.176478 59.2250 + 80 0.0000 2.253079 61.3094 + 81 0.0000 2.308426 62.8155 + 82 0.0000 2.332990 63.4839 + 83 0.0000 2.379761 64.7566 + 84 0.0000 2.421757 65.8994 + 85 0.0000 2.452215 66.7282 + 86 0.0000 2.467235 67.1369 + 87 0.0000 2.488082 67.7042 + 88 0.0000 2.513831 68.4048 + 89 0.0000 2.553666 69.4888 + 90 0.0000 2.584392 70.3249 + 91 0.0000 2.605425 70.8972 + 92 0.0000 2.661167 72.4140 + 93 0.0000 2.681665 72.9718 + 94 0.0000 2.753876 74.9368 + 95 0.0000 2.805641 76.3454 + 96 0.0000 2.819746 76.7292 + 97 0.0000 2.915282 79.3288 + 98 0.0000 2.963613 80.6440 + 99 0.0000 2.973732 80.9194 + 100 0.0000 3.104668 84.4823 + 101 0.0000 3.170165 86.2646 + 102 0.0000 3.227469 87.8239 + 103 0.0000 3.489829 94.9631 + 104 0.0000 3.691729 100.4570 + 105 0.0000 3.852399 104.8291 + 106 0.0000 4.026506 109.5668 + 107 0.0000 4.157719 113.1373 + 108 0.0000 4.199191 114.2658 + 109 0.0000 4.318276 117.5063 + 110 0.0000 4.359400 118.6253 + 111 0.0000 4.385914 119.3468 + 112 0.0000 4.545283 123.6834 + 113 0.0000 4.610200 125.4499 + 114 0.0000 4.663673 126.9050 + 115 0.0000 4.744667 129.1090 + 116 0.0000 4.813999 130.9956 + 117 0.0000 4.873181 132.6060 + 118 0.0000 4.944379 134.5434 + 119 0.0000 4.976641 135.4213 + 120 0.0000 5.059249 137.6692 + 121 0.0000 5.104097 138.8895 + 122 0.0000 5.179475 140.9407 + 123 0.0000 5.214755 141.9007 + 124 0.0000 5.245467 142.7364 + 125 0.0000 5.283049 143.7591 + 126 0.0000 5.384849 146.5292 + 127 0.0000 5.465245 148.7169 + 128 0.0000 5.510304 149.9430 + 129 0.0000 5.700627 155.1220 + 130 0.0000 5.756498 156.6423 + 131 0.0000 5.949276 161.8880 + 132 0.0000 6.161609 167.6659 + 133 0.0000 6.396817 174.0662 + 134 0.0000 6.483728 176.4312 + 135 0.0000 6.515140 177.2860 + 136 0.0000 6.687059 181.9641 + 137 0.0000 6.712834 182.6655 + 138 0.0000 6.780055 184.4947 + 139 0.0000 6.809921 185.3074 + 140 0.0000 6.857967 186.6148 + 141 0.0000 7.071658 192.4296 + 142 0.0000 7.113242 193.5612 + 143 0.0000 7.136592 194.1965 + 144 0.0000 7.207618 196.1293 + 145 0.0000 7.249229 197.2616 + 146 0.0000 7.267402 197.7561 + 147 0.0000 7.324578 199.3119 + 148 0.0000 7.385592 200.9722 + 149 0.0000 7.461827 203.0466 + 150 0.0000 7.470628 203.2861 + 151 0.0000 7.531046 204.9302 + 152 0.0000 7.570561 206.0054 + 153 0.0000 7.668507 208.6707 + 154 0.0000 7.672441 208.7777 + 155 0.0000 7.905011 215.1063 + 156 0.0000 7.995710 217.5743 + 157 0.0000 8.368271 227.7122 + 158 0.0000 14.004015 381.0686 + 159 0.0000 14.898334 405.4043 + 160 0.0000 15.966201 434.4624 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.687572 -562.9374 + 1 1.0000 -20.624516 -561.2216 + 2 1.0000 -15.806839 -430.1260 + 3 1.0000 -1.614307 -43.9275 + 4 1.0000 -1.378610 -37.5139 + 5 1.0000 -0.958954 -26.0945 + 6 1.0000 -0.768072 -20.9003 + 7 1.0000 -0.736424 -20.0391 + 8 1.0000 -0.696387 -18.9497 + 9 1.0000 -0.605951 -16.4888 + 10 1.0000 -0.531475 -14.4622 + 11 1.0000 -0.464321 -12.6348 + 12 0.0000 0.031323 0.8524 + 13 0.0000 0.066416 1.8073 + 14 0.0000 0.092763 2.5242 + 15 0.0000 0.107797 2.9333 + 16 0.0000 0.114520 3.1162 + 17 0.0000 0.154507 4.2044 + 18 0.0000 0.157640 4.2896 + 19 0.0000 0.171833 4.6758 + 20 0.0000 0.179670 4.8891 + 21 0.0000 0.191139 5.2012 + 22 0.0000 0.201918 5.4945 + 23 0.0000 0.234202 6.3730 + 24 0.0000 0.269015 7.3203 + 25 0.0000 0.282069 7.6755 + 26 0.0000 0.308259 8.3881 + 27 0.0000 0.333892 9.0857 + 28 0.0000 0.341351 9.2886 + 29 0.0000 0.361838 9.8461 + 30 0.0000 0.422561 11.4985 + 31 0.0000 0.511976 13.9316 + 32 0.0000 0.531773 14.4703 + 33 0.0000 0.536977 14.6119 + 34 0.0000 0.560064 15.2401 + 35 0.0000 0.604198 16.4411 + 36 0.0000 0.633618 17.2416 + 37 0.0000 0.645336 17.5605 + 38 0.0000 0.699364 19.0307 + 39 0.0000 0.714617 19.4457 + 40 0.0000 0.733650 19.9636 + 41 0.0000 0.744377 20.2555 + 42 0.0000 0.767361 20.8810 + 43 0.0000 0.783439 21.3184 + 44 0.0000 0.814935 22.1755 + 45 0.0000 0.823497 22.4085 + 46 0.0000 0.851618 23.1737 + 47 0.0000 0.882006 24.0006 + 48 0.0000 0.908218 24.7139 + 49 0.0000 0.946398 25.7528 + 50 0.0000 0.973999 26.5039 + 51 0.0000 0.982008 26.7218 + 52 0.0000 0.993903 27.0455 + 53 0.0000 1.019969 27.7548 + 54 0.0000 1.049839 28.5676 + 55 0.0000 1.088979 29.6326 + 56 0.0000 1.156692 31.4752 + 57 0.0000 1.208730 32.8912 + 58 0.0000 1.225690 33.3527 + 59 0.0000 1.280262 34.8377 + 60 0.0000 1.339057 36.4376 + 61 0.0000 1.412269 38.4298 + 62 0.0000 1.461725 39.7756 + 63 0.0000 1.510611 41.1058 + 64 0.0000 1.531613 41.6773 + 65 0.0000 1.568298 42.6756 + 66 0.0000 1.602833 43.6153 + 67 0.0000 1.631680 44.4003 + 68 0.0000 1.653908 45.0051 + 69 0.0000 1.728411 47.0324 + 70 0.0000 1.750041 47.6210 + 71 0.0000 1.784105 48.5480 + 72 0.0000 1.921541 52.2878 + 73 0.0000 1.938649 52.7533 + 74 0.0000 1.964810 53.4652 + 75 0.0000 2.002173 54.4819 + 76 0.0000 2.046347 55.6839 + 77 0.0000 2.074741 56.4566 + 78 0.0000 2.153905 58.6107 + 79 0.0000 2.176478 59.2250 + 80 0.0000 2.253079 61.3094 + 81 0.0000 2.308426 62.8155 + 82 0.0000 2.332990 63.4839 + 83 0.0000 2.379761 64.7566 + 84 0.0000 2.421757 65.8994 + 85 0.0000 2.452215 66.7282 + 86 0.0000 2.467235 67.1369 + 87 0.0000 2.488082 67.7042 + 88 0.0000 2.513831 68.4048 + 89 0.0000 2.553666 69.4888 + 90 0.0000 2.584392 70.3249 + 91 0.0000 2.605425 70.8972 + 92 0.0000 2.661167 72.4140 + 93 0.0000 2.681665 72.9718 + 94 0.0000 2.753876 74.9368 + 95 0.0000 2.805641 76.3454 + 96 0.0000 2.819746 76.7292 + 97 0.0000 2.915282 79.3288 + 98 0.0000 2.963613 80.6440 + 99 0.0000 2.973732 80.9194 + 100 0.0000 3.104668 84.4823 + 101 0.0000 3.170165 86.2646 + 102 0.0000 3.227469 87.8239 + 103 0.0000 3.489829 94.9631 + 104 0.0000 3.691729 100.4570 + 105 0.0000 3.852399 104.8291 + 106 0.0000 4.026506 109.5668 + 107 0.0000 4.157719 113.1373 + 108 0.0000 4.199191 114.2658 + 109 0.0000 4.318276 117.5063 + 110 0.0000 4.359400 118.6253 + 111 0.0000 4.385914 119.3468 + 112 0.0000 4.545283 123.6834 + 113 0.0000 4.610200 125.4499 + 114 0.0000 4.663673 126.9050 + 115 0.0000 4.744667 129.1090 + 116 0.0000 4.813999 130.9956 + 117 0.0000 4.873181 132.6060 + 118 0.0000 4.944379 134.5434 + 119 0.0000 4.976641 135.4213 + 120 0.0000 5.059249 137.6692 + 121 0.0000 5.104097 138.8895 + 122 0.0000 5.179475 140.9407 + 123 0.0000 5.214755 141.9007 + 124 0.0000 5.245467 142.7364 + 125 0.0000 5.283049 143.7591 + 126 0.0000 5.384849 146.5292 + 127 0.0000 5.465245 148.7169 + 128 0.0000 5.510304 149.9430 + 129 0.0000 5.700627 155.1220 + 130 0.0000 5.756498 156.6423 + 131 0.0000 5.949276 161.8880 + 132 0.0000 6.161609 167.6659 + 133 0.0000 6.396817 174.0662 + 134 0.0000 6.483728 176.4312 + 135 0.0000 6.515140 177.2860 + 136 0.0000 6.687059 181.9641 + 137 0.0000 6.712834 182.6655 + 138 0.0000 6.780055 184.4947 + 139 0.0000 6.809921 185.3074 + 140 0.0000 6.857967 186.6148 + 141 0.0000 7.071658 192.4296 + 142 0.0000 7.113242 193.5612 + 143 0.0000 7.136592 194.1965 + 144 0.0000 7.207618 196.1293 + 145 0.0000 7.249229 197.2616 + 146 0.0000 7.267402 197.7561 + 147 0.0000 7.324578 199.3119 + 148 0.0000 7.385592 200.9722 + 149 0.0000 7.461827 203.0466 + 150 0.0000 7.470628 203.2861 + 151 0.0000 7.531046 204.9302 + 152 0.0000 7.570561 206.0054 + 153 0.0000 7.668507 208.6707 + 154 0.0000 7.672441 208.7777 + 155 0.0000 7.905011 215.1063 + 156 0.0000 7.995710 217.5743 + 157 0.0000 8.368271 227.7122 + 158 0.0000 14.004015 381.0686 + 159 0.0000 14.898334 405.4043 + 160 0.0000 15.966201 434.4624 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.360241 0.000000 + 1 N : 0.356434 0.000000 + 2 O : -0.247191 0.000000 + 3 H : 0.250998 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.846885 s : 3.846885 + pz : 1.717856 p : 4.479150 + px : 1.298250 + py : 1.463045 + dz2 : 0.003254 d : 0.029818 + dxz : 0.006289 + dyz : 0.001521 + dx2y2 : 0.014171 + dxy : 0.004582 + f0 : 0.000731 f : 0.004388 + f+1 : 0.000878 + f-1 : 0.000138 + f+2 : 0.000570 + f-2 : 0.000262 + f+3 : 0.000930 + f-3 : 0.000879 + 1 N s : 3.832755 s : 3.832755 + pz : 0.788479 p : 2.639009 + px : 0.786553 + py : 1.063977 + dz2 : 0.032794 d : 0.140253 + dxz : 0.030599 + dyz : 0.018200 + dx2y2 : 0.037843 + dxy : 0.020817 + f0 : 0.002486 f : 0.031548 + f+1 : 0.004525 + f-1 : 0.004243 + f+2 : 0.003556 + f-2 : 0.004822 + f+3 : 0.005488 + f-3 : 0.006429 + 2 O s : 3.874002 s : 3.874002 + pz : 1.214802 p : 4.303658 + px : 1.735492 + py : 1.353365 + dz2 : 0.021712 d : 0.062010 + dxz : 0.006204 + dyz : 0.011299 + dx2y2 : 0.008604 + dxy : 0.014192 + f0 : 0.000890 f : 0.007521 + f+1 : 0.000290 + f-1 : 0.001919 + f+2 : 0.001300 + f-2 : 0.001212 + f+3 : 0.001046 + f-3 : 0.000864 + 3 H s : 0.640970 s : 0.640970 + pz : 0.040130 p : 0.087700 + px : 0.024670 + py : 0.022899 + dz2 : 0.004102 d : 0.020333 + dxz : 0.001084 + dyz : 0.004242 + dx2y2 : 0.002268 + dxy : 0.008636 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.577875 0.000000 + 1 N : -0.240599 0.000000 + 2 O : 0.246409 0.000000 + 3 H : -0.583685 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.132529 s : 3.132529 + pz : 1.401793 p : 3.948769 + px : 1.205052 + py : 1.341924 + dz2 : 0.033787 d : 0.263499 + dxz : 0.062920 + dyz : 0.028076 + dx2y2 : 0.080067 + dxy : 0.058651 + f0 : 0.007511 f : 0.077328 + f+1 : 0.015182 + f-1 : 0.000548 + f+2 : 0.013666 + f-2 : 0.007702 + f+3 : 0.011422 + f-3 : 0.021296 + 1 N s : 3.033668 s : 3.033668 + pz : 0.851845 p : 2.833514 + px : 0.850655 + py : 1.131014 + dz2 : 0.152886 d : 0.928198 + dxz : 0.219596 + dyz : 0.168370 + dx2y2 : 0.222169 + dxy : 0.165178 + f0 : 0.036501 f : 0.445219 + f+1 : 0.054201 + f-1 : 0.053357 + f+2 : 0.079368 + f-2 : 0.079210 + f+3 : 0.066249 + f-3 : 0.076333 + 2 O s : 3.310299 s : 3.310299 + pz : 1.199937 p : 3.998247 + px : 1.432994 + py : 1.365315 + dz2 : 0.040193 d : 0.328411 + dxz : 0.056978 + dyz : 0.105309 + dx2y2 : 0.083445 + dxy : 0.042487 + f0 : 0.010667 f : 0.116634 + f+1 : 0.007018 + f-1 : 0.020897 + f+2 : 0.031225 + f-2 : 0.020968 + f+3 : 0.007774 + f-3 : 0.018085 + 3 H s : 0.623056 s : 0.623056 + pz : 0.176374 p : 0.567253 + px : 0.138917 + py : 0.251961 + dz2 : 0.062721 d : 0.393377 + dxz : 0.037164 + dyz : 0.106580 + dx2y2 : 0.089250 + dxy : 0.097661 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3602 8.0000 -0.3602 1.8204 1.8204 0.0000 + 1 N 6.6436 7.0000 0.3564 2.5724 2.5724 -0.0000 + 2 O 8.2472 8.0000 -0.2472 1.7765 1.7765 0.0000 + 3 H 0.7490 1.0000 0.2510 1.0031 1.0031 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8095 B( 0-O , 3-H ) : 0.9497 B( 1-N , 2-O ) : 1.7124 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.434 sec +Sum of individual times .... 2.230 sec ( 91.6%) + +Fock matrix formation .... 1.820 sec ( 74.8%) +Diagonalization .... 0.196 sec ( 8.1%) +Density matrix formation .... 0.014 sec ( 0.6%) +Population analysis .... 0.030 sec ( 1.2%) +Initial guess .... 0.010 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.2%) +DIIS solution .... 0.159 sec ( 6.5%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.204 sec +Reference energy ... -204.708551564 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.379 sec +AO-integral generation ... 0.142 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.385 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.024 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.027 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.030 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.038 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.023 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.346 sec +AO-integral generation ... 0.239 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.051 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.149 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.250 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090269190 +EMP2(bb)= -0.090269190 +EMP2(ab)= -0.517406014 + +Initial guess performed in 0.132 sec +E(0) ... -204.708551564 +E(MP2) ... -0.697944394 +Initial E(tot) ... -205.406495959 + ... 0.189583482 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.406495959 -0.697944394 -0.000000000 0.021536861 2.71 0.000002842 + *** Turning on DIIS *** + 1 -205.377625761 -0.669074196 0.028870198 0.009832338 2.70 0.056997107 + 2 -205.397289814 -0.688738250 -0.019664053 0.004531401 2.77 0.059908358 + 3 -205.401115501 -0.692563937 -0.003825687 0.001746270 2.80 0.073776947 + 4 -205.402695358 -0.694143794 -0.001579857 0.001461579 2.77 0.080278134 + 5 -205.403238453 -0.694686889 -0.000543094 0.000902846 2.88 0.085589788 + 6 -205.403343486 -0.694791922 -0.000105033 0.000560994 2.80 0.088356653 + 7 -205.403391008 -0.694839443 -0.000047521 0.000278946 2.82 0.089759743 + 8 -205.403403812 -0.694852248 -0.000012804 0.000132294 2.84 0.090392704 + 9 -205.403400088 -0.694848524 0.000003724 0.000073291 2.80 0.090608521 + 10 -205.403406087 -0.694854523 -0.000005999 0.000042267 2.74 0.090699389 + 11 -205.403402380 -0.694850815 0.000003707 0.000029024 2.75 0.090692211 + 12 -205.403404703 -0.694853138 -0.000002323 0.000017914 2.75 0.090714141 + 13 -205.403404436 -0.694852871 0.000000267 0.000010808 2.76 0.090708336 + 14 -205.403404793 -0.694853229 -0.000000358 0.000005083 2.75 0.090715349 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.708551564 +E(CORR) ... -0.694853229 +E(TOT) ... -205.403404793 +Singles norm **1/2 ... 0.090715349 ( 0.045357674, 0.045357674) +T1 diagnostic ... 0.021381813 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.058450 + 9a-> 13a 9b-> 13b 0.049096 + 9a-> 13a 8b-> 13b 0.040367 + 8a-> 13a 9b-> 13b 0.040367 + 8b-> 13b -1b-> -1b 0.033802 + 8a-> 13a -1a-> -1a 0.033802 + 11a-> 25a 11b-> 25b 0.032289 + 10a-> 13a -1a-> -1a 0.029682 + 10b-> 13b -1b-> -1b 0.029682 + 11a-> 13a 11b-> 13b 0.029150 + 5a-> 13a 5b-> 13b 0.029067 + 11b-> 25b -1b-> -1b 0.025029 + 11a-> 25a -1a-> -1a 0.025029 + 8a-> 22a 8b-> 13b 0.021319 + 8a-> 13a 8b-> 22b 0.021319 + 10a-> 13a 9b-> 13b 0.020808 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034809022 + alpha-alpha-alpha ... -0.000882445 ( 2.5%) + alpha-alpha-beta ... -0.016522066 ( 47.5%) + alpha-beta -beta ... -0.016522066 ( 47.5%) + beta -beta -beta ... -0.000882445 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034809022 + +Final correlation energy ... -0.729662251 +E(CCSD) ... -205.403404793 +E(CCSD(T)) ... -205.438213815 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.211958820 sqrt= 1.100890013 +W(HF) = 0.825110543 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.292390 -0.000000 + 1 N : 0.176051 -0.000000 + 2 O : -0.122278 0.000000 + 3 H : 0.238618 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.829545 s : 3.829545 + pz : 1.675343 p : 4.394339 + px : 1.281466 + py : 1.437529 + dz2 : 0.010298 d : 0.060390 + dxz : 0.012276 + dyz : 0.008110 + dx2y2 : 0.017850 + dxy : 0.011855 + f0 : 0.001233 f : 0.008116 + f+1 : 0.001433 + f-1 : 0.000788 + f+2 : 0.001029 + f-2 : 0.000892 + f+3 : 0.001334 + f-3 : 0.001407 + 1 N s : 3.885838 s : 3.885838 + pz : 0.850579 p : 2.738406 + px : 0.835244 + py : 1.052583 + dz2 : 0.035618 d : 0.169181 + dxz : 0.039937 + dyz : 0.022499 + dx2y2 : 0.044097 + dxy : 0.027030 + f0 : 0.002513 f : 0.030523 + f+1 : 0.004656 + f-1 : 0.003596 + f+2 : 0.003390 + f-2 : 0.004726 + f+3 : 0.005255 + f-3 : 0.006388 + 2 O s : 3.860712 s : 3.860712 + pz : 1.186968 p : 4.168103 + px : 1.658023 + py : 1.323112 + dz2 : 0.023236 d : 0.083519 + dxz : 0.012945 + dyz : 0.014110 + dx2y2 : 0.014619 + dxy : 0.018609 + f0 : 0.001211 f : 0.009944 + f+1 : 0.000857 + f-1 : 0.001857 + f+2 : 0.001626 + f-2 : 0.001587 + f+3 : 0.001470 + f-3 : 0.001336 + 3 H s : 0.650717 s : 0.650717 + pz : 0.045062 p : 0.092985 + px : 0.028173 + py : 0.019750 + dz2 : 0.003734 d : 0.017681 + dxz : 0.001228 + dyz : 0.003421 + dx2y2 : 0.001491 + dxy : 0.007808 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.587327 -0.000000 + 1 N : -0.286965 0.000000 + 2 O : 0.286840 0.000000 + 3 H : -0.587202 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.138271 s : 3.138271 + pz : 1.370338 p : 3.895051 + px : 1.201920 + py : 1.322793 + dz2 : 0.039697 d : 0.294921 + dxz : 0.069624 + dyz : 0.035142 + dx2y2 : 0.086662 + dxy : 0.063797 + f0 : 0.008638 f : 0.084430 + f+1 : 0.015903 + f-1 : 0.001172 + f+2 : 0.015283 + f-2 : 0.008657 + f+3 : 0.013018 + f-3 : 0.021760 + 1 N s : 3.038790 s : 3.038790 + pz : 0.888072 p : 2.878190 + px : 0.872061 + py : 1.118056 + dz2 : 0.151831 d : 0.934604 + dxz : 0.222391 + dyz : 0.174746 + dx2y2 : 0.225175 + dxy : 0.160460 + f0 : 0.037137 f : 0.435381 + f+1 : 0.050645 + f-1 : 0.053329 + f+2 : 0.077434 + f-2 : 0.076171 + f+3 : 0.066723 + f-3 : 0.073943 + 2 O s : 3.312671 s : 3.312671 + pz : 1.184344 p : 3.916797 + px : 1.384868 + py : 1.347584 + dz2 : 0.050819 d : 0.358493 + dxz : 0.061222 + dyz : 0.110038 + dx2y2 : 0.087955 + dxy : 0.048458 + f0 : 0.012607 f : 0.125200 + f+1 : 0.007836 + f-1 : 0.024392 + f+2 : 0.030988 + f-2 : 0.021892 + f+3 : 0.009420 + f-3 : 0.018065 + 3 H s : 0.624732 s : 0.624732 + pz : 0.182893 p : 0.579801 + px : 0.138984 + py : 0.257924 + dz2 : 0.061061 d : 0.382669 + dxz : 0.035899 + dyz : 0.103403 + dx2y2 : 0.087876 + dxy : 0.094431 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2924 8.0000 -0.2924 2.1833 1.7209 0.4624 + 1 N 6.8239 7.0000 0.1761 2.8444 2.3545 0.4899 + 2 O 8.1223 8.0000 -0.1223 2.1664 1.6674 0.4990 + 3 H 0.7614 1.0000 0.2386 1.0211 0.9463 0.0749 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7390 B( 0-O , 3-H ) : 0.8839 B( 1-N , 2-O ) : 1.5613 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 56.815 sec + +Fock Matrix Formation ... 0.204 sec ( 0.4%) +Initial Guess ... 0.132 sec ( 0.2%) +DIIS Solver ... 1.756 sec ( 3.1%) +State Vector Update ... 0.089 sec ( 0.2%) +Sigma-vector construction ... 39.796 sec ( 70.0%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.025 sec ( 0.1% of sigma) + (0-ext) ... 0.072 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (2-ext) ... 0.988 sec ( 2.5% of sigma) + (4-ext) ... 22.018 sec ( 55.3% of sigma) + ... 1.376 sec ( 3.5% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.120 sec ( 0.3% of sigma) + Fock-dressing ... 2.240 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.079 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.071 sec ( 25.3% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.951 sec ( 12.2% of ALL) + I/O of integral and amplitudes ... 0.646 sec ( 9.3% of (T)) + External N**7 contributions ... 3.919 sec ( 56.4% of (T)) + Internal N**7 contributions ... 0.307 sec ( 4.4% of (T)) + N**6 triples energy contributions ... 1.572 sec ( 22.6% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.438213815291 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.007070139 0.002484318 -0.009529739 + 2 N : 0.008038667 0.001336653 0.007870696 + 3 O : -0.003610114 -0.002054366 -0.005931683 + 4 H : 0.002641585 -0.001766604 0.007590726 + +Norm of the cartesian gradient ... 0.019886817 +RMS gradient ... 0.005740829 +MAX gradient ... 0.009529739 + +------- +TIMINGS +------- + +Total numerical gradient time ... 369.521 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: -390.64 cm**-1 ***imaginary mode*** + 7: 570.03 cm**-1 + 8: 770.85 cm**-1 + 9: 1207.64 cm**-1 + 10: 1688.19 cm**-1 + 11: 3693.68 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 -0.077874 -0.410811 0.165785 0.051120 -0.056076 -0.002764 + 1 0.024459 -0.112625 -0.123256 0.062149 0.038921 -0.056356 + 2 -0.047251 0.355316 0.011400 -0.010898 0.018161 -0.027039 + 3 0.083545 0.152530 -0.398723 0.052572 -0.063531 0.000444 + 4 0.038803 0.106482 0.216178 -0.047918 -0.562613 -0.000294 + 5 0.041823 -0.226749 0.079438 -0.046390 0.412154 -0.000405 + 6 -0.012042 0.319557 0.214250 -0.037792 0.131968 -0.000492 + 7 -0.031948 0.011194 -0.044197 -0.017651 0.454216 -0.000152 + 8 -0.043205 -0.149245 -0.116724 0.032169 -0.389123 0.000496 + 9 0.266224 -0.671136 -0.491331 -0.942090 -0.321746 0.045506 + 10 -0.420340 0.130262 -0.346160 -0.040415 -0.009114 0.900972 + 11 0.854563 -0.119887 0.567852 0.307006 0.160692 0.426922 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 7: 570.03 0.017499 88.43 0.009580 ( 0.061388 0.023775 -0.072430) + 8: 770.85 0.039859 201.43 0.016136 (-0.102253 0.003429 0.075290) + 9: 1207.64 0.002678 13.54 0.000692 (-0.019719 0.014890 0.009030) + 10: 1688.19 0.033840 171.01 0.006255 (-0.058076 -0.017966 0.050594) + 11: 3693.68 0.009896 50.01 0.000836 (-0.011147 0.018549 0.019176) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 7 +The total number of vibrations considered is 5 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 570.03 E(vib) ... 0.11 +freq. 770.85 E(vib) ... 0.05 +freq. 1207.64 E(vib) ... 0.01 +freq. 1688.19 E(vib) ... 0.00 +freq. 3693.68 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.43821381 Eh +Zero point energy ... 0.01806677 Eh 11.34 kcal/mol +Thermal vibrational correction ... 0.00028297 Eh 0.18 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.41703153 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00311552 Eh 1.96 kcal/mol +Non-thermal (ZPE) correction 0.01806677 Eh 11.34 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02118229 Eh 13.29 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.41703153 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.41608732 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.687868 0.408584 0.362938 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00037189 Eh 0.23 kcal/mol +Rotational entropy ... 0.00994505 Eh 6.24 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02811926 Eh 17.65 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00994505 Eh 6.24 kcal/mol| +| sn= 2 | S(rot)= 0.00929060 Eh 5.83 kcal/mol| +| sn= 3 | S(rot)= 0.00890777 Eh 5.59 kcal/mol| +| sn= 4 | S(rot)= 0.00863614 Eh 5.42 kcal/mol| +| sn= 5 | S(rot)= 0.00842545 Eh 5.29 kcal/mol| +| sn= 6 | S(rot)= 0.00825331 Eh 5.18 kcal/mol| +| sn= 7 | S(rot)= 0.00810776 Eh 5.09 kcal/mol| +| sn= 8 | S(rot)= 0.00798169 Eh 5.01 kcal/mol| +| sn= 9 | S(rot)= 0.00787048 Eh 4.94 kcal/mol| +| sn=10 | S(rot)= 0.00777100 Eh 4.88 kcal/mol| +| sn=11 | S(rot)= 0.00768101 Eh 4.82 kcal/mol| +| sn=12 | S(rot)= 0.00759885 Eh 4.77 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.41608732 Eh +Total entropy correction ... -0.02811926 Eh -17.65 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44420658 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00599276 Eh -3.76 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.438213814 Eh +Current gradient norm .... 0.019886815 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + -0.016892033 0.098973710 0.175647667 0.476096118 0.501461732 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999378741 +Lowest eigenvalues of augmented Hessian: + -0.000142109 0.093854533 0.175316760 0.475713346 0.501316510 +Length of the computed step .... 0.035265807 +The final length of the internal step .... 0.035265807 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0143972056 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0068639148 RMS(Int)= 0.0143979178 + Iter 1: RMS(Cart)= 0.0000319879 RMS(Int)= 0.0000534016 + Iter 2: RMS(Cart)= 0.0000003055 RMS(Int)= 0.0000003008 + Iter 3: RMS(Cart)= 0.0000000029 RMS(Int)= 0.0000000042 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000005 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0020734833 0.0001000000 NO + MAX gradient 0.0033955031 0.0003000000 NO + RMS step 0.0143972056 0.0020000000 NO + MAX step 0.0320566549 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0170 Max(Angles) 0.63 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4845 0.003396 -0.0170 1.4676 + 2. B(O 2,N 1) 1.1715 0.001394 0.0012 1.1727 + 3. B(H 3,O 0) 0.9731 0.001788 -0.0018 0.9713 + 4. A(N 1,O 0,H 3) 103.97 -0.000309 0.63 104.60 + 5. A(O 0,N 1,O 2) 111.90 -0.003006 0.51 112.41 + 6. D(O 2,N 1,O 0,H 3) -57.27 -0.014330 0.00 -57.27 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.754051 -0.332315 0.365734 + N 0.585380 -0.530564 -0.200297 + O 0.884191 0.319874 -0.950395 + H -0.715518 0.543004 0.784959 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.424949 -0.627984 0.691137 + 1 N 7.0000 0 14.007 1.106207 -1.002620 -0.378507 + 2 O 8.0000 0 15.999 1.670878 0.604474 -1.795987 + 3 H 1.0000 0 1.008 -1.352134 1.026130 1.483357 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.467572092377 0.00000000 0.00000000 + O 2 1 0 1.172680223259 112.41432682 0.00000000 + H 1 2 3 0.971296891113 104.59593457 302.72727287 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.773309336378 0.00000000 0.00000000 + O 2 1 0 2.216044464625 112.41432682 0.00000000 + H 1 2 3 1.835485118933 104.59593457 302.72727287 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2235 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2706 + la=0 lb=0: 553 shell pairs + la=1 lb=0: 537 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.895358118392 Eh + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.658e-04 +Time for diagonalization ... 0.005 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.005 sec +Total time needed ... 0.011 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7098711137 0.000000000000 0.00048461 0.00001332 0.0026059 0.7000 + 1 -204.7099137498 -0.000042636149 0.00039758 0.00001110 0.0020371 0.7000 + ***Turning on DIIS*** + 2 -204.7099491626 -0.000035412751 0.00101381 0.00002873 0.0015722 0.0000 + 3 -204.7096901689 0.000258993691 0.00036260 0.00001283 0.0004474 0.0000 + 4 -204.7102736112 -0.000583442322 0.00013637 0.00000385 0.0001125 0.0000 + 5 -204.7099769241 0.000296687081 0.00003871 0.00000152 0.0000428 0.0000 + 6 -204.7099524303 0.000024493865 0.00001863 0.00000075 0.0000325 0.0000 + 7 -204.7101180403 -0.000165610049 0.00001244 0.00000051 0.0000177 0.0000 + 8 -204.7100167932 0.000101247109 0.00001325 0.00000059 0.0000110 0.0000 + 9 -204.7100683268 -0.000051533576 0.00000835 0.00000034 0.0000067 0.0000 + 10 -204.7100700599 -0.000001733159 0.00000328 0.00000011 0.0000032 0.0000 + 11 -204.7100583985 0.000011661450 0.00000104 0.00000004 0.0000018 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + +Total Energy : -204.71006621 Eh -5570.44410 eV + Last Energy change ... -7.8105e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.0140e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 5 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.560 sec +Reference energy ... -204.710064070 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 11.872 sec +AO-integral generation ... 0.412 sec +Half transformation ... 0.189 sec +K-integral sorting ... 9.305 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.056 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.057 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.076 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.088 s ( 0.001 ms/b) + 159120 b 0 skpd 0.038 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.084 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.074 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.055 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.098 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.055 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.789 sec +AO-integral generation ... 0.588 sec +Half transformation ... 0.098 sec +J-integral sorting ... 0.078 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.283 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.445 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090107875 +EMP2(bb)= -0.090107875 +EMP2(ab)= -0.516245371 + +Initial guess performed in 0.194 sec +E(0) ... -204.710064070 +E(MP2) ... -0.696461121 +Initial E(tot) ... -205.406525192 + ... 0.188183522 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.406525192 -0.696461121 -0.000000000 0.021685832 5.62 0.000000791 + *** Turning on DIIS *** + 1 -205.378311112 -0.668247042 0.028214079 0.009500311 5.27 0.056447280 + 2 -205.397745884 -0.687681814 -0.019434772 0.004599013 5.28 0.059487252 + 3 -205.401530778 -0.691466708 -0.003784894 0.001676665 5.87 0.073211991 + 4 -205.403087976 -0.693023906 -0.001557198 0.001394464 6.62 0.079655364 + 5 -205.403618338 -0.693554267 -0.000530361 0.000861426 5.26 0.084854586 + 6 -205.403720593 -0.693656523 -0.000102256 0.000531065 5.43 0.087523587 + 7 -205.403765627 -0.693701557 -0.000045034 0.000265242 6.45 0.088833934 + 8 -205.403777253 -0.693713182 -0.000011626 0.000128764 6.89 0.089423301 + 9 -205.403773800 -0.693709729 0.000003453 0.000075234 6.19 0.089629023 + 10 -205.403779314 -0.693715243 -0.000005514 0.000043171 6.04 0.089713492 + 11 -205.403775807 -0.693711736 0.000003507 0.000029362 7.74 0.089708656 + 12 -205.403778129 -0.693714059 -0.000002323 0.000017775 8.38 0.089729215 + 13 -205.403777790 -0.693713719 0.000000340 0.000010239 6.87 0.089724303 + 14 -205.403778187 -0.693714116 -0.000000397 0.000004556 5.70 0.089731485 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.710064070 +E(CORR) ... -0.693714116 +E(TOT) ... -205.403778187 +Singles norm **1/2 ... 0.089731485 ( 0.044865742, 0.044865742) +T1 diagnostic ... 0.021149914 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.056173 + 9a-> 13a 9b-> 13b 0.050231 + 8a-> 13a 9b-> 13b 0.039662 + 9a-> 13a 8b-> 13b 0.039662 + 8b-> 13b -1b-> -1b 0.034303 + 8a-> 13a -1a-> -1a 0.034303 + 11a-> 13a 11b-> 13b 0.030086 + 5a-> 13a 5b-> 13b 0.028405 + 10a-> 13a -1a-> -1a 0.028041 + 10b-> 13b -1b-> -1b 0.028041 + 11a-> 25a 11b-> 25b 0.026763 + 11b-> 25b -1b-> -1b 0.022971 + 11a-> 25a -1a-> -1a 0.022971 + 10a-> 13a 9b-> 13b 0.022171 + 9a-> 13a 10b-> 13b 0.022171 + 8a-> 22a 8b-> 13b 0.020603 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034504325 + alpha-alpha-alpha ... -0.000879568 ( 2.5%) + alpha-alpha-beta ... -0.016372594 ( 47.5%) + alpha-beta -beta ... -0.016372594 ( 47.5%) + beta -beta -beta ... -0.000879568 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034504325 + +Final correlation energy ... -0.728218441 +E(CCSD) ... -205.403778187 +E(CCSD(T)) ... -205.438282512 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210279750 sqrt= 1.100127152 +W(HF) = 0.826255252 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 125.358 sec + +Fock Matrix Formation ... 0.560 sec ( 0.4%) +Initial Guess ... 0.194 sec ( 0.2%) +DIIS Solver ... 5.963 sec ( 4.8%) +State Vector Update ... 0.305 sec ( 0.2%) +Sigma-vector construction ... 87.334 sec ( 69.7%) + <0|H|D> ... 0.008 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.051 sec ( 0.1% of sigma) + (0-ext) ... 0.160 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.061 sec ( 0.1% of sigma) + (2-ext) ... 2.218 sec ( 2.5% of sigma) + (4-ext) ... 51.413 sec ( 58.9% of sigma) + ... 4.323 sec ( 4.9% of sigma) + ... 0.007 sec ( 0.0% of sigma) + (1-ext) ... 0.023 sec ( 0.0% of sigma) + (1-ext) ... 0.223 sec ( 0.3% of sigma) + Fock-dressing ... 5.708 sec ( 6.5% of sigma) + (ik|jl)-dressing ... 0.172 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 18.484 sec ( 21.2% of sigma) + Pair energies ... 0.026 sec ( 0.0% of sigma) +Total Time for computing (T) ... 15.948 sec ( 12.7% of ALL) + I/O of integral and amplitudes ... 2.168 sec ( 13.6% of (T)) + External N**7 contributions ... 8.869 sec ( 55.6% of (T)) + Internal N**7 contributions ... 1.021 sec ( 6.4% of (T)) + N**6 triples energy contributions ... 3.716 sec ( 23.3% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.438282511633 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.003681628 0.003012968 -0.010254545 + 2 N : 0.004036383 0.004568619 0.008524341 + 3 O : -0.002900709 -0.003933943 -0.005553103 + 4 H : 0.002545955 -0.003647644 0.007283308 + +Norm of the cartesian gradient ... 0.019109627 +RMS gradient ... 0.005516474 +MAX gradient ... 0.010254545 + +------- +TIMINGS +------- + +Total numerical gradient time ... 751.808 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.438282512 Eh +Current gradient norm .... 0.019109627 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999998308 +Lowest eigenvalues of augmented Hessian: + -0.000000370 0.098057621 0.176053864 0.476024105 0.501723112 +Length of the computed step .... 0.001839626 +The final length of the internal step .... 0.001839626 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0007510243 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0003611679 RMS(Int)= 0.0007510212 + Iter 1: RMS(Cart)= 0.0000000544 RMS(Int)= 0.0000000964 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000686974 0.0000050000 NO + RMS gradient 0.0000921902 0.0001000000 YES + MAX gradient 0.0001952378 0.0003000000 YES + RMS step 0.0007510243 0.0020000000 YES + MAX step 0.0017326849 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0009 Max(Angles) 0.03 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4676 -0.000195 0.0009 1.4685 + 2. B(O 2,N 1) 1.1727 -0.000040 -0.0001 1.1726 + 3. B(H 3,O 0) 0.9713 -0.000043 0.0000 0.9713 + 4. A(N 1,O 0,H 3) 104.60 0.000008 -0.03 104.57 + 5. A(O 0,N 1,O 2) 112.41 0.000097 -0.02 112.40 + 6. D(O 2,N 1,O 0,H 3) -57.27 -0.015157 -0.00 -57.27 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.754487 -0.332324 0.365898 + N 0.585796 -0.530651 -0.200466 + O 0.884229 0.319899 -0.950438 + H -0.715537 0.543076 0.785006 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.425773 -0.628001 0.691447 + 1 N 7.0000 0 14.007 1.106994 -1.002785 -0.378826 + 2 O 8.0000 0 15.999 1.670951 0.604521 -1.796067 + 3 H 1.0000 0 1.008 -1.352169 1.026266 1.483446 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.468488989733 0.00000000 0.00000000 + O 2 1 0 1.172584808914 112.39563957 0.00000000 + H 1 2 3 0.971336377104 104.56800777 302.72727287 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.775042021273 0.00000000 0.00000000 + O 2 1 0 2.215864157644 112.39563957 0.00000000 + H 1 2 3 1.835559736642 104.56800777 302.72727287 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2235 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2706 + la=0 lb=0: 553 shell pairs + la=1 lb=0: 537 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.880669493848 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.8806694938 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.659e-04 +Time for diagonalization ... 0.006 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.005 sec +Total time needed ... 0.013 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7099930521 0.000000000000 0.00002650 0.00000068 0.0001437 0.7000 + 1 -204.7099931643 -0.000000112186 0.00002176 0.00000057 0.0001126 0.7000 + ***Turning on DIIS*** + 2 -204.7099932576 -0.000000093330 0.00005637 0.00000151 0.0000872 0.0000 + 3 -204.7100029154 -0.000009657799 0.00001763 0.00000064 0.0000227 0.0000 + 4 -204.7099862695 0.000016645894 0.00000668 0.00000019 0.0000062 0.0000 + 5 -204.7099969787 -0.000010709207 0.00000220 0.00000008 0.0000026 0.0000 + 6 -204.7099963905 0.000000588168 0.00000077 0.00000003 0.0000014 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70999217 Eh -5570.44208 eV + +Components: +Nuclear Repulsion : 68.88066949 Eh 1874.33831 eV +Electronic Energy : -273.59066167 Eh -7444.78039 eV +One Electron Energy: -417.42315040 Eh -11358.66139 eV +Two Electron Energy: 143.83248873 Eh 3913.88100 eV + +Virial components: +Potential Energy : -408.94305794 Eh -11127.90634 eV +Kinetic Energy : 204.23306577 Eh 5557.46426 eV +Virial Ratio : 2.00233521 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 4.2169e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.0123e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.0946e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.2838e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.684612 -562.8569 + 1 1.0000 -20.626744 -561.2822 + 2 1.0000 -15.804646 -430.0663 + 3 1.0000 -1.613053 -43.8934 + 4 1.0000 -1.384201 -37.6660 + 5 1.0000 -0.959194 -26.1010 + 6 1.0000 -0.770707 -20.9720 + 7 1.0000 -0.736416 -20.0389 + 8 1.0000 -0.697215 -18.9722 + 9 1.0000 -0.604308 -16.4441 + 10 1.0000 -0.533002 -14.5037 + 11 1.0000 -0.464985 -12.6529 + 12 0.0000 0.030983 0.8431 + 13 0.0000 0.067758 1.8438 + 14 0.0000 0.093134 2.5343 + 15 0.0000 0.108317 2.9475 + 16 0.0000 0.114284 3.1098 + 17 0.0000 0.154420 4.2020 + 18 0.0000 0.157123 4.2755 + 19 0.0000 0.172357 4.6901 + 20 0.0000 0.179493 4.8843 + 21 0.0000 0.191448 5.2096 + 22 0.0000 0.202445 5.5088 + 23 0.0000 0.234784 6.3888 + 24 0.0000 0.269683 7.3384 + 25 0.0000 0.286875 7.8063 + 26 0.0000 0.309513 8.4223 + 27 0.0000 0.335451 9.1281 + 28 0.0000 0.341475 9.2920 + 29 0.0000 0.362375 9.8607 + 30 0.0000 0.422472 11.4961 + 31 0.0000 0.512360 13.9420 + 32 0.0000 0.532302 14.4847 + 33 0.0000 0.537007 14.6127 + 34 0.0000 0.561138 15.2694 + 35 0.0000 0.604660 16.4536 + 36 0.0000 0.634099 17.2547 + 37 0.0000 0.645756 17.5719 + 38 0.0000 0.700103 19.0508 + 39 0.0000 0.715066 19.4579 + 40 0.0000 0.734021 19.9737 + 41 0.0000 0.742075 20.1929 + 42 0.0000 0.767719 20.8907 + 43 0.0000 0.783019 21.3070 + 44 0.0000 0.814328 22.1590 + 45 0.0000 0.823938 22.4205 + 46 0.0000 0.852449 23.1963 + 47 0.0000 0.882389 24.0110 + 48 0.0000 0.908220 24.7139 + 49 0.0000 0.946534 25.7565 + 50 0.0000 0.974688 26.5226 + 51 0.0000 0.980572 26.6827 + 52 0.0000 0.993865 27.0444 + 53 0.0000 1.019446 27.7405 + 54 0.0000 1.050652 28.5897 + 55 0.0000 1.088859 29.6294 + 56 0.0000 1.157566 31.4990 + 57 0.0000 1.209670 32.9168 + 58 0.0000 1.227876 33.4122 + 59 0.0000 1.281409 34.8689 + 60 0.0000 1.337362 36.3915 + 61 0.0000 1.412037 38.4235 + 62 0.0000 1.458892 39.6985 + 63 0.0000 1.511598 41.1327 + 64 0.0000 1.536240 41.8032 + 65 0.0000 1.569623 42.7116 + 66 0.0000 1.605182 43.6792 + 67 0.0000 1.634526 44.4777 + 68 0.0000 1.654043 45.0088 + 69 0.0000 1.730652 47.0934 + 70 0.0000 1.752266 47.6816 + 71 0.0000 1.787606 48.6432 + 72 0.0000 1.921826 52.2955 + 73 0.0000 1.944805 52.9208 + 74 0.0000 1.968913 53.5769 + 75 0.0000 2.004362 54.5415 + 76 0.0000 2.047523 55.7159 + 77 0.0000 2.078804 56.5671 + 78 0.0000 2.153943 58.6118 + 79 0.0000 2.177260 59.2463 + 80 0.0000 2.255958 61.3877 + 81 0.0000 2.309499 62.8447 + 82 0.0000 2.333820 63.5065 + 83 0.0000 2.380827 64.7856 + 84 0.0000 2.423372 65.9433 + 85 0.0000 2.453995 66.7766 + 86 0.0000 2.466772 67.1243 + 87 0.0000 2.492496 67.8243 + 88 0.0000 2.512875 68.3788 + 89 0.0000 2.553460 69.4832 + 90 0.0000 2.582394 70.2705 + 91 0.0000 2.606719 70.9324 + 92 0.0000 2.665315 72.5269 + 93 0.0000 2.683595 73.0243 + 94 0.0000 2.762918 75.1828 + 95 0.0000 2.814252 76.5797 + 96 0.0000 2.821212 76.7691 + 97 0.0000 2.924218 79.5720 + 98 0.0000 2.968761 80.7841 + 99 0.0000 2.983128 81.1751 + 100 0.0000 3.117849 84.8410 + 101 0.0000 3.169857 86.2562 + 102 0.0000 3.227678 87.8296 + 103 0.0000 3.498392 95.1961 + 104 0.0000 3.694928 100.5441 + 105 0.0000 3.858811 105.0036 + 106 0.0000 4.025737 109.5459 + 107 0.0000 4.160199 113.2048 + 108 0.0000 4.200544 114.3026 + 109 0.0000 4.319775 117.5470 + 110 0.0000 4.362920 118.7211 + 111 0.0000 4.392502 119.5261 + 112 0.0000 4.546419 123.7144 + 113 0.0000 4.614809 125.5753 + 114 0.0000 4.671920 127.1294 + 115 0.0000 4.749539 129.2415 + 116 0.0000 4.815831 131.0454 + 117 0.0000 4.873978 132.6277 + 118 0.0000 4.950039 134.6974 + 119 0.0000 4.983182 135.5993 + 120 0.0000 5.062685 137.7627 + 121 0.0000 5.107660 138.9865 + 122 0.0000 5.182418 141.0207 + 123 0.0000 5.218985 142.0158 + 124 0.0000 5.247692 142.7970 + 125 0.0000 5.284451 143.7972 + 126 0.0000 5.389648 146.6598 + 127 0.0000 5.480738 149.1385 + 128 0.0000 5.517937 150.1507 + 129 0.0000 5.703005 155.1866 + 130 0.0000 5.759819 156.7326 + 131 0.0000 5.959214 162.1585 + 132 0.0000 6.161325 167.6582 + 133 0.0000 6.405260 174.2960 + 134 0.0000 6.485910 176.4906 + 135 0.0000 6.517596 177.3528 + 136 0.0000 6.686240 181.9418 + 137 0.0000 6.712221 182.6488 + 138 0.0000 6.780578 184.5089 + 139 0.0000 6.810135 185.3132 + 140 0.0000 6.862887 186.7486 + 141 0.0000 7.082814 192.7332 + 142 0.0000 7.116944 193.6619 + 143 0.0000 7.149133 194.5378 + 144 0.0000 7.211434 196.2331 + 145 0.0000 7.249612 197.2720 + 146 0.0000 7.272170 197.8858 + 147 0.0000 7.324888 199.3203 + 148 0.0000 7.390844 201.1151 + 149 0.0000 7.464521 203.1199 + 150 0.0000 7.478336 203.4959 + 151 0.0000 7.538309 205.1278 + 152 0.0000 7.573101 206.0746 + 153 0.0000 7.677116 208.9049 + 154 0.0000 7.690570 209.2711 + 155 0.0000 7.908133 215.1912 + 156 0.0000 8.028040 218.4541 + 157 0.0000 8.375527 227.9097 + 158 0.0000 14.020827 381.5261 + 159 0.0000 15.008477 408.4014 + 160 0.0000 15.957557 434.2272 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.684612 -562.8569 + 1 1.0000 -20.626744 -561.2822 + 2 1.0000 -15.804646 -430.0663 + 3 1.0000 -1.613053 -43.8934 + 4 1.0000 -1.384201 -37.6660 + 5 1.0000 -0.959194 -26.1010 + 6 1.0000 -0.770707 -20.9720 + 7 1.0000 -0.736416 -20.0389 + 8 1.0000 -0.697215 -18.9722 + 9 1.0000 -0.604308 -16.4441 + 10 1.0000 -0.533002 -14.5037 + 11 1.0000 -0.464985 -12.6529 + 12 0.0000 0.030983 0.8431 + 13 0.0000 0.067758 1.8438 + 14 0.0000 0.093134 2.5343 + 15 0.0000 0.108317 2.9475 + 16 0.0000 0.114284 3.1098 + 17 0.0000 0.154420 4.2020 + 18 0.0000 0.157123 4.2755 + 19 0.0000 0.172357 4.6901 + 20 0.0000 0.179493 4.8843 + 21 0.0000 0.191448 5.2096 + 22 0.0000 0.202445 5.5088 + 23 0.0000 0.234784 6.3888 + 24 0.0000 0.269683 7.3384 + 25 0.0000 0.286875 7.8063 + 26 0.0000 0.309513 8.4223 + 27 0.0000 0.335451 9.1281 + 28 0.0000 0.341475 9.2920 + 29 0.0000 0.362375 9.8607 + 30 0.0000 0.422472 11.4961 + 31 0.0000 0.512360 13.9420 + 32 0.0000 0.532302 14.4847 + 33 0.0000 0.537007 14.6127 + 34 0.0000 0.561138 15.2694 + 35 0.0000 0.604660 16.4536 + 36 0.0000 0.634099 17.2547 + 37 0.0000 0.645756 17.5719 + 38 0.0000 0.700103 19.0508 + 39 0.0000 0.715066 19.4579 + 40 0.0000 0.734021 19.9737 + 41 0.0000 0.742075 20.1929 + 42 0.0000 0.767719 20.8907 + 43 0.0000 0.783019 21.3070 + 44 0.0000 0.814328 22.1590 + 45 0.0000 0.823938 22.4205 + 46 0.0000 0.852449 23.1963 + 47 0.0000 0.882389 24.0110 + 48 0.0000 0.908220 24.7139 + 49 0.0000 0.946534 25.7565 + 50 0.0000 0.974688 26.5226 + 51 0.0000 0.980572 26.6827 + 52 0.0000 0.993865 27.0444 + 53 0.0000 1.019446 27.7405 + 54 0.0000 1.050652 28.5897 + 55 0.0000 1.088859 29.6294 + 56 0.0000 1.157566 31.4990 + 57 0.0000 1.209670 32.9168 + 58 0.0000 1.227876 33.4122 + 59 0.0000 1.281409 34.8689 + 60 0.0000 1.337362 36.3915 + 61 0.0000 1.412037 38.4235 + 62 0.0000 1.458892 39.6985 + 63 0.0000 1.511598 41.1327 + 64 0.0000 1.536240 41.8032 + 65 0.0000 1.569623 42.7116 + 66 0.0000 1.605182 43.6792 + 67 0.0000 1.634526 44.4777 + 68 0.0000 1.654043 45.0088 + 69 0.0000 1.730652 47.0934 + 70 0.0000 1.752266 47.6816 + 71 0.0000 1.787606 48.6432 + 72 0.0000 1.921826 52.2955 + 73 0.0000 1.944805 52.9208 + 74 0.0000 1.968913 53.5769 + 75 0.0000 2.004362 54.5415 + 76 0.0000 2.047523 55.7159 + 77 0.0000 2.078804 56.5671 + 78 0.0000 2.153943 58.6118 + 79 0.0000 2.177260 59.2463 + 80 0.0000 2.255958 61.3877 + 81 0.0000 2.309499 62.8447 + 82 0.0000 2.333820 63.5065 + 83 0.0000 2.380827 64.7856 + 84 0.0000 2.423372 65.9433 + 85 0.0000 2.453995 66.7766 + 86 0.0000 2.466772 67.1243 + 87 0.0000 2.492496 67.8243 + 88 0.0000 2.512875 68.3788 + 89 0.0000 2.553460 69.4832 + 90 0.0000 2.582394 70.2705 + 91 0.0000 2.606719 70.9324 + 92 0.0000 2.665315 72.5269 + 93 0.0000 2.683595 73.0243 + 94 0.0000 2.762918 75.1828 + 95 0.0000 2.814252 76.5797 + 96 0.0000 2.821212 76.7691 + 97 0.0000 2.924218 79.5720 + 98 0.0000 2.968761 80.7841 + 99 0.0000 2.983128 81.1751 + 100 0.0000 3.117849 84.8410 + 101 0.0000 3.169857 86.2562 + 102 0.0000 3.227678 87.8296 + 103 0.0000 3.498392 95.1961 + 104 0.0000 3.694928 100.5441 + 105 0.0000 3.858811 105.0036 + 106 0.0000 4.025737 109.5459 + 107 0.0000 4.160199 113.2048 + 108 0.0000 4.200544 114.3026 + 109 0.0000 4.319775 117.5470 + 110 0.0000 4.362920 118.7211 + 111 0.0000 4.392502 119.5261 + 112 0.0000 4.546419 123.7144 + 113 0.0000 4.614809 125.5753 + 114 0.0000 4.671920 127.1294 + 115 0.0000 4.749539 129.2415 + 116 0.0000 4.815831 131.0454 + 117 0.0000 4.873978 132.6277 + 118 0.0000 4.950039 134.6974 + 119 0.0000 4.983182 135.5993 + 120 0.0000 5.062685 137.7627 + 121 0.0000 5.107660 138.9865 + 122 0.0000 5.182418 141.0207 + 123 0.0000 5.218985 142.0158 + 124 0.0000 5.247692 142.7970 + 125 0.0000 5.284451 143.7972 + 126 0.0000 5.389648 146.6598 + 127 0.0000 5.480738 149.1385 + 128 0.0000 5.517937 150.1507 + 129 0.0000 5.703005 155.1866 + 130 0.0000 5.759819 156.7326 + 131 0.0000 5.959214 162.1585 + 132 0.0000 6.161325 167.6582 + 133 0.0000 6.405260 174.2960 + 134 0.0000 6.485910 176.4906 + 135 0.0000 6.517596 177.3528 + 136 0.0000 6.686240 181.9418 + 137 0.0000 6.712221 182.6488 + 138 0.0000 6.780578 184.5089 + 139 0.0000 6.810135 185.3132 + 140 0.0000 6.862887 186.7486 + 141 0.0000 7.082814 192.7332 + 142 0.0000 7.116944 193.6619 + 143 0.0000 7.149133 194.5378 + 144 0.0000 7.211434 196.2331 + 145 0.0000 7.249612 197.2720 + 146 0.0000 7.272170 197.8858 + 147 0.0000 7.324888 199.3203 + 148 0.0000 7.390844 201.1151 + 149 0.0000 7.464521 203.1199 + 150 0.0000 7.478336 203.4959 + 151 0.0000 7.538309 205.1278 + 152 0.0000 7.573101 206.0746 + 153 0.0000 7.677116 208.9049 + 154 0.0000 7.690570 209.2711 + 155 0.0000 7.908133 215.1912 + 156 0.0000 8.028040 218.4541 + 157 0.0000 8.375527 227.9097 + 158 0.0000 14.020827 381.5261 + 159 0.0000 15.008477 408.4014 + 160 0.0000 15.957557 434.2272 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.349104 0.000000 + 1 N : 0.352390 0.000000 + 2 O : -0.252200 0.000000 + 3 H : 0.248914 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.841720 s : 3.841720 + pz : 1.713303 p : 4.472751 + px : 1.295804 + py : 1.463644 + dz2 : 0.003410 d : 0.030160 + dxz : 0.006350 + dyz : 0.001479 + dx2y2 : 0.014047 + dxy : 0.004874 + f0 : 0.000721 f : 0.004473 + f+1 : 0.000910 + f-1 : 0.000131 + f+2 : 0.000569 + f-2 : 0.000274 + f+3 : 0.000942 + f-3 : 0.000924 + 1 N s : 3.832626 s : 3.832626 + pz : 0.787800 p : 2.642176 + px : 0.785014 + py : 1.069362 + dz2 : 0.033215 d : 0.140945 + dxz : 0.030563 + dyz : 0.018380 + dx2y2 : 0.037894 + dxy : 0.020893 + f0 : 0.002473 f : 0.031863 + f+1 : 0.004675 + f-1 : 0.004252 + f+2 : 0.003651 + f-2 : 0.004820 + f+3 : 0.005458 + f-3 : 0.006533 + 2 O s : 3.873917 s : 3.873917 + pz : 1.214272 p : 4.309103 + px : 1.736062 + py : 1.358769 + dz2 : 0.021664 d : 0.061700 + dxz : 0.006255 + dyz : 0.011172 + dx2y2 : 0.008522 + dxy : 0.014088 + f0 : 0.000893 f : 0.007480 + f+1 : 0.000298 + f-1 : 0.001901 + f+2 : 0.001306 + f-2 : 0.001196 + f+3 : 0.001027 + f-3 : 0.000859 + 3 H s : 0.641459 s : 0.641459 + pz : 0.040555 p : 0.088814 + px : 0.025167 + py : 0.023092 + dz2 : 0.004210 d : 0.020814 + dxz : 0.001172 + dyz : 0.004310 + dx2y2 : 0.002284 + dxy : 0.008837 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.583696 0.000000 + 1 N : -0.251502 0.000000 + 2 O : 0.246604 0.000000 + 3 H : -0.578797 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.125426 s : 3.125426 + pz : 1.395782 p : 3.941093 + px : 1.206184 + py : 1.339127 + dz2 : 0.034920 d : 0.269761 + dxz : 0.064156 + dyz : 0.028781 + dx2y2 : 0.080940 + dxy : 0.060963 + f0 : 0.007634 f : 0.080024 + f+1 : 0.015921 + f-1 : 0.000561 + f+2 : 0.014004 + f-2 : 0.008106 + f+3 : 0.011581 + f-3 : 0.022216 + 1 N s : 3.026498 s : 3.026498 + pz : 0.850230 p : 2.835770 + px : 0.855192 + py : 1.130347 + dz2 : 0.156056 d : 0.939153 + dxz : 0.223008 + dyz : 0.168702 + dx2y2 : 0.223991 + dxy : 0.167397 + f0 : 0.036802 f : 0.450082 + f+1 : 0.055782 + f-1 : 0.053332 + f+2 : 0.080589 + f-2 : 0.079589 + f+3 : 0.066413 + f-3 : 0.077574 + 2 O s : 3.310217 s : 3.310217 + pz : 1.199296 p : 3.999490 + px : 1.433631 + py : 1.366563 + dz2 : 0.040220 d : 0.326955 + dxz : 0.057022 + dyz : 0.104639 + dx2y2 : 0.083044 + dxy : 0.042031 + f0 : 0.010696 f : 0.116734 + f+1 : 0.007242 + f-1 : 0.020704 + f+2 : 0.031367 + f-2 : 0.020928 + f+3 : 0.007701 + f-3 : 0.018096 + 3 H s : 0.621844 s : 0.621844 + pz : 0.175863 p : 0.564916 + px : 0.137708 + py : 0.251345 + dz2 : 0.062936 d : 0.392037 + dxz : 0.037136 + dyz : 0.106056 + dx2y2 : 0.089012 + dxy : 0.096897 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3491 8.0000 -0.3491 1.8186 1.8186 0.0000 + 1 N 6.6476 7.0000 0.3524 2.5641 2.5641 -0.0000 + 2 O 8.2522 8.0000 -0.2522 1.7677 1.7677 -0.0000 + 3 H 0.7511 1.0000 0.2489 1.0065 1.0065 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8076 B( 0-O , 3-H ) : 0.9507 B( 1-N , 2-O ) : 1.7040 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 3 sec + +Total time .... 3.320 sec +Sum of individual times .... 2.834 sec ( 85.4%) + +Fock matrix formation .... 2.426 sec ( 73.1%) +Diagonalization .... 0.174 sec ( 5.2%) +Density matrix formation .... 0.018 sec ( 0.5%) +Population analysis .... 0.068 sec ( 2.1%) +Initial guess .... 0.026 sec ( 0.8%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.014 sec ( 0.4%) +DIIS solution .... 0.122 sec ( 3.7%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.542 sec +Reference energy ... -204.709993563 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 10.989 sec +AO-integral generation ... 0.363 sec +Half transformation ... 0.181 sec +K-integral sorting ... 8.524 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.057 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.062 s ( 0.000 ms/b) + 277134 b 0 skpd 0.079 s ( 0.000 ms/b) +: : 151164 b 0 skpd 0.097 s ( 0.001 ms/b) + 159120 b 0 skpd 0.036 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.078 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.074 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.055 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.103 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.063 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.821 sec +AO-integral generation ... 0.613 sec +Half transformation ... 0.095 sec +J-integral sorting ... 0.082 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.233 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.386 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090115594 +EMP2(bb)= -0.090115594 +EMP2(ab)= -0.516302194 + +Initial guess performed in 0.186 sec +E(0) ... -204.709993563 +E(MP2) ... -0.696533383 +Initial E(tot) ... -205.406526945 + ... 0.188252312 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.406526945 -0.696533383 -0.000000000 0.021678544 7.12 0.000002170 + *** Turning on DIIS *** + 1 -205.378280407 -0.668286844 0.028246539 0.009518923 6.38 0.056475977 + 2 -205.397726596 -0.687733034 -0.019446190 0.004595547 6.22 0.059509021 + 3 -205.401513490 -0.691519927 -0.003786893 0.001680683 6.36 0.073241369 + 4 -205.403071839 -0.693078276 -0.001558349 0.001398217 5.00 0.079687852 + 5 -205.403602880 -0.693609317 -0.000531042 0.000863689 5.14 0.084893314 + 6 -205.403705291 -0.693711728 -0.000102411 0.000532629 5.41 0.087567733 + 7 -205.403750456 -0.693756893 -0.000045165 0.000265942 6.21 0.088882845 + 8 -205.403762139 -0.693768577 -0.000011684 0.000128542 5.94 0.089474314 + 9 -205.403758672 -0.693765109 0.000003468 0.000075120 6.27 0.089680448 + 10 -205.403764210 -0.693770647 -0.000005538 0.000043118 6.22 0.089765221 + 11 -205.403760693 -0.693767130 0.000003517 0.000029343 6.16 0.089760249 + 12 -205.403763015 -0.693769452 -0.000002323 0.000017782 6.47 0.089780877 + 13 -205.403762679 -0.693769117 0.000000336 0.000010270 7.68 0.089775907 + 14 -205.403763074 -0.693769511 -0.000000395 0.000004583 6.21 0.089783080 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.709993563 +E(CORR) ... -0.693769511 +E(TOT) ... -205.403763074 +Singles norm **1/2 ... 0.089783080 ( 0.044891540, 0.044891540) +T1 diagnostic ... 0.021162075 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.056301 + 9a-> 13a 9b-> 13b 0.050166 + 8a-> 13a 9b-> 13b 0.039701 + 9a-> 13a 8b-> 13b 0.039701 + 8a-> 13a -1a-> -1a 0.034277 + 8b-> 13b -1b-> -1b 0.034277 + 11a-> 13a 11b-> 13b 0.030040 + 5a-> 13a 5b-> 13b 0.028441 + 10b-> 13b -1b-> -1b 0.028133 + 10a-> 13a -1a-> -1a 0.028133 + 11a-> 25a 11b-> 25b 0.027162 + 11a-> 25a -1a-> -1a 0.023143 + 11b-> 25b -1b-> -1b 0.023143 + 10a-> 13a 9b-> 13b 0.022092 + 9a-> 13a 10b-> 13b 0.022092 + 8a-> 13a 8b-> 22b 0.020646 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034519609 + alpha-alpha-alpha ... -0.000879714 ( 2.5%) + alpha-alpha-beta ... -0.016380090 ( 47.5%) + alpha-beta -beta ... -0.016380090 ( 47.5%) + beta -beta -beta ... -0.000879714 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034519609 + +Final correlation energy ... -0.728289120 +E(CCSD) ... -205.403763074 +E(CCSD(T)) ... -205.438282683 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210363325 sqrt= 1.100165136 +W(HF) = 0.826198199 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.281227 -0.000000 + 1 N : 0.172221 0.000000 + 2 O : -0.128147 -0.000000 + 3 H : 0.237153 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.824217 s : 3.824217 + pz : 1.670664 p : 4.388144 + px : 1.279285 + py : 1.438195 + dz2 : 0.010453 d : 0.060685 + dxz : 0.012296 + dyz : 0.008073 + dx2y2 : 0.017696 + dxy : 0.012167 + f0 : 0.001225 f : 0.008181 + f+1 : 0.001455 + f-1 : 0.000782 + f+2 : 0.001030 + f-2 : 0.000901 + f+3 : 0.001349 + f-3 : 0.001440 + 1 N s : 3.886495 s : 3.886495 + pz : 0.850464 p : 2.740343 + px : 0.831765 + py : 1.058115 + dz2 : 0.035950 d : 0.170139 + dxz : 0.040028 + dyz : 0.022742 + dx2y2 : 0.044367 + dxy : 0.027052 + f0 : 0.002499 f : 0.030802 + f+1 : 0.004784 + f-1 : 0.003610 + f+2 : 0.003468 + f-2 : 0.004726 + f+3 : 0.005223 + f-3 : 0.006492 + 2 O s : 3.860521 s : 3.860521 + pz : 1.186046 p : 4.174402 + px : 1.660241 + py : 1.328115 + dz2 : 0.023212 d : 0.083295 + dxz : 0.012955 + dyz : 0.014045 + dx2y2 : 0.014607 + dxy : 0.018477 + f0 : 0.001214 f : 0.009929 + f+1 : 0.000864 + f-1 : 0.001851 + f+2 : 0.001636 + f-2 : 0.001575 + f+3 : 0.001454 + f-3 : 0.001335 + 3 H s : 0.650968 s : 0.650968 + pz : 0.045245 p : 0.093722 + px : 0.028590 + py : 0.019888 + dz2 : 0.003830 d : 0.018157 + dxz : 0.001311 + dyz : 0.003489 + dx2y2 : 0.001515 + dxy : 0.008012 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.593045 0.000000 + 1 N : -0.297015 0.000000 + 2 O : 0.286611 -0.000000 + 3 H : -0.582641 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.131405 s : 3.131405 + pz : 1.364515 p : 3.887366 + px : 1.202716 + py : 1.320136 + dz2 : 0.040785 d : 0.301050 + dxz : 0.070844 + dyz : 0.035888 + dx2y2 : 0.087456 + dxy : 0.066078 + f0 : 0.008747 f : 0.087134 + f+1 : 0.016674 + f-1 : 0.001186 + f+2 : 0.015608 + f-2 : 0.009077 + f+3 : 0.013195 + f-3 : 0.022647 + 1 N s : 3.031842 s : 3.031842 + pz : 0.886740 p : 2.879297 + px : 0.874905 + py : 1.117652 + dz2 : 0.154629 d : 0.945862 + dxz : 0.226158 + dyz : 0.175059 + dx2y2 : 0.227286 + dxy : 0.162729 + f0 : 0.037415 f : 0.440014 + f+1 : 0.052101 + f-1 : 0.053281 + f+2 : 0.078485 + f-2 : 0.076672 + f+3 : 0.066891 + f-3 : 0.075169 + 2 O s : 3.312605 s : 3.312605 + pz : 1.183338 p : 3.918419 + px : 1.386555 + py : 1.348525 + dz2 : 0.050868 d : 0.357147 + dxz : 0.061298 + dyz : 0.109361 + dx2y2 : 0.087585 + dxy : 0.048036 + f0 : 0.012658 f : 0.125218 + f+1 : 0.008069 + f-1 : 0.024181 + f+2 : 0.031103 + f-2 : 0.021820 + f+3 : 0.009333 + f-3 : 0.018053 + 3 H s : 0.623705 s : 0.623705 + pz : 0.182092 p : 0.577330 + px : 0.137991 + py : 0.257247 + dz2 : 0.061271 d : 0.381606 + dxz : 0.035911 + dyz : 0.102968 + dx2y2 : 0.087660 + dxy : 0.093796 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2812 8.0000 -0.2812 2.1787 1.7214 0.4573 + 1 N 6.8278 7.0000 0.1722 2.8359 2.3494 0.4865 + 2 O 8.1281 8.0000 -0.1281 2.1565 1.6580 0.4985 + 3 H 0.7628 1.0000 0.2372 1.0239 0.9494 0.0744 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7404 B( 0-O , 3-H ) : 0.8844 B( 1-N , 2-O ) : 1.5527 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 120.981 sec + +Fock Matrix Formation ... 0.542 sec ( 0.4%) +Initial Guess ... 0.186 sec ( 0.2%) +DIIS Solver ... 5.819 sec ( 4.8%) +State Vector Update ... 0.294 sec ( 0.2%) +Sigma-vector construction ... 86.688 sec ( 71.7%) + <0|H|D> ... 0.010 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.058 sec ( 0.1% of sigma) + (0-ext) ... 0.178 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.060 sec ( 0.1% of sigma) + (2-ext) ... 2.102 sec ( 2.4% of sigma) + (4-ext) ... 52.212 sec ( 60.2% of sigma) + ... 4.400 sec ( 5.1% of sigma) + ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.023 sec ( 0.0% of sigma) + (1-ext) ... 0.224 sec ( 0.3% of sigma) + Fock-dressing ... 5.533 sec ( 6.4% of sigma) + (ik|jl)-dressing ... 0.205 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 17.274 sec ( 19.9% of sigma) + Pair energies ... 0.026 sec ( 0.0% of sigma) +Total Time for computing (T) ... 13.430 sec ( 11.1% of ALL) + I/O of integral and amplitudes ... 2.263 sec ( 16.9% of (T)) + External N**7 contributions ... 6.467 sec ( 48.2% of (T)) + Internal N**7 contributions ... 0.633 sec ( 4.7% of (T)) + N**6 triples energy contributions ... 2.497 sec ( 18.6% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.438282682985 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.016.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.016.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.384261, -0.284755 -0.456974) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.90826 -0.17480 -0.60219 +Nuclear contribution : -0.86406 0.65305 0.96208 + ----------------------------------------- +Total Dipole Moment : 0.04420 0.47825 0.35989 + ----------------------------------------- +Magnitude (a.u.) : 0.60017 +Magnitude (Debye) : 1.52550 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.732021 0.411492 0.365931 +Rotational constants in MHz : 81903.920447 12336.211391 10970.329627 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.068667 0.313820 0.506952 +x,y,z [Debye]: -0.174538 0.797668 1.288571 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.384261, -0.284755 -0.456974) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.93882 -0.10788 -0.72315 +Nuclear contribution : -0.86406 0.65305 0.96208 + ----------------------------------------- +Total Dipole Moment : 0.07476 0.54517 0.23893 + ----------------------------------------- +Magnitude (a.u.) : 0.59990 +Magnitude (Debye) : 1.52484 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.732021 0.411492 0.365931 +Rotational constants in MHz : 81903.920447 12336.211391 10970.329627 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.042741 0.385780 0.457419 +x,y,z [Debye]: 0.108639 0.980575 1.162667 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 17 * + * * + * Dihedral ( 2, 1, 0, 3) : -49.09090909 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0360586228 RMS(Int)= 0.0008486874 + Iter 1: RMS(Cart)= 0.0002143037 RMS(Int)= 0.0000120989 + Iter 2: RMS(Cart)= 0.0000030551 RMS(Int)= 0.0000001733 + Iter 3: RMS(Cart)= 0.0000000437 RMS(Int)= 0.0000000025 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4694 0.000000 + 2. B(O 2,N 1) 1.1742 0.000000 + 3. B(H 3,O 0) 0.9736 0.000000 + 4. A(N 1,O 0,H 3) 104.4103 0.000000 + 5. A(O 0,N 1,O 2) 112.2561 0.000000 + 6. D(O 2,N 1,O 0,H 3) -49.0909 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.745359 -0.346522 0.392865 + N 0.574152 -0.550359 -0.220726 + O 0.879854 0.339016 -0.923773 + H -0.708646 0.557866 0.751635 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.408524 -0.654831 0.742407 + 1 N 7.0000 0 14.007 1.084989 -1.040029 -0.417112 + 2 O 8.0000 0 15.999 1.662684 0.640647 -1.745679 + 3 H 1.0000 0 1.008 -1.339148 1.054213 1.420384 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.468488989733 0.00000000 0.00000000 + O 2 1 0 1.172584808914 112.39563957 0.00000000 + H 1 2 3 0.971336377104 104.56800777 302.72727287 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.775042021273 0.00000000 0.00000000 + O 2 1 0 2.215864157644 112.39563957 0.00000000 + H 1 2 3 1.835559736642 104.56800777 302.72727287 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2237 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2709 + la=0 lb=0: 554 shell pairs + la=1 lb=0: 538 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.860608933324 Eh + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.8606089333 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.633e-04 +Time for diagonalization ... 0.005 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.003 sec +Total time needed ... 0.009 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7069308582 0.000000000000 0.00179609 0.00005049 0.0171863 0.7000 + 1 -204.7077394239 -0.000808565716 0.00162549 0.00004675 0.0142918 0.7000 + ***Turning on DIIS*** + 2 -204.7084396788 -0.000700254891 0.00438470 0.00012939 0.0116758 0.0000 + 3 -204.7123863487 -0.003946669895 0.00196484 0.00006047 0.0048153 0.0000 + 4 -204.7099662641 0.002420084576 0.00092921 0.00003176 0.0019337 0.0000 + 5 -204.7119831196 -0.002016855467 0.00072764 0.00002702 0.0010917 0.0000 + 6 -204.7111255160 0.000857603604 0.00077958 0.00003202 0.0007160 0.0000 + 7 -204.7107414107 0.000384105252 0.00035707 0.00001607 0.0002795 0.0000 + 8 -204.7115210517 -0.000779640985 0.00018769 0.00000927 0.0001846 0.0000 + 9 -204.7110299581 0.000491093647 0.00016198 0.00000557 0.0001197 0.0000 + 10 -204.7111488328 -0.000118874701 0.00004995 0.00000205 0.0000749 0.0000 + 11 -204.7112579105 -0.000109077731 0.00003090 0.00000089 0.0000320 0.0000 + 12 -204.7111909816 0.000066928903 0.00000806 0.00000026 0.0000087 0.0000 + 13 -204.7112099174 -0.000018935845 0.00000213 0.00000009 0.0000029 0.0000 + 14 -204.7112069550 0.000002962397 0.00000092 0.00000004 0.0000020 0.0000 + 15 -204.7112072763 -0.000000321232 0.00000079 0.00000003 0.0000019 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 16 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71120841 Eh -5570.47518 eV + +Components: +Nuclear Repulsion : 68.86060893 Eh 1873.79243 eV +Electronic Energy : -273.57181735 Eh -7444.26761 eV +One Electron Energy: -417.37673574 Eh -11357.39838 eV +Two Electron Energy: 143.80491839 Eh 3913.13077 eV + +Virial components: +Potential Energy : -408.92765975 Eh -11127.48733 eV +Kinetic Energy : 204.21645134 Eh 5557.01215 eV +Virial Ratio : 2.00242271 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.1373e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.1212e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.3578e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.9691e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.683861 -562.8365 + 1 1.0000 -20.629058 -561.3452 + 2 1.0000 -15.806276 -430.1106 + 3 1.0000 -1.612343 -43.8741 + 4 1.0000 -1.384054 -37.6620 + 5 1.0000 -0.960142 -26.1268 + 6 1.0000 -0.769771 -20.9465 + 7 1.0000 -0.737249 -20.0616 + 8 1.0000 -0.694840 -18.9076 + 9 1.0000 -0.606795 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2.5382 + 15 0.0000 0.109222 2.9721 + 16 0.0000 0.115612 3.1460 + 17 0.0000 0.153319 4.1720 + 18 0.0000 0.157695 4.2911 + 19 0.0000 0.170811 4.6480 + 20 0.0000 0.180647 4.9157 + 21 0.0000 0.192049 5.2259 + 22 0.0000 0.202380 5.5070 + 23 0.0000 0.234094 6.3700 + 24 0.0000 0.266210 7.2439 + 25 0.0000 0.285159 7.7596 + 26 0.0000 0.308720 8.4007 + 27 0.0000 0.335804 9.1377 + 28 0.0000 0.343534 9.3480 + 29 0.0000 0.369252 10.0479 + 30 0.0000 0.422031 11.4841 + 31 0.0000 0.513394 13.9701 + 32 0.0000 0.530762 14.4428 + 33 0.0000 0.534844 14.5538 + 34 0.0000 0.560803 15.2602 + 35 0.0000 0.607418 16.5287 + 36 0.0000 0.633701 17.2439 + 37 0.0000 0.647396 17.6165 + 38 0.0000 0.695629 18.9290 + 39 0.0000 0.710272 19.3275 + 40 0.0000 0.735297 20.0085 + 41 0.0000 0.742481 20.2039 + 42 0.0000 0.767746 20.8914 + 43 0.0000 0.782748 21.2997 + 44 0.0000 0.815120 22.1805 + 45 0.0000 0.827641 22.5213 + 46 0.0000 0.849778 23.1236 + 47 0.0000 0.881083 23.9755 + 48 0.0000 0.915614 24.9151 + 49 0.0000 0.942607 25.6496 + 50 0.0000 0.973335 26.4858 + 51 0.0000 0.980031 26.6680 + 52 0.0000 1.008357 27.4388 + 53 0.0000 1.020013 27.7560 + 54 0.0000 1.054489 28.6941 + 55 0.0000 1.087507 29.5926 + 56 0.0000 1.160052 31.5666 + 57 0.0000 1.202841 32.7310 + 58 0.0000 1.228818 33.4378 + 59 0.0000 1.279420 34.8148 + 60 0.0000 1.351415 36.7739 + 61 0.0000 1.412352 38.4320 + 62 0.0000 1.451637 39.5010 + 63 0.0000 1.517338 41.2889 + 64 0.0000 1.536240 41.8032 + 65 0.0000 1.550514 42.1916 + 66 0.0000 1.609664 43.8012 + 67 0.0000 1.630353 44.3642 + 68 0.0000 1.653907 45.0051 + 69 0.0000 1.726986 46.9937 + 70 0.0000 1.759416 47.8761 + 71 0.0000 1.791735 48.7556 + 72 0.0000 1.913700 52.0744 + 73 0.0000 1.953509 53.1577 + 74 0.0000 1.965598 53.4866 + 75 0.0000 2.003821 54.5267 + 76 0.0000 2.046545 55.6893 + 77 0.0000 2.071865 56.3783 + 78 0.0000 2.159154 58.7536 + 79 0.0000 2.171171 59.0806 + 80 0.0000 2.249211 61.2041 + 81 0.0000 2.306584 62.7653 + 82 0.0000 2.341540 63.7165 + 83 0.0000 2.389431 65.0197 + 84 0.0000 2.418085 65.7994 + 85 0.0000 2.450642 66.6854 + 86 0.0000 2.473479 67.3068 + 87 0.0000 2.490854 67.7796 + 88 0.0000 2.521266 68.6071 + 89 0.0000 2.554103 69.5007 + 90 0.0000 2.579578 70.1939 + 91 0.0000 2.610855 71.0450 + 92 0.0000 2.651687 72.1561 + 93 0.0000 2.691242 73.2324 + 94 0.0000 2.760082 75.1056 + 95 0.0000 2.803548 76.2884 + 96 0.0000 2.820531 76.7506 + 97 0.0000 2.918977 79.4294 + 98 0.0000 2.964563 80.6699 + 99 0.0000 2.988029 81.3084 + 100 0.0000 3.118891 84.8693 + 101 0.0000 3.171242 86.2939 + 102 0.0000 3.228404 87.8493 + 103 0.0000 3.496465 95.1437 + 104 0.0000 3.688991 100.3826 + 105 0.0000 3.865714 105.1914 + 106 0.0000 4.020946 109.4155 + 107 0.0000 4.154276 113.0436 + 108 0.0000 4.190996 114.0428 + 109 0.0000 4.333674 117.9253 + 110 0.0000 4.361554 118.6839 + 111 0.0000 4.382475 119.2532 + 112 0.0000 4.541655 123.5847 + 113 0.0000 4.597156 125.0950 + 114 0.0000 4.666786 126.9897 + 115 0.0000 4.767833 129.7393 + 116 0.0000 4.811378 130.9243 + 117 0.0000 4.868200 132.4705 + 118 0.0000 4.955355 134.8421 + 119 0.0000 4.986120 135.6792 + 120 0.0000 5.065418 137.8370 + 121 0.0000 5.103628 138.8768 + 122 0.0000 5.180892 140.9792 + 123 0.0000 5.223969 142.1514 + 124 0.0000 5.248181 142.8103 + 125 0.0000 5.279103 143.6517 + 126 0.0000 5.379607 146.3865 + 127 0.0000 5.458671 148.5380 + 128 0.0000 5.520096 150.2095 + 129 0.0000 5.699979 155.1043 + 130 0.0000 5.765398 156.8845 + 131 0.0000 5.950782 161.9290 + 132 0.0000 6.159924 167.6201 + 133 0.0000 6.394219 173.9956 + 134 0.0000 6.487481 176.5333 + 135 0.0000 6.519635 177.4083 + 136 0.0000 6.686127 181.9388 + 137 0.0000 6.716155 182.7559 + 138 0.0000 6.779299 184.4741 + 139 0.0000 6.804208 185.1519 + 140 0.0000 6.871992 186.9964 + 141 0.0000 7.081170 192.6884 + 142 0.0000 7.118690 193.7094 + 143 0.0000 7.152192 194.6210 + 144 0.0000 7.203367 196.0136 + 145 0.0000 7.245170 197.1511 + 146 0.0000 7.262351 197.6186 + 147 0.0000 7.320590 199.2034 + 148 0.0000 7.388319 201.0464 + 149 0.0000 7.461917 203.0491 + 150 0.0000 7.483972 203.6492 + 151 0.0000 7.524640 204.7559 + 152 0.0000 7.558508 205.6775 + 153 0.0000 7.664107 208.5509 + 154 0.0000 7.711175 209.8317 + 155 0.0000 7.897145 214.8922 + 156 0.0000 8.047469 218.9828 + 157 0.0000 8.357411 227.4167 + 158 0.0000 14.002795 381.0354 + 159 0.0000 14.953662 406.9098 + 160 0.0000 15.888253 432.3414 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.347125 0.000000 + 1 N : 0.355974 0.000000 + 2 O : -0.259490 0.000000 + 3 H : 0.250641 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.838507 s : 3.838507 + pz : 1.718941 p : 4.472866 + px : 1.314882 + py : 1.439043 + dz2 : 0.004154 d : 0.031173 + dxz : 0.006833 + dyz : 0.001050 + dx2y2 : 0.014520 + dxy : 0.004616 + f0 : 0.000684 f : 0.004580 + f+1 : 0.000957 + f-1 : 0.000157 + f+2 : 0.000579 + f-2 : 0.000397 + f+3 : 0.000887 + f-3 : 0.000919 + 1 N s : 3.837762 s : 3.837762 + pz : 0.767651 p : 2.633588 + px : 0.772753 + py : 1.093184 + dz2 : 0.031786 d : 0.140799 + dxz : 0.030043 + dyz : 0.020218 + dx2y2 : 0.038030 + dxy : 0.020722 + f0 : 0.001973 f : 0.031877 + f+1 : 0.004514 + f-1 : 0.004630 + f+2 : 0.003435 + f-2 : 0.004924 + f+3 : 0.005728 + f-3 : 0.006673 + 2 O s : 3.871659 s : 3.871659 + pz : 1.234702 p : 4.318327 + px : 1.718490 + py : 1.365136 + dz2 : 0.020089 d : 0.061964 + dxz : 0.005545 + dyz : 0.012160 + dx2y2 : 0.008864 + dxy : 0.015306 + f0 : 0.000667 f : 0.007540 + f+1 : 0.000218 + f-1 : 0.002029 + f+2 : 0.001341 + f-2 : 0.001162 + f+3 : 0.001138 + f-3 : 0.000985 + 3 H s : 0.641161 s : 0.641161 + pz : 0.040306 p : 0.087549 + px : 0.025472 + py : 0.021772 + dz2 : 0.003096 d : 0.020649 + dxz : 0.000493 + dyz : 0.005708 + dx2y2 : 0.001869 + dxy : 0.009483 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.582409 0.000000 + 1 N : -0.248487 0.000000 + 2 O : 0.245315 0.000000 + 3 H : -0.579237 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.127664 s : 3.127664 + pz : 1.395496 p : 3.939850 + px : 1.215104 + py : 1.329250 + dz2 : 0.035101 d : 0.270017 + dxz : 0.066494 + dyz : 0.028233 + dx2y2 : 0.079302 + dxy : 0.060887 + f0 : 0.007803 f : 0.080060 + f+1 : 0.015179 + f-1 : 0.000599 + f+2 : 0.013801 + f-2 : 0.009519 + f+3 : 0.010858 + f-3 : 0.022300 + 1 N s : 3.028121 s : 3.028121 + pz : 0.822183 p : 2.832593 + px : 0.845284 + py : 1.165126 + dz2 : 0.155024 d : 0.937448 + dxz : 0.215204 + dyz : 0.166086 + dx2y2 : 0.230757 + dxy : 0.170378 + f0 : 0.033463 f : 0.450325 + f+1 : 0.052766 + f-1 : 0.053893 + f+2 : 0.079009 + f-2 : 0.080725 + f+3 : 0.069423 + f-3 : 0.081046 + 2 O s : 3.308400 s : 3.308400 + pz : 1.193718 p : 4.003108 + px : 1.420936 + py : 1.388453 + dz2 : 0.038826 d : 0.326833 + dxz : 0.053394 + dyz : 0.098762 + dx2y2 : 0.090828 + dxy : 0.045023 + f0 : 0.010134 f : 0.116344 + f+1 : 0.006008 + f-1 : 0.019628 + f+2 : 0.030030 + f-2 : 0.020811 + f+3 : 0.008988 + f-3 : 0.020744 + 3 H s : 0.620964 s : 0.620964 + pz : 0.168788 p : 0.562784 + px : 0.138033 + py : 0.255962 + dz2 : 0.056233 d : 0.395490 + dxz : 0.033199 + dyz : 0.109663 + dx2y2 : 0.093216 + dxy : 0.103178 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3471 8.0000 -0.3471 1.8215 1.8215 -0.0000 + 1 N 6.6440 7.0000 0.3560 2.5601 2.5601 0.0000 + 2 O 8.2595 8.0000 -0.2595 1.7581 1.7581 -0.0000 + 3 H 0.7494 1.0000 0.2506 1.0066 1.0066 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8128 B( 0-O , 3-H ) : 0.9472 B( 1-N , 2-O ) : 1.6922 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 5 sec + +Total time .... 5.711 sec +Sum of individual times .... 5.313 sec ( 93.0%) + +Fock matrix formation .... 4.617 sec ( 80.8%) +Diagonalization .... 0.332 sec ( 5.8%) +Density matrix formation .... 0.024 sec ( 0.4%) +Population analysis .... 0.067 sec ( 1.2%) +Initial guess .... 0.018 sec ( 0.3%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.011 sec ( 0.2%) +DIIS solution .... 0.257 sec ( 4.5%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.502 sec +Reference energy ... -204.711208337 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 9.842 sec +AO-integral generation ... 0.324 sec +Half transformation ... 0.173 sec +K-integral sorting ... 7.774 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.053 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.060 s ( 0.000 ms/b) + 277134 b 0 skpd 0.091 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.072 s ( 0.000 ms/b) +: 159120 b 0 skpd 0.041 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.086 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.065 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.059 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.099 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.053 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.780 sec +AO-integral generation ... 0.598 sec +Half transformation ... 0.084 sec +J-integral sorting ... 0.074 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.227 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.364 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090336798 +EMP2(bb)= -0.090336798 +EMP2(ab)= -0.516976718 + +Initial guess performed in 0.191 sec +E(0) ... -204.711208337 +E(MP2) ... -0.697650313 +Initial E(tot) ... -205.408858650 + ... 0.189064676 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.408858650 -0.697650313 -0.000000000 0.022927894 5.53 0.000002814 + *** Turning on DIIS *** + 1 -205.379953509 -0.668745173 0.028905141 0.009981617 6.31 0.057432737 + 2 -205.399586538 -0.688378201 -0.019633028 0.004929321 5.97 0.060437990 + 3 -205.403391741 -0.692183405 -0.003805204 0.001890602 6.25 0.074599921 + 4 -205.404980336 -0.693772000 -0.001588595 0.001595201 5.62 0.081345513 + 5 -205.405539644 -0.694331307 -0.000559308 0.000962891 6.46 0.086955763 + 6 -205.405651642 -0.694443305 -0.000111998 0.000592069 5.50 0.089888040 + 7 -205.405701805 -0.694493468 -0.000050163 0.000276556 7.06 0.091346809 + 8 -205.405715178 -0.694506841 -0.000013373 0.000131254 6.63 0.091970495 + 9 -205.405711056 -0.694502719 0.000004122 0.000060051 4.61 0.092166939 + 10 -205.405717062 -0.694508726 -0.000006007 0.000036383 4.91 0.092248853 + 11 -205.405713596 -0.694505259 0.000003466 0.000025761 5.06 0.092237431 + 12 -205.405715344 -0.694507007 -0.000001748 0.000016674 5.56 0.092256598 + 13 -205.405715181 -0.694506844 0.000000162 0.000010053 5.17 0.092251488 + 14 -205.405715485 -0.694507149 -0.000000304 0.000005012 6.65 0.092256959 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.711208337 +E(CORR) ... -0.694507149 +E(TOT) ... -205.405715485 +Singles norm **1/2 ... 0.092256959 ( 0.046128479, 0.046128479) +T1 diagnostic ... 0.021745174 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.059078 + 9a-> 13a 9b-> 13b 0.042892 + 8a-> 13a -1a-> -1a 0.036841 + 8b-> 13b -1b-> -1b 0.036841 + 9a-> 13a 8b-> 13b 0.036787 + 8a-> 13a 9b-> 13b 0.036787 + 10a-> 13a -1a-> -1a 0.031997 + 10b-> 13b -1b-> -1b 0.031997 + 11a-> 25a 11b-> 25b 0.031177 + 11a-> 13a 11b-> 13b 0.029477 + 5a-> 13a 5b-> 13b 0.028363 + 11b-> 25b -1b-> -1b 0.026164 + 11a-> 25a -1a-> -1a 0.026164 + 10a-> 13a 10b-> 13b 0.024422 + 9a-> 13a 10b-> 13b 0.023476 + 10a-> 13a 9b-> 13b 0.023476 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034823782 + alpha-alpha-alpha ... -0.000890472 ( 2.6%) + alpha-alpha-beta ... -0.016521419 ( 47.4%) + alpha-beta -beta ... -0.016521419 ( 47.4%) + beta -beta -beta ... -0.000890472 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034823782 + +Final correlation energy ... -0.729330931 +E(CCSD) ... -205.405715485 +E(CCSD(T)) ... -205.440539267 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.211718516 sqrt= 1.100780866 +W(HF) = 0.825274176 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.274188 -0.000000 + 1 N : 0.171868 -0.000000 + 2 O : -0.135591 0.000000 + 3 H : 0.237910 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.822312 s : 3.822312 + pz : 1.671171 p : 4.381965 + px : 1.296896 + py : 1.413898 + dz2 : 0.011143 d : 0.061618 + dxz : 0.012608 + dyz : 0.007785 + dx2y2 : 0.018133 + dxy : 0.011950 + f0 : 0.001186 f : 0.008292 + f+1 : 0.001526 + f-1 : 0.000805 + f+2 : 0.001006 + f-2 : 0.000999 + f+3 : 0.001320 + f-3 : 0.001449 + 1 N s : 3.890447 s : 3.890447 + pz : 0.840722 p : 2.737150 + px : 0.822657 + py : 1.073770 + dz2 : 0.035446 d : 0.169655 + dxz : 0.038944 + dyz : 0.024140 + dx2y2 : 0.044568 + dxy : 0.026558 + f0 : 0.002149 f : 0.030879 + f+1 : 0.004620 + f-1 : 0.003940 + f+2 : 0.003254 + f-2 : 0.004861 + f+3 : 0.005410 + f-3 : 0.006645 + 2 O s : 3.858533 s : 3.858533 + pz : 1.204154 p : 4.183306 + px : 1.644358 + py : 1.334794 + dz2 : 0.022265 d : 0.083749 + dxz : 0.012265 + dyz : 0.014688 + dx2y2 : 0.015072 + dxy : 0.019458 + f0 : 0.001059 f : 0.010004 + f+1 : 0.000786 + f-1 : 0.001962 + f+2 : 0.001664 + f-2 : 0.001554 + f+3 : 0.001536 + f-3 : 0.001443 + 3 H s : 0.652093 s : 0.652093 + pz : 0.045267 p : 0.091846 + px : 0.029009 + py : 0.017570 + dz2 : 0.002827 d : 0.018151 + dxz : 0.000757 + dyz : 0.004834 + dx2y2 : 0.001108 + dxy : 0.008625 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.593721 -0.000000 + 1 N : -0.295837 -0.000000 + 2 O : 0.284315 0.000000 + 3 H : -0.582199 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.134133 s : 3.134133 + pz : 1.361635 p : 3.883362 + px : 1.210513 + py : 1.311214 + dz2 : 0.041141 d : 0.301548 + dxz : 0.073325 + dyz : 0.035195 + dx2y2 : 0.085950 + dxy : 0.065938 + f0 : 0.008857 f : 0.087236 + f+1 : 0.016127 + f-1 : 0.001280 + f+2 : 0.015399 + f-2 : 0.010423 + f+3 : 0.012421 + f-3 : 0.022730 + 1 N s : 3.033381 s : 3.033381 + pz : 0.865530 p : 2.878785 + px : 0.867102 + py : 1.146153 + dz2 : 0.153972 d : 0.943598 + dxz : 0.218793 + dyz : 0.172088 + dx2y2 : 0.233546 + dxy : 0.165198 + f0 : 0.034273 f : 0.440073 + f+1 : 0.048579 + f-1 : 0.053559 + f+2 : 0.077539 + f-2 : 0.077873 + f+3 : 0.069765 + f-3 : 0.078486 + 2 O s : 3.310617 s : 3.310617 + pz : 1.176803 p : 3.922266 + px : 1.375373 + py : 1.370090 + dz2 : 0.049779 d : 0.357814 + dxz : 0.057785 + dyz : 0.103848 + dx2y2 : 0.095094 + dxy : 0.051308 + f0 : 0.011657 f : 0.124988 + f+1 : 0.006867 + f-1 : 0.023602 + f+2 : 0.029921 + f-2 : 0.021602 + f+3 : 0.010772 + f-3 : 0.020567 + 3 H s : 0.623324 s : 0.623324 + pz : 0.174401 p : 0.574156 + px : 0.138339 + py : 0.261415 + dz2 : 0.054931 d : 0.384719 + dxz : 0.032270 + dyz : 0.105751 + dx2y2 : 0.091973 + dxy : 0.099793 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2742 8.0000 -0.2742 2.1907 1.7305 0.4602 + 1 N 6.8281 7.0000 0.1719 2.8364 2.3505 0.4859 + 2 O 8.1356 8.0000 -0.1356 2.1509 1.6519 0.4990 + 3 H 0.7621 1.0000 0.2379 1.0239 0.9492 0.0747 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7504 B( 0-O , 2-O ) : 0.1005 B( 0-O , 3-H ) : 0.8796 +B( 1-N , 2-O ) : 1.5410 + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 115.799 sec + +Fock Matrix Formation ... 0.502 sec ( 0.4%) +Initial Guess ... 0.191 sec ( 0.2%) +DIIS Solver ... 5.647 sec ( 4.9%) +State Vector Update ... 0.295 sec ( 0.3%) +Sigma-vector construction ... 81.368 sec ( 70.3%) + <0|H|D> ... 0.008 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.047 sec ( 0.1% of sigma) + (0-ext) ... 0.154 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.059 sec ( 0.1% of sigma) + (2-ext) ... 2.148 sec ( 2.6% of sigma) + (4-ext) ... 48.113 sec ( 59.1% of sigma) + ... 3.276 sec ( 4.0% of sigma) + ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.021 sec ( 0.0% of sigma) + (1-ext) ... 0.225 sec ( 0.3% of sigma) + Fock-dressing ... 5.600 sec ( 6.9% of sigma) + (ik|jl)-dressing ... 0.170 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 17.521 sec ( 21.5% of sigma) + Pair energies ... 0.025 sec ( 0.0% of sigma) +Total Time for computing (T) ... 14.832 sec ( 12.8% of ALL) + I/O of integral and amplitudes ... 1.199 sec ( 8.1% of (T)) + External N**7 contributions ... 5.777 sec ( 38.9% of (T)) + Internal N**7 contributions ... 0.448 sec ( 3.0% of (T)) + N**6 triples energy contributions ... 2.266 sec ( 15.3% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.440539267292 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.008274383 0.002758791 -0.010668989 + 2 N : 0.009330191 0.001425453 0.008675211 + 3 O : -0.004280992 -0.002277985 -0.006569765 + 4 H : 0.003225184 -0.001906259 0.008563542 + +Norm of the cartesian gradient ... 0.022545402 +RMS gradient ... 0.006508297 +MAX gradient ... 0.010668989 + +------- +TIMINGS +------- + +Total numerical gradient time ... 695.328 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: -287.32 cm**-1 ***imaginary mode*** + 7: 606.67 cm**-1 + 8: 780.97 cm**-1 + 9: 1243.76 cm**-1 + 10: 1688.80 cm**-1 + 11: 3685.00 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 0.093120 -0.341958 -0.161145 0.053906 -0.053332 -0.002401 + 1 -0.021227 -0.109966 0.114895 0.067382 0.043527 -0.058081 + 2 0.040677 0.327899 0.019811 -0.016964 0.021082 -0.023156 + 3 -0.097510 0.109119 0.362439 0.055606 -0.065986 0.000618 + 4 -0.033703 0.110829 -0.207295 -0.047325 -0.569625 -0.000272 + 5 -0.036877 -0.206538 -0.105344 -0.050464 0.362919 -0.000398 + 6 0.011183 0.293448 -0.185029 -0.044037 0.135164 -0.000390 + 7 0.028339 0.006712 0.045077 -0.023571 0.455780 -0.000106 + 8 0.046442 -0.137146 0.112249 0.039758 -0.351250 0.000369 + 9 -0.300513 -0.746351 0.458089 -0.929330 -0.381909 0.035720 + 10 0.355443 0.098794 0.341457 -0.037746 -0.009603 0.927341 + 11 -0.870337 -0.157610 -0.632221 0.339460 0.197362 0.367214 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 7: 606.67 0.014812 74.85 0.007619 ( 0.047302 0.025355 -0.068837) + 8: 780.97 0.042768 216.13 0.017089 ( 0.101579 -0.001991 -0.082262) + 9: 1243.76 0.002124 10.73 0.000533 (-0.016204 0.015091 0.006529) + 10: 1688.80 0.032686 165.18 0.006040 (-0.056708 -0.018592 0.049784) + 11: 3685.00 0.009509 48.05 0.000805 (-0.010785 0.018851 0.018263) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 7 +The total number of vibrations considered is 5 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 606.67 E(vib) ... 0.10 +freq. 780.97 E(vib) ... 0.05 +freq. 1243.76 E(vib) ... 0.01 +freq. 1688.80 E(vib) ... 0.00 +freq. 3685.00 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.44053927 Eh +Zero point energy ... 0.01823721 Eh 11.44 kcal/mol +Thermal vibrational correction ... 0.00025669 Eh 0.16 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.41921282 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00308924 Eh 1.94 kcal/mol +Non-thermal (ZPE) correction 0.01823721 Eh 11.44 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02132644 Eh 13.38 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.41921282 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.41826861 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.703411 0.413699 0.365403 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00033359 Eh 0.21 kcal/mol +Rotational entropy ... 0.00993326 Eh 6.23 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02806917 Eh 17.61 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00993326 Eh 6.23 kcal/mol| +| sn= 2 | S(rot)= 0.00927881 Eh 5.82 kcal/mol| +| sn= 3 | S(rot)= 0.00889597 Eh 5.58 kcal/mol| +| sn= 4 | S(rot)= 0.00862435 Eh 5.41 kcal/mol| +| sn= 5 | S(rot)= 0.00841366 Eh 5.28 kcal/mol| +| sn= 6 | S(rot)= 0.00824152 Eh 5.17 kcal/mol| +| sn= 7 | S(rot)= 0.00809597 Eh 5.08 kcal/mol| +| sn= 8 | S(rot)= 0.00796989 Eh 5.00 kcal/mol| +| sn= 9 | S(rot)= 0.00785869 Eh 4.93 kcal/mol| +| sn=10 | S(rot)= 0.00775921 Eh 4.87 kcal/mol| +| sn=11 | S(rot)= 0.00766922 Eh 4.81 kcal/mol| +| sn=12 | S(rot)= 0.00758706 Eh 4.76 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.41826861 Eh +Total entropy correction ... -0.02806917 Eh -17.61 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44633779 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00579852 Eh -3.64 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.440539266 Eh +Current gradient norm .... 0.022545294 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + -0.013556129 0.108213248 0.184689717 0.483337142 0.523027665 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999388426 +Lowest eigenvalues of augmented Hessian: + -0.000147918 0.101558817 0.183746062 0.483148924 0.522884123 +Length of the computed step .... 0.034989591 +The final length of the internal step .... 0.034989591 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0142844407 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0068982361 RMS(Int)= 0.0142856342 + Iter 1: RMS(Cart)= 0.0000211951 RMS(Int)= 0.0000384454 + Iter 2: RMS(Cart)= 0.0000001982 RMS(Int)= 0.0000001607 + Iter 3: RMS(Cart)= 0.0000000014 RMS(Int)= 0.0000000023 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000006 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0020784022 0.0001000000 NO + MAX gradient 0.0037721380 0.0003000000 NO + RMS step 0.0142844407 0.0020000000 NO + MAX step 0.0327602464 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0173 Max(Angles) 0.49 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4694 0.003772 -0.0173 1.4521 + 2. B(O 2,N 1) 1.1742 0.001088 0.0016 1.1758 + 3. B(H 3,O 0) 0.9736 0.001516 -0.0014 0.9723 + 4. A(N 1,O 0,H 3) 104.41 0.000064 0.46 104.87 + 5. A(O 0,N 1,O 2) 112.26 -0.002864 0.49 112.74 + 6. D(O 2,N 1,O 0,H 3) -49.09 -0.016431 -0.00 -49.09 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.737692 -0.346462 0.389967 + N 0.565891 -0.547723 -0.217215 + O 0.880003 0.338265 -0.923508 + H -0.708202 0.555920 0.750757 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.394036 -0.654718 0.736930 + 1 N 7.0000 0 14.007 1.069380 -1.035046 -0.410478 + 2 O 8.0000 0 15.999 1.662965 0.639228 -1.745177 + 3 H 1.0000 0 1.008 -1.338308 1.050536 1.418725 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.452069406376 0.00000000 0.00000000 + O 2 1 0 1.175793260604 112.74124951 0.00000000 + H 1 2 3 0.972281347699 104.86689923 310.90909071 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.744013505497 0.00000000 0.00000000 + O 2 1 0 2.221927252652 112.74124951 0.00000000 + H 1 2 3 1.837345472270 104.86689923 310.90909071 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2237 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2709 + la=0 lb=0: 554 shell pairs + la=1 lb=0: 538 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.138121593351 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.605e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7124481091 0.000000000000 0.00050322 0.00001363 0.0027821 0.7000 + 1 -204.7124918284 -0.000043719302 0.00041323 0.00001139 0.0021643 0.7000 + ***Turning on DIIS*** + 2 -204.7125281440 -0.000036315620 0.00105514 0.00002954 0.0016640 0.0000 + 3 -204.7122609745 0.000267169497 0.00037998 0.00001328 0.0004690 0.0000 + 4 -204.7128662471 -0.000605272516 0.00015374 0.00000399 0.0001335 0.0000 + 5 -204.7126552105 0.000211036521 0.00003821 0.00000131 0.0000426 0.0000 + 6 -204.7124329521 0.000222258397 0.00001772 0.00000062 0.0000451 0.0000 + 7 -204.7126740700 -0.000241117851 0.00000892 0.00000035 0.0000191 0.0000 + 8 -204.7126309659 0.000043104052 0.00000849 0.00000029 0.0000101 0.0000 + 9 -204.7126260946 0.000004871321 0.00000525 0.00000023 0.0000074 0.0000 + 10 -204.7126598403 -0.000033745678 0.00000296 0.00000013 0.0000022 0.0000 + 11 -204.7126420275 0.000017812792 0.00000175 0.00000007 0.0000014 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + +Total Energy : -204.71264737 Eh -5570.51433 eV + Last Energy change ... -5.3471e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.2864e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 2 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.214 sec +Reference energy ... -204.712645993 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.423 sec +AO-integral generation ... 0.143 sec +Half transformation ... 0.079 sec +K-integral sorting ... 5.422 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.028 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.032 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.017 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.030 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.023 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.023 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.349 sec +AO-integral generation ... 0.243 sec +Half transformation ... 0.042 sec +J-integral sorting ... 0.051 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.150 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.251 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090193381 +EMP2(bb)= -0.090193381 +EMP2(ab)= -0.515888509 + +Initial guess performed in 0.131 sec +E(0) ... -204.712645993 +E(MP2) ... -0.696275270 +Initial E(tot) ... -205.408921263 + ... 0.187745433 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.408921263 -0.696275270 -0.000000000 0.023144947 3.23 0.000001206 + *** Turning on DIIS *** + 1 -205.380618979 -0.667972986 0.028302284 0.009636708 3.13 0.056895626 + 2 -205.400034791 -0.687388799 -0.019415813 0.005011413 3.33 0.060027038 + 3 -205.403800173 -0.691154180 -0.003765382 0.001793949 2.84 0.074033682 + 4 -205.405366946 -0.692720954 -0.001566773 0.001505900 3.04 0.080712156 + 5 -205.405911953 -0.693265961 -0.000545007 0.000910700 2.95 0.086177487 + 6 -205.406020004 -0.693374011 -0.000108051 0.000556965 2.97 0.088979208 + 7 -205.406067035 -0.693421043 -0.000047031 0.000262910 3.17 0.090324987 + 8 -205.406078999 -0.693433007 -0.000011964 0.000122728 3.32 0.090899405 + 9 -205.406075165 -0.693429173 0.000003834 0.000062152 3.11 0.091084049 + 10 -205.406080646 -0.693434654 -0.000005481 0.000037348 2.99 0.091159522 + 11 -205.406077370 -0.693431378 0.000003276 0.000026381 3.12 0.091149597 + 12 -205.406079135 -0.693433142 -0.000001764 0.000016723 3.05 0.091167692 + 13 -205.406078933 -0.693432940 0.000000202 0.000009643 3.23 0.091162993 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.712645993 +E(CORR) ... -0.693432940 +E(TOT) ... -205.406078933 +Singles norm **1/2 ... 0.091162993 ( 0.045581496, 0.045581496) +T1 diagnostic ... 0.021487323 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.056646 + 9a-> 13a 9b-> 13b 0.043548 + 8a-> 13a -1a-> -1a 0.037435 + 8b-> 13b -1b-> -1b 0.037435 + 9a-> 13a 8b-> 13b 0.035939 + 8a-> 13a 9b-> 13b 0.035939 + 11a-> 13a 11b-> 13b 0.030364 + 10b-> 13b -1b-> -1b 0.029857 + 10a-> 13a -1a-> -1a 0.029857 + 5a-> 13a 5b-> 13b 0.027655 + 10a-> 13a 10b-> 13b 0.026188 + 9a-> 13a 10b-> 13b 0.024907 + 10a-> 13a 9b-> 13b 0.024907 + 8a-> 13a 10b-> 13b 0.022653 + 10a-> 13a 8b-> 13b 0.022653 + 11a-> 25a 11b-> 25b 0.022580 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034532213 + alpha-alpha-alpha ... -0.000887592 ( 2.6%) + alpha-alpha-beta ... -0.016378514 ( 47.4%) + alpha-beta -beta ... -0.016378514 ( 47.4%) + beta -beta -beta ... -0.000887592 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034532213 + +Final correlation energy ... -0.727965152 +E(CCSD) ... -205.406078933 +E(CCSD(T)) ... -205.440611145 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210041795 sqrt= 1.100018998 +W(HF) = 0.826417735 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 59.107 sec + +Fock Matrix Formation ... 0.214 sec ( 0.4%) +Initial Guess ... 0.131 sec ( 0.2%) +DIIS Solver ... 2.205 sec ( 3.7%) +State Vector Update ... 0.095 sec ( 0.2%) +Sigma-vector construction ... 41.176 sec ( 69.7%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.025 sec ( 0.1% of sigma) + (0-ext) ... 0.070 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (2-ext) ... 0.970 sec ( 2.4% of sigma) + (4-ext) ... 23.680 sec ( 57.5% of sigma) + ... 1.536 sec ( 3.7% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.111 sec ( 0.3% of sigma) + Fock-dressing ... 2.110 sec ( 5.1% of sigma) + (ik|jl)-dressing ... 0.077 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.900 sec ( 24.0% of sigma) + Pair energies ... 0.006 sec ( 0.0% of sigma) +Total Time for computing (T) ... 7.357 sec ( 12.4% of ALL) + I/O of integral and amplitudes ... 0.890 sec ( 12.1% of (T)) + External N**7 contributions ... 4.148 sec ( 56.4% of (T)) + Internal N**7 contributions ... 0.345 sec ( 4.7% of (T)) + N**6 triples energy contributions ... 1.749 sec ( 23.8% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.440611145035 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.005037113 0.002712201 -0.011972926 + 2 N : 0.005090395 0.004618332 0.010198933 + 3 O : -0.003496724 -0.003852441 -0.006675854 + 4 H : 0.003443442 -0.003478092 0.008449847 + +Norm of the cartesian gradient ... 0.022233501 +RMS gradient ... 0.006418259 +MAX gradient ... 0.011972926 + +------- +TIMINGS +------- + +Total numerical gradient time ... 371.448 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.440611145 Eh +Current gradient norm .... 0.022233501 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999998692 +Lowest eigenvalues of augmented Hessian: + -0.000000453 0.104412151 0.185894609 0.483674699 0.528025887 +Length of the computed step .... 0.001617588 +The final length of the internal step .... 0.001617588 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0006603774 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0003416725 RMS(Int)= 0.0006603643 + Iter 1: RMS(Cart)= 0.0000000597 RMS(Int)= 0.0000001101 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000718789 0.0000050000 NO + RMS gradient 0.0001531741 0.0001000000 NO + MAX gradient 0.0002861602 0.0003000000 YES + RMS step 0.0006603774 0.0020000000 YES + MAX step 0.0014594250 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0008 Max(Angles) 0.03 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4521 -0.000149 0.0008 1.4528 + 2. B(O 2,N 1) 1.1758 0.000173 -0.0002 1.1756 + 3. B(H 3,O 0) 0.9723 0.000011 -0.0000 0.9723 + 4. A(N 1,O 0,H 3) 104.87 -0.000081 0.00 104.87 + 5. A(O 0,N 1,O 2) 112.74 0.000286 -0.03 112.71 + 6. D(O 2,N 1,O 0,H 3) -49.09 -0.017340 -0.00 -49.09 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.737921 -0.346343 0.390051 + N 0.566332 -0.547890 -0.217446 + O 0.879933 0.338235 -0.923463 + H -0.708342 0.555997 0.750858 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.394469 -0.654493 0.737089 + 1 N 7.0000 0 14.007 1.070212 -1.035361 -0.410913 + 2 O 8.0000 0 15.999 1.662832 0.639172 -1.745093 + 3 H 1.0000 0 1.008 -1.338572 1.050683 1.418916 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.452841700796 0.00000000 0.00000000 + O 2 1 0 1.175594814943 112.70777049 0.00000000 + H 1 2 3 0.972252475411 104.86921373 310.90909070 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.745472930446 0.00000000 0.00000000 + O 2 1 0 2.221552244701 112.70777049 0.00000000 + H 1 2 3 1.837290911554 104.86921373 310.90909070 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2237 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2709 + la=0 lb=0: 554 shell pairs + la=1 lb=0: 538 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.130242306497 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.606e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7126135719 0.000000000000 0.00002222 0.00000067 0.0001374 0.7000 + 1 -204.7126136865 -0.000000114575 0.00001785 0.00000057 0.0001060 0.7000 + ***Turning on DIIS*** + 2 -204.7126137815 -0.000000094984 0.00004612 0.00000152 0.0000844 0.0000 + 3 -204.7126093784 0.000004403066 0.00001624 0.00000065 0.0000251 0.0000 + 4 -204.7126137107 -0.000004332303 0.00000513 0.00000019 0.0000060 0.0000 + 5 -204.7126157701 -0.000002059363 0.00000305 0.00000007 0.0000026 0.0000 + 6 -204.7126185022 -0.000002732112 0.00000081 0.00000003 0.0000019 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + +Total Energy : -204.71261374 Eh -5570.51342 eV + Last Energy change ... 4.7578e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.3038e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.205 sec +Reference energy ... -204.712614090 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.301 sec +AO-integral generation ... 0.144 sec +Half transformation ... 0.079 sec +K-integral sorting ... 5.303 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.027 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.031 s ( 0.000 ms/b) + 151164 b 0 skpd 0.037 s ( 0.000 ms/b) +: 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.342 sec +AO-integral generation ... 0.239 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.048 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.160 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.250 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090195661 +EMP2(bb)= -0.090195661 +EMP2(ab)= -0.515914949 + +Initial guess performed in 0.133 sec +E(0) ... -204.712614090 +E(MP2) ... -0.696306272 +Initial E(tot) ... -205.408920362 + ... 0.187777824 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.408920362 -0.696306272 -0.000000000 0.023127195 3.27 0.000001665 + *** Turning on DIIS *** + 1 -205.380605074 -0.667990984 0.028315288 0.009653860 4.30 0.056907624 + 2 -205.400025766 -0.687411676 -0.019420692 0.005005467 3.63 0.060034473 + 3 -205.403792059 -0.691177969 -0.003766293 0.001798764 2.95 0.074044249 + 4 -205.405359146 -0.692745056 -0.001567087 0.001510227 3.21 0.080723424 + 5 -205.405904467 -0.693290377 -0.000545321 0.000913093 3.04 0.086193364 + 6 -205.406012664 -0.693398574 -0.000108196 0.000558479 3.37 0.089000511 + 7 -205.406059815 -0.693445725 -0.000047152 0.000263396 3.07 0.090351067 + 8 -205.406071835 -0.693457745 -0.000012019 0.000123052 3.01 0.090927401 + 9 -205.406067988 -0.693453898 0.000003847 0.000061987 3.12 0.091112357 + 10 -205.406073487 -0.693459397 -0.000005499 0.000037266 2.91 0.091188054 + 11 -205.406070207 -0.693456117 0.000003280 0.000026327 2.91 0.091178057 + 12 -205.406071966 -0.693457877 -0.000001760 0.000016706 2.94 0.091196180 + 13 -205.406071767 -0.693457677 0.000000199 0.000009655 2.92 0.091191465 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.712614090 +E(CORR) ... -0.693457677 +E(TOT) ... -205.406071767 +Singles norm **1/2 ... 0.091191465 ( 0.045595732, 0.045595732) +T1 diagnostic ... 0.021494034 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.056781 + 9a-> 13a 9b-> 13b 0.043485 + 8a-> 13a -1a-> -1a 0.037391 + 8b-> 13b -1b-> -1b 0.037391 + 8a-> 13a 9b-> 13b 0.035971 + 9a-> 13a 8b-> 13b 0.035971 + 11a-> 13a 11b-> 13b 0.030313 + 10a-> 13a -1a-> -1a 0.029964 + 10b-> 13b -1b-> -1b 0.029964 + 5a-> 13a 5b-> 13b 0.027682 + 10a-> 13a 10b-> 13b 0.026081 + 10a-> 13a 9b-> 13b 0.024814 + 9a-> 13a 10b-> 13b 0.024814 + 11a-> 25a 11b-> 25b 0.022979 + 8a-> 13a 10b-> 13b 0.022629 + 10a-> 13a 8b-> 13b 0.022629 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034539594 + alpha-alpha-alpha ... -0.000887624 ( 2.6%) + alpha-alpha-beta ... -0.016382173 ( 47.4%) + alpha-beta -beta ... -0.016382173 ( 47.4%) + beta -beta -beta ... -0.000887624 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034539594 + +Final correlation energy ... -0.727997271 +E(CCSD) ... -205.406071767 +E(CCSD(T)) ... -205.440611361 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210084977 sqrt= 1.100038625 +W(HF) = 0.826388244 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 59.793 sec + +Fock Matrix Formation ... 0.205 sec ( 0.3%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 2.208 sec ( 3.7%) +State Vector Update ... 0.102 sec ( 0.2%) +Sigma-vector construction ... 42.333 sec ( 70.8%) + <0|H|D> ... 0.005 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.024 sec ( 0.1% of sigma) + (0-ext) ... 0.070 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (2-ext) ... 0.940 sec ( 2.2% of sigma) + (4-ext) ... 24.593 sec ( 58.1% of sigma) + ... 1.447 sec ( 3.4% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.114 sec ( 0.3% of sigma) + Fock-dressing ... 2.072 sec ( 4.9% of sigma) + (ik|jl)-dressing ... 0.075 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.271 sec ( 24.3% of sigma) + Pair energies ... 0.007 sec ( 0.0% of sigma) +Total Time for computing (T) ... 7.012 sec ( 11.7% of ALL) + I/O of integral and amplitudes ... 0.690 sec ( 9.8% of (T)) + External N**7 contributions ... 3.890 sec ( 55.5% of (T)) + Internal N**7 contributions ... 0.308 sec ( 4.4% of (T)) + N**6 triples energy contributions ... 1.627 sec ( 23.2% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.440611361281 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.005127984 0.002856201 -0.011916907 + 2 N : 0.005370620 0.004533892 0.010012932 + 3 O : -0.003636106 -0.003908066 -0.006533785 + 4 H : 0.003393470 -0.003482027 0.008437760 + +Norm of the cartesian gradient ... 0.022184361 +RMS gradient ... 0.006404073 +MAX gradient ... 0.011916907 + +------- +TIMINGS +------- + +Total numerical gradient time ... 369.827 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.440611361 Eh +Current gradient norm .... 0.022184361 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999994 +Lowest eigenvalues of augmented Hessian: + -0.000000002 0.110554228 0.188535175 0.476500998 0.519118838 +Length of the computed step .... 0.000112823 +The final length of the internal step .... 0.000112823 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0000460600 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0000286610 RMS(Int)= 0.0000460600 + Iter 1: RMS(Cart)= 0.0000000003 RMS(Int)= 0.0000000004 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000002162 0.0000050000 YES + RMS gradient 0.0000095775 0.0001000000 YES + MAX gradient 0.0000154968 0.0003000000 YES + RMS step 0.0000460600 0.0020000000 YES + MAX step 0.0001054278 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4528 0.000015 -0.0001 1.4528 + 2. B(O 2,N 1) 1.1756 0.000009 0.0000 1.1756 + 3. B(H 3,O 0) 0.9723 0.000002 -0.0000 0.9722 + 4. A(N 1,O 0,H 3) 104.87 -0.000003 0.00 104.87 + 5. A(O 0,N 1,O 2) 112.71 0.000015 -0.00 112.71 + 6. D(O 2,N 1,O 0,H 3) -49.09 -0.017292 0.00 -49.09 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.737891 -0.346339 0.390032 + N 0.566313 -0.547895 -0.217433 + O 0.879911 0.338238 -0.923447 + H -0.708333 0.555996 0.750848 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.394411 -0.654485 0.737054 + 1 N 7.0000 0 14.007 1.070177 -1.035372 -0.410888 + 2 O 8.0000 0 15.999 1.662791 0.639177 -1.745063 + 3 H 1.0000 0 1.008 -1.338555 1.050680 1.418897 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.452785910812 0.00000000 0.00000000 + O 2 1 0 1.175598652791 112.70663287 0.00000000 + H 1 2 3 0.972249630504 104.87114689 310.90909070 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.745367502654 0.00000000 0.00000000 + O 2 1 0 2.221559497181 112.70663287 0.00000000 + H 1 2 3 1.837285535459 104.87114689 310.90909070 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2237 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2709 + la=0 lb=0: 554 shell pairs + la=1 lb=0: 538 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.131434732963 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.1314347330 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.606e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.003 sec +Total time needed ... 0.006 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7126190515 0.000000000000 0.00000168 0.00000004 0.0000085 0.7000 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 1 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71261905 Eh -5570.51356 eV + +Components: +Nuclear Repulsion : 69.13143473 Eh 1881.16198 eV +Electronic Energy : -273.84405378 Eh -7451.67554 eV +One Electron Energy: -417.90883584 Eh -11371.87756 eV +Two Electron Energy: 144.06478206 Eh 3920.20202 eV + +Virial components: +Potential Energy : -408.94903319 Eh -11128.06893 eV +Kinetic Energy : 204.23641414 Eh 5557.55537 eV +Virial Ratio : 2.00233164 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -3.3054e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.3919e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.5354e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.6474e-06 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.680676 -562.7498 + 1 1.0000 -20.631629 -561.4152 + 2 1.0000 -15.804060 -430.0503 + 3 1.0000 -1.611138 -43.8413 + 4 1.0000 -1.389800 -37.8184 + 5 1.0000 -0.960584 -26.1388 + 6 1.0000 -0.772260 -21.0143 + 7 1.0000 -0.737407 -20.0659 + 8 1.0000 -0.695881 -18.9359 + 9 1.0000 -0.605171 -16.4675 + 10 1.0000 -0.533781 -14.5249 + 11 1.0000 -0.467253 -12.7146 + 12 0.0000 0.031006 0.8437 + 13 0.0000 0.069213 1.8834 + 14 0.0000 0.093666 2.5488 + 15 0.0000 0.109700 2.9851 + 16 0.0000 0.115326 3.1382 + 17 0.0000 0.153187 4.1684 + 18 0.0000 0.157157 4.2765 + 19 0.0000 0.171306 4.6615 + 20 0.0000 0.180392 4.9087 + 21 0.0000 0.192365 5.2345 + 22 0.0000 0.202922 5.5218 + 23 0.0000 0.234602 6.3838 + 24 0.0000 0.266342 7.2475 + 25 0.0000 0.290158 7.8956 + 26 0.0000 0.310242 8.4421 + 27 0.0000 0.337781 9.1915 + 28 0.0000 0.343666 9.3516 + 29 0.0000 0.370083 10.0705 + 30 0.0000 0.421926 11.4812 + 31 0.0000 0.513975 13.9860 + 32 0.0000 0.531169 14.4539 + 33 0.0000 0.534855 14.5541 + 34 0.0000 0.561761 15.2863 + 35 0.0000 0.607740 16.5374 + 36 0.0000 0.634298 17.2601 + 37 0.0000 0.647706 17.6250 + 38 0.0000 0.696146 18.9431 + 39 0.0000 0.710739 19.3402 + 40 0.0000 0.734585 19.9891 + 41 0.0000 0.741246 20.1703 + 42 0.0000 0.767867 20.8947 + 43 0.0000 0.782801 21.3011 + 44 0.0000 0.814134 22.1537 + 45 0.0000 0.828761 22.5517 + 46 0.0000 0.850725 23.1494 + 47 0.0000 0.881569 23.9887 + 48 0.0000 0.915846 24.9214 + 49 0.0000 0.942498 25.6467 + 50 0.0000 0.973207 26.4823 + 51 0.0000 0.979114 26.6431 + 52 0.0000 1.008295 27.4371 + 53 0.0000 1.019216 27.7343 + 54 0.0000 1.055499 28.7216 + 55 0.0000 1.087548 29.5937 + 56 0.0000 1.161114 31.5955 + 57 0.0000 1.203870 32.7590 + 58 0.0000 1.231017 33.4977 + 59 0.0000 1.280061 34.8322 + 60 0.0000 1.349673 36.7265 + 61 0.0000 1.412291 38.4304 + 62 0.0000 1.449043 39.4305 + 63 0.0000 1.518072 41.3088 + 64 0.0000 1.540762 41.9263 + 65 0.0000 1.551311 42.2133 + 66 0.0000 1.612858 43.8881 + 67 0.0000 1.632923 44.4341 + 68 0.0000 1.654099 45.0103 + 69 0.0000 1.729926 47.0737 + 70 0.0000 1.761570 47.9348 + 71 0.0000 1.794772 48.8382 + 72 0.0000 1.913477 52.0683 + 73 0.0000 1.958604 53.2963 + 74 0.0000 1.969828 53.6017 + 75 0.0000 2.007235 54.6196 + 76 0.0000 2.047886 55.7258 + 77 0.0000 2.076147 56.4948 + 78 0.0000 2.157800 58.7167 + 79 0.0000 2.172907 59.1278 + 80 0.0000 2.252310 61.2885 + 81 0.0000 2.307543 62.7914 + 82 0.0000 2.343221 63.7623 + 83 0.0000 2.389518 65.0221 + 84 0.0000 2.419752 65.8448 + 85 0.0000 2.452230 66.7286 + 86 0.0000 2.471752 67.2598 + 87 0.0000 2.495906 67.9171 + 88 0.0000 2.521935 68.6253 + 89 0.0000 2.554900 69.5224 + 90 0.0000 2.577579 70.1395 + 91 0.0000 2.612574 71.0917 + 92 0.0000 2.655584 72.2621 + 93 0.0000 2.692673 73.2714 + 94 0.0000 2.767747 75.3142 + 95 0.0000 2.808048 76.4109 + 96 0.0000 2.824737 76.8650 + 97 0.0000 2.930421 79.7408 + 98 0.0000 2.971219 80.8510 + 99 0.0000 2.997755 81.5731 + 100 0.0000 3.130680 85.1901 + 101 0.0000 3.170504 86.2738 + 102 0.0000 3.228741 87.8585 + 103 0.0000 3.505914 95.4008 + 104 0.0000 3.691452 100.4495 + 105 0.0000 3.872589 105.3785 + 106 0.0000 4.020681 109.4083 + 107 0.0000 4.155825 113.0857 + 108 0.0000 4.192117 114.0733 + 109 0.0000 4.336934 118.0140 + 110 0.0000 4.365152 118.7818 + 111 0.0000 4.387694 119.3952 + 112 0.0000 4.542259 123.6012 + 113 0.0000 4.600728 125.1922 + 114 0.0000 4.674572 127.2016 + 115 0.0000 4.773545 129.8948 + 116 0.0000 4.812125 130.9446 + 117 0.0000 4.869060 132.4939 + 118 0.0000 4.961444 135.0078 + 119 0.0000 4.992398 135.8501 + 120 0.0000 5.068785 137.9286 + 121 0.0000 5.107074 138.9706 + 122 0.0000 5.183514 141.0506 + 123 0.0000 5.228514 142.2751 + 124 0.0000 5.249852 142.8557 + 125 0.0000 5.279606 143.6654 + 126 0.0000 5.384826 146.5286 + 127 0.0000 5.473596 148.9441 + 128 0.0000 5.526231 150.3764 + 129 0.0000 5.702349 155.1688 + 130 0.0000 5.769121 156.9858 + 131 0.0000 5.958651 162.1431 + 132 0.0000 6.161805 167.6713 + 133 0.0000 6.402533 174.2218 + 134 0.0000 6.490060 176.6035 + 135 0.0000 6.521958 177.4715 + 136 0.0000 6.686046 181.9366 + 137 0.0000 6.716240 182.7582 + 138 0.0000 6.780106 184.4961 + 139 0.0000 6.804378 185.1565 + 140 0.0000 6.878298 187.1680 + 141 0.0000 7.089891 192.9258 + 142 0.0000 7.122281 193.8071 + 143 0.0000 7.162832 194.9106 + 144 0.0000 7.206769 196.1062 + 145 0.0000 7.247164 197.2053 + 146 0.0000 7.267792 197.7667 + 147 0.0000 7.320460 199.1998 + 148 0.0000 7.392471 201.1594 + 149 0.0000 7.465109 203.1359 + 150 0.0000 7.494748 203.9425 + 151 0.0000 7.533139 204.9871 + 152 0.0000 7.560724 205.7378 + 153 0.0000 7.671531 208.7530 + 154 0.0000 7.731510 210.3851 + 155 0.0000 7.901237 215.0036 + 156 0.0000 8.080288 219.8758 + 157 0.0000 8.363646 227.5864 + 158 0.0000 14.024663 381.6305 + 159 0.0000 15.064772 409.9333 + 160 0.0000 15.873734 431.9463 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.680676 -562.7498 + 1 1.0000 -20.631629 -561.4152 + 2 1.0000 -15.804060 -430.0503 + 3 1.0000 -1.611138 -43.8413 + 4 1.0000 -1.389800 -37.8184 + 5 1.0000 -0.960584 -26.1388 + 6 1.0000 -0.772260 -21.0143 + 7 1.0000 -0.737407 -20.0659 + 8 1.0000 -0.695881 -18.9359 + 9 1.0000 -0.605171 -16.4675 + 10 1.0000 -0.533781 -14.5249 + 11 1.0000 -0.467253 -12.7146 + 12 0.0000 0.031006 0.8437 + 13 0.0000 0.069213 1.8834 + 14 0.0000 0.093666 2.5488 + 15 0.0000 0.109700 2.9851 + 16 0.0000 0.115326 3.1382 + 17 0.0000 0.153187 4.1684 + 18 0.0000 0.157157 4.2765 + 19 0.0000 0.171306 4.6615 + 20 0.0000 0.180392 4.9087 + 21 0.0000 0.192365 5.2345 + 22 0.0000 0.202922 5.5218 + 23 0.0000 0.234602 6.3838 + 24 0.0000 0.266342 7.2475 + 25 0.0000 0.290158 7.8956 + 26 0.0000 0.310242 8.4421 + 27 0.0000 0.337781 9.1915 + 28 0.0000 0.343666 9.3516 + 29 0.0000 0.370083 10.0705 + 30 0.0000 0.421926 11.4812 + 31 0.0000 0.513975 13.9860 + 32 0.0000 0.531169 14.4539 + 33 0.0000 0.534855 14.5541 + 34 0.0000 0.561761 15.2863 + 35 0.0000 0.607740 16.5374 + 36 0.0000 0.634298 17.2601 + 37 0.0000 0.647706 17.6250 + 38 0.0000 0.696146 18.9431 + 39 0.0000 0.710739 19.3402 + 40 0.0000 0.734585 19.9891 + 41 0.0000 0.741246 20.1703 + 42 0.0000 0.767867 20.8947 + 43 0.0000 0.782801 21.3011 + 44 0.0000 0.814134 22.1537 + 45 0.0000 0.828761 22.5517 + 46 0.0000 0.850725 23.1494 + 47 0.0000 0.881569 23.9887 + 48 0.0000 0.915846 24.9214 + 49 0.0000 0.942498 25.6467 + 50 0.0000 0.973207 26.4823 + 51 0.0000 0.979114 26.6431 + 52 0.0000 1.008295 27.4371 + 53 0.0000 1.019216 27.7343 + 54 0.0000 1.055499 28.7216 + 55 0.0000 1.087548 29.5937 + 56 0.0000 1.161114 31.5955 + 57 0.0000 1.203870 32.7590 + 58 0.0000 1.231017 33.4977 + 59 0.0000 1.280061 34.8322 + 60 0.0000 1.349673 36.7265 + 61 0.0000 1.412291 38.4304 + 62 0.0000 1.449043 39.4305 + 63 0.0000 1.518072 41.3088 + 64 0.0000 1.540762 41.9263 + 65 0.0000 1.551311 42.2133 + 66 0.0000 1.612858 43.8881 + 67 0.0000 1.632923 44.4341 + 68 0.0000 1.654099 45.0103 + 69 0.0000 1.729926 47.0737 + 70 0.0000 1.761570 47.9348 + 71 0.0000 1.794772 48.8382 + 72 0.0000 1.913477 52.0683 + 73 0.0000 1.958604 53.2963 + 74 0.0000 1.969828 53.6017 + 75 0.0000 2.007235 54.6196 + 76 0.0000 2.047886 55.7258 + 77 0.0000 2.076147 56.4948 + 78 0.0000 2.157800 58.7167 + 79 0.0000 2.172907 59.1278 + 80 0.0000 2.252310 61.2885 + 81 0.0000 2.307543 62.7914 + 82 0.0000 2.343221 63.7623 + 83 0.0000 2.389518 65.0221 + 84 0.0000 2.419752 65.8448 + 85 0.0000 2.452230 66.7286 + 86 0.0000 2.471752 67.2598 + 87 0.0000 2.495906 67.9171 + 88 0.0000 2.521935 68.6253 + 89 0.0000 2.554900 69.5224 + 90 0.0000 2.577579 70.1395 + 91 0.0000 2.612574 71.0917 + 92 0.0000 2.655584 72.2621 + 93 0.0000 2.692673 73.2714 + 94 0.0000 2.767747 75.3142 + 95 0.0000 2.808048 76.4109 + 96 0.0000 2.824737 76.8650 + 97 0.0000 2.930421 79.7408 + 98 0.0000 2.971219 80.8510 + 99 0.0000 2.997755 81.5731 + 100 0.0000 3.130680 85.1901 + 101 0.0000 3.170504 86.2738 + 102 0.0000 3.228741 87.8585 + 103 0.0000 3.505914 95.4008 + 104 0.0000 3.691452 100.4495 + 105 0.0000 3.872589 105.3785 + 106 0.0000 4.020681 109.4083 + 107 0.0000 4.155825 113.0857 + 108 0.0000 4.192117 114.0733 + 109 0.0000 4.336934 118.0140 + 110 0.0000 4.365152 118.7818 + 111 0.0000 4.387694 119.3952 + 112 0.0000 4.542259 123.6012 + 113 0.0000 4.600728 125.1922 + 114 0.0000 4.674572 127.2016 + 115 0.0000 4.773545 129.8948 + 116 0.0000 4.812125 130.9446 + 117 0.0000 4.869060 132.4939 + 118 0.0000 4.961444 135.0078 + 119 0.0000 4.992398 135.8501 + 120 0.0000 5.068785 137.9286 + 121 0.0000 5.107074 138.9706 + 122 0.0000 5.183514 141.0506 + 123 0.0000 5.228514 142.2751 + 124 0.0000 5.249852 142.8557 + 125 0.0000 5.279606 143.6654 + 126 0.0000 5.384826 146.5286 + 127 0.0000 5.473596 148.9441 + 128 0.0000 5.526231 150.3764 + 129 0.0000 5.702349 155.1688 + 130 0.0000 5.769121 156.9858 + 131 0.0000 5.958651 162.1431 + 132 0.0000 6.161805 167.6713 + 133 0.0000 6.402533 174.2218 + 134 0.0000 6.490060 176.6035 + 135 0.0000 6.521958 177.4715 + 136 0.0000 6.686046 181.9366 + 137 0.0000 6.716240 182.7582 + 138 0.0000 6.780106 184.4961 + 139 0.0000 6.804378 185.1565 + 140 0.0000 6.878298 187.1680 + 141 0.0000 7.089891 192.9258 + 142 0.0000 7.122281 193.8071 + 143 0.0000 7.162832 194.9106 + 144 0.0000 7.206769 196.1062 + 145 0.0000 7.247164 197.2053 + 146 0.0000 7.267792 197.7667 + 147 0.0000 7.320460 199.1998 + 148 0.0000 7.392471 201.1594 + 149 0.0000 7.465109 203.1359 + 150 0.0000 7.494748 203.9425 + 151 0.0000 7.533139 204.9871 + 152 0.0000 7.560724 205.7378 + 153 0.0000 7.671531 208.7530 + 154 0.0000 7.731510 210.3851 + 155 0.0000 7.901237 215.0036 + 156 0.0000 8.080288 219.8758 + 157 0.0000 8.363646 227.5864 + 158 0.0000 14.024663 381.6305 + 159 0.0000 15.064772 409.9333 + 160 0.0000 15.873734 431.9463 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.335445 0.000000 + 1 N : 0.351119 0.000000 + 2 O : -0.264731 0.000000 + 3 H : 0.249056 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.833292 s : 3.833292 + pz : 1.714398 p : 4.465857 + px : 1.311829 + py : 1.439631 + dz2 : 0.004361 d : 0.031619 + dxz : 0.006880 + dyz : 0.001041 + dx2y2 : 0.014410 + dxy : 0.004927 + f0 : 0.000675 f : 0.004676 + f+1 : 0.000991 + f-1 : 0.000149 + f+2 : 0.000579 + f-2 : 0.000418 + f+3 : 0.000900 + f-3 : 0.000963 + 1 N s : 3.837893 s : 3.837893 + pz : 0.766896 p : 2.637220 + px : 0.771638 + py : 1.098686 + dz2 : 0.032318 d : 0.141564 + dxz : 0.029974 + dyz : 0.020390 + dx2y2 : 0.038109 + dxy : 0.020773 + f0 : 0.001952 f : 0.032204 + f+1 : 0.004672 + f-1 : 0.004653 + f+2 : 0.003519 + f-2 : 0.004926 + f+3 : 0.005711 + f-3 : 0.006770 + 2 O s : 3.871614 s : 3.871614 + pz : 1.234237 p : 4.324138 + px : 1.719792 + py : 1.370109 + dz2 : 0.020009 d : 0.061489 + dxz : 0.005560 + dyz : 0.012009 + dx2y2 : 0.008764 + dxy : 0.015147 + f0 : 0.000671 f : 0.007490 + f+1 : 0.000224 + f-1 : 0.002007 + f+2 : 0.001348 + f-2 : 0.001144 + f+3 : 0.001116 + f-3 : 0.000979 + 3 H s : 0.641410 s : 0.641410 + pz : 0.040649 p : 0.088457 + px : 0.025827 + py : 0.021980 + dz2 : 0.003178 d : 0.021077 + dxz : 0.000568 + dyz : 0.005787 + dx2y2 : 0.001879 + dxy : 0.009665 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.587998 0.000000 + 1 N : -0.259686 0.000000 + 2 O : 0.245412 0.000000 + 3 H : -0.573724 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.120656 s : 3.120656 + pz : 1.389560 p : 3.931708 + px : 1.216059 + py : 1.326089 + dz2 : 0.036320 d : 0.276662 + dxz : 0.067708 + dyz : 0.029043 + dx2y2 : 0.080211 + dxy : 0.063380 + f0 : 0.007940 f : 0.082977 + f+1 : 0.015943 + f-1 : 0.000596 + f+2 : 0.014145 + f-2 : 0.010016 + f+3 : 0.011059 + f-3 : 0.023278 + 1 N s : 3.020638 s : 3.020638 + pz : 0.820687 p : 2.834824 + px : 0.850174 + py : 1.163963 + dz2 : 0.158435 d : 0.948750 + dxz : 0.218460 + dyz : 0.166545 + dx2y2 : 0.232453 + dxy : 0.172857 + f0 : 0.033747 f : 0.455474 + f+1 : 0.054384 + f-1 : 0.053915 + f+2 : 0.080174 + f-2 : 0.081311 + f+3 : 0.069691 + f-3 : 0.082250 + 2 O s : 3.308307 s : 3.308307 + pz : 1.193202 p : 4.004637 + px : 1.422218 + py : 1.389217 + dz2 : 0.038826 d : 0.325235 + dxz : 0.053451 + dyz : 0.098095 + dx2y2 : 0.090260 + dxy : 0.044602 + f0 : 0.010157 f : 0.116409 + f+1 : 0.006216 + f-1 : 0.019439 + f+2 : 0.030129 + f-2 : 0.020819 + f+3 : 0.008903 + f-3 : 0.020745 + 3 H s : 0.619436 s : 0.619436 + pz : 0.167983 p : 0.560053 + px : 0.136883 + py : 0.255187 + dz2 : 0.056375 d : 0.394234 + dxz : 0.033267 + dyz : 0.109074 + dx2y2 : 0.092969 + dxy : 0.102549 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3354 8.0000 -0.3354 1.8195 1.8195 0.0000 + 1 N 6.6489 7.0000 0.3511 2.5515 2.5515 0.0000 + 2 O 8.2647 8.0000 -0.2647 1.7484 1.7484 0.0000 + 3 H 0.7509 1.0000 0.2491 1.0096 1.0096 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8112 B( 0-O , 3-H ) : 0.9475 B( 1-N , 2-O ) : 1.6830 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.530 sec +Sum of individual times .... 0.294 sec ( 55.5%) + +Fock matrix formation .... 0.215 sec ( 40.6%) +Diagonalization .... 0.022 sec ( 4.2%) +Density matrix formation .... 0.002 sec ( 0.4%) +Population analysis .... 0.032 sec ( 6.1%) +Initial guess .... 0.010 sec ( 1.9%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 1.0%) +DIIS solution .... 0.012 sec ( 2.3%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.227 sec +Reference energy ... -204.712619053 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.591 sec +AO-integral generation ... 0.145 sec +Half transformation ... 0.081 sec +K-integral sorting ... 5.576 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.027 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.032 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.036 s ( 0.000 ms/b) + 159120 b 0 skpd 0.020 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.025 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.025 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.355 sec +AO-integral generation ... 0.247 sec +Half transformation ... 0.044 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.160 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.254 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090195229 +EMP2(bb)= -0.090195229 +EMP2(ab)= -0.515911490 + +Initial guess performed in 0.133 sec +E(0) ... -204.712619053 +E(MP2) ... -0.696301949 +Initial E(tot) ... -205.408921002 + ... 0.187773423 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.408921002 -0.696301949 -0.000000000 0.023127455 2.94 0.000008256 + *** Turning on DIIS *** + 1 -205.380607340 -0.667988287 0.028313662 0.009652832 2.86 0.056903692 + 2 -205.400027266 -0.687408213 -0.019419926 0.005005657 3.07 0.060030598 + 3 -205.403793345 -0.691174292 -0.003766079 0.001798732 2.89 0.074039271 + 4 -205.405360289 -0.692741236 -0.001566944 0.001510108 2.98 0.080717908 + 5 -205.405905529 -0.693286475 -0.000545240 0.000913041 3.01 0.086187177 + 6 -205.406013711 -0.693394658 -0.000108183 0.000558417 2.98 0.088994037 + 7 -205.406060855 -0.693441802 -0.000047144 0.000263363 3.04 0.090344430 + 8 -205.406072872 -0.693453819 -0.000012017 0.000123013 2.97 0.090920730 + 9 -205.406069026 -0.693449972 0.000003847 0.000061989 3.19 0.091105669 + 10 -205.406074523 -0.693455470 -0.000005497 0.000037267 2.95 0.091181353 + 11 -205.406071244 -0.693452191 0.000003279 0.000026328 4.03 0.091171360 + 12 -205.406073004 -0.693453950 -0.000001760 0.000016706 3.43 0.091189482 + 13 -205.406072804 -0.693453751 0.000000199 0.000009653 3.80 0.091184768 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.712619053 +E(CORR) ... -0.693453751 +E(TOT) ... -205.406072804 +Singles norm **1/2 ... 0.091184768 ( 0.045592384, 0.045592384) +T1 diagnostic ... 0.021492456 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.056775 + 9a-> 13a 9b-> 13b 0.043486 + 8a-> 13a -1a-> -1a 0.037393 + 8b-> 13b -1b-> -1b 0.037393 + 9a-> 13a 8b-> 13b 0.035968 + 8a-> 13a 9b-> 13b 0.035968 + 11a-> 13a 11b-> 13b 0.030314 + 10b-> 13b -1b-> -1b 0.029962 + 10a-> 13a -1a-> -1a 0.029962 + 5a-> 13a 5b-> 13b 0.027680 + 10a-> 13a 10b-> 13b 0.026086 + 9a-> 13a 10b-> 13b 0.024817 + 10a-> 13a 9b-> 13b 0.024817 + 11a-> 25a 11b-> 25b 0.022951 + 8a-> 13a 10b-> 13b 0.022631 + 10a-> 13a 8b-> 13b 0.022631 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034538576 + alpha-alpha-alpha ... -0.000887613 ( 2.6%) + alpha-alpha-beta ... -0.016381675 ( 47.4%) + alpha-beta -beta ... -0.016381675 ( 47.4%) + beta -beta -beta ... -0.000887613 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034538576 + +Final correlation energy ... -0.727992327 +E(CCSD) ... -205.406072804 +E(CCSD(T)) ... -205.440611380 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210077920 sqrt= 1.100035418 +W(HF) = 0.826393064 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.262398 0.000000 + 1 N : 0.167288 -0.000000 + 2 O : -0.141672 0.000000 + 3 H : 0.236782 -0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.816943 s : 3.816943 + pz : 1.666490 p : 4.375073 + px : 1.294033 + py : 1.414550 + dz2 : 0.011344 d : 0.062014 + dxz : 0.012610 + dyz : 0.007780 + dx2y2 : 0.017999 + dxy : 0.012281 + f0 : 0.001179 f : 0.008368 + f+1 : 0.001549 + f-1 : 0.000798 + f+2 : 0.001008 + f-2 : 0.001015 + f+3 : 0.001336 + f-3 : 0.001483 + 1 N s : 3.891286 s : 3.891286 + pz : 0.840563 p : 2.739631 + px : 0.819688 + py : 1.079380 + dz2 : 0.035850 d : 0.170626 + dxz : 0.038994 + dyz : 0.024375 + dx2y2 : 0.044846 + dxy : 0.026561 + f0 : 0.002127 f : 0.031169 + f+1 : 0.004755 + f-1 : 0.003963 + f+2 : 0.003321 + f-2 : 0.004867 + f+3 : 0.005391 + f-3 : 0.006743 + 2 O s : 3.858378 s : 3.858378 + pz : 1.203203 p : 4.189911 + px : 1.647290 + py : 1.339418 + dz2 : 0.022214 d : 0.083398 + dxz : 0.012250 + dyz : 0.014601 + dx2y2 : 0.015040 + dxy : 0.019293 + f0 : 0.001062 f : 0.009985 + f+1 : 0.000792 + f-1 : 0.001954 + f+2 : 0.001675 + f-2 : 0.001541 + f+3 : 0.001519 + f-3 : 0.001442 + 3 H s : 0.652225 s : 0.652225 + pz : 0.045387 p : 0.092399 + px : 0.029277 + py : 0.017734 + dz2 : 0.002901 d : 0.018594 + dxz : 0.000829 + dyz : 0.004919 + dx2y2 : 0.001130 + dxy : 0.008814 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.599182 0.000000 + 1 N : -0.306173 -0.000000 + 2 O : 0.284047 0.000000 + 3 H : -0.577056 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.127354 s : 3.127354 + pz : 1.355915 p : 3.875217 + px : 1.211096 + py : 1.308206 + dz2 : 0.042333 d : 0.308082 + dxz : 0.074510 + dyz : 0.036048 + dx2y2 : 0.086803 + dxy : 0.068390 + f0 : 0.008978 f : 0.090165 + f+1 : 0.016946 + f-1 : 0.001280 + f+2 : 0.015721 + f-2 : 0.010931 + f+3 : 0.012643 + f-3 : 0.023666 + 1 N s : 3.026083 s : 3.026083 + pz : 0.864328 p : 2.880018 + px : 0.870421 + py : 1.145270 + dz2 : 0.156904 d : 0.955102 + dxz : 0.222392 + dyz : 0.172538 + dx2y2 : 0.235538 + dxy : 0.167730 + f0 : 0.034535 f : 0.444970 + f+1 : 0.050071 + f-1 : 0.053542 + f+2 : 0.078544 + f-2 : 0.078562 + f+3 : 0.070028 + f-3 : 0.079687 + 2 O s : 3.310547 s : 3.310547 + pz : 1.175840 p : 3.924075 + px : 1.377669 + py : 1.370565 + dz2 : 0.049799 d : 0.356348 + dxz : 0.057883 + dyz : 0.103170 + dx2y2 : 0.094570 + dxy : 0.050926 + f0 : 0.011699 f : 0.124984 + f+1 : 0.007088 + f-1 : 0.023400 + f+2 : 0.029998 + f-2 : 0.021583 + f+3 : 0.010671 + f-3 : 0.020546 + 3 H s : 0.622026 s : 0.622026 + pz : 0.173327 p : 0.571280 + px : 0.137366 + py : 0.260586 + dz2 : 0.055077 d : 0.383750 + dxz : 0.032366 + dyz : 0.105269 + dx2y2 : 0.091746 + dxy : 0.099292 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2624 8.0000 -0.2624 2.1855 1.7304 0.4551 + 1 N 6.8327 7.0000 0.1673 2.8275 2.3449 0.4826 + 2 O 8.1417 8.0000 -0.1417 2.1403 1.6418 0.4985 + 3 H 0.7632 1.0000 0.2368 1.0263 0.9520 0.0743 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7517 B( 0-O , 3-H ) : 0.8796 B( 1-N , 2-O ) : 1.5317 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 59.793 sec + +Fock Matrix Formation ... 0.227 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 2.234 sec ( 3.7%) +State Vector Update ... 0.108 sec ( 0.2%) +Sigma-vector construction ... 41.802 sec ( 69.9%) + <0|H|D> ... 0.005 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (0-ext) ... 0.071 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (2-ext) ... 0.943 sec ( 2.3% of sigma) + (4-ext) ... 23.736 sec ( 56.8% of sigma) + ... 1.638 sec ( 3.9% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.112 sec ( 0.3% of sigma) + Fock-dressing ... 2.275 sec ( 5.4% of sigma) + (ik|jl)-dressing ... 0.077 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.231 sec ( 24.5% of sigma) + Pair energies ... 0.008 sec ( 0.0% of sigma) +Total Time for computing (T) ... 7.131 sec ( 11.9% of ALL) + I/O of integral and amplitudes ... 0.768 sec ( 10.8% of (T)) + External N**7 contributions ... 3.923 sec ( 55.0% of (T)) + Internal N**7 contributions ... 0.332 sec ( 4.7% of (T)) + N**6 triples energy contributions ... 1.775 sec ( 24.9% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.440611380223 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.017.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.017.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.381480, -0.291160 -0.435033) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.85108 -0.18817 -0.57568 +Nuclear contribution : -0.85580 0.66844 0.91940 + ----------------------------------------- +Total Dipole Moment : -0.00471 0.48027 0.34371 + ----------------------------------------- +Magnitude (a.u.) : 0.59061 +Magnitude (Debye) : 1.50121 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.745190 0.417001 0.368669 +Rotational constants in MHz : 82298.730413 12501.364386 11052.426422 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.088967 0.375702 0.446937 +x,y,z [Debye]: -0.226136 0.954958 1.136024 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.381480, -0.291160 -0.435033) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.87405 -0.11800 -0.68234 +Nuclear contribution : -0.85580 0.66844 0.91940 + ----------------------------------------- +Total Dipole Moment : 0.01826 0.55044 0.23706 + ----------------------------------------- +Magnitude (a.u.) : 0.59959 +Magnitude (Debye) : 1.52404 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.745190 0.417001 0.368669 +Rotational constants in MHz : 82298.730413 12501.364386 11052.426422 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.010152 0.445644 0.401010 +x,y,z [Debye]: 0.025805 1.132736 1.019287 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 18 * + * * + * Dihedral ( 2, 1, 0, 3) : -40.90909091 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0350422274 RMS(Int)= 0.0008827165 + Iter 1: RMS(Cart)= 0.0002166136 RMS(Int)= 0.0000130905 + Iter 2: RMS(Cart)= 0.0000032123 RMS(Int)= 0.0000001950 + Iter 3: RMS(Cart)= 0.0000000479 RMS(Int)= 0.0000000029 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4538 0.000000 + 2. B(O 2,N 1) 1.1771 0.000000 + 3. B(H 3,O 0) 0.9744 0.000000 + 4. A(N 1,O 0,H 3) 104.7003 0.000000 + 5. A(O 0,N 1,O 2) 112.5575 0.000000 + 6. D(O 2,N 1,O 0,H 3) -40.9091 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.726915 -0.358241 0.417961 + N 0.553393 -0.565326 -0.238972 + O 0.877188 0.355123 -0.897387 + H -0.703665 0.568444 0.718398 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.373671 -0.676978 0.789832 + 1 N 7.0000 0 14.007 1.045762 -1.068311 -0.451593 + 2 O 8.0000 0 15.999 1.657645 0.671086 -1.695815 + 3 H 1.0000 0 1.008 -1.329734 1.074203 1.357576 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.452785910812 0.00000000 0.00000000 + O 2 1 0 1.175598652791 112.70663287 0.00000000 + H 1 2 3 0.972249630504 104.87114689 310.90909070 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.745367502654 0.00000000 0.00000000 + O 2 1 0 2.221559497181 112.70663287 0.00000000 + H 1 2 3 1.837285535459 104.87114689 310.90909070 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2239 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2712 + la=0 lb=0: 554 shell pairs + la=1 lb=0: 540 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.110826183601 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.1108261836 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.584e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7098916127 0.000000000000 0.00187116 0.00005119 0.0164267 0.7000 + 1 -204.7106785178 -0.000786905139 0.00168688 0.00004746 0.0136717 0.7000 + ***Turning on DIIS*** + 2 -204.7113612808 -0.000682762991 0.00451052 0.00013132 0.0111787 0.0000 + 3 -204.7150959517 -0.003734670951 0.00203934 0.00006088 0.0047037 0.0000 + 4 -204.7128859211 0.002210030646 0.00096285 0.00003176 0.0019037 0.0000 + 5 -204.7148148739 -0.001928952767 0.00063659 0.00002668 0.0010603 0.0000 + 6 -204.7140166186 0.000798255286 0.00073084 0.00003189 0.0007048 0.0000 + 7 -204.7136272628 0.000389355753 0.00036993 0.00001657 0.0002906 0.0000 + 8 -204.7143838823 -0.000756619476 0.00018288 0.00000929 0.0001793 0.0000 + 9 -204.7139136405 0.000470241836 0.00015573 0.00000520 0.0001202 0.0000 + 10 -204.7140107133 -0.000097072858 0.00004957 0.00000195 0.0000717 0.0000 + 11 -204.7141191420 -0.000108428653 0.00003009 0.00000085 0.0000309 0.0000 + 12 -204.7140591623 0.000059979645 0.00000813 0.00000025 0.0000084 0.0000 + 13 -204.7140758992 -0.000016736862 0.00000218 0.00000008 0.0000030 0.0000 + 14 -204.7140733580 0.000002541147 0.00000099 0.00000004 0.0000018 0.0000 + 15 -204.7140735770 -0.000000218994 0.00000069 0.00000003 0.0000018 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 16 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71407451 Eh -5570.55317 eV + +Components: +Nuclear Repulsion : 69.11082618 Eh 1880.60119 eV +Electronic Energy : -273.82490070 Eh -7451.15436 eV +One Electron Energy: -417.86120360 Eh -11370.58142 eV +Two Electron Energy: 144.03630291 Eh 3919.42706 eV + +Virial components: +Potential Energy : -408.93370426 Eh -11127.65181 eV +Kinetic Energy : 204.21962975 Eh 5557.09864 eV +Virial Ratio : 2.00242114 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -9.3540e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.6214e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.3139e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.2457e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.679920 -562.7292 + 1 1.0000 -20.633984 -561.4792 + 2 1.0000 -15.805709 -430.0952 + 3 1.0000 -1.610532 -43.8248 + 4 1.0000 -1.389619 -37.8135 + 5 1.0000 -0.961529 -26.1645 + 6 1.0000 -0.771400 -20.9909 + 7 1.0000 -0.738249 -20.0888 + 8 1.0000 -0.693176 -18.8623 + 9 1.0000 -0.608195 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195.7899 + 145 0.0000 7.243323 197.1008 + 146 0.0000 7.257493 197.4864 + 147 0.0000 7.316101 199.0812 + 148 0.0000 7.390356 201.1018 + 149 0.0000 7.459046 202.9710 + 150 0.0000 7.496746 203.9968 + 151 0.0000 7.524112 204.7415 + 152 0.0000 7.548451 205.4038 + 153 0.0000 7.657340 208.3668 + 154 0.0000 7.760478 211.1733 + 155 0.0000 7.883695 214.5263 + 156 0.0000 8.104999 220.5482 + 157 0.0000 8.345121 227.0823 + 158 0.0000 14.017143 381.4258 + 159 0.0000 15.001223 408.2040 + 160 0.0000 15.799130 429.9162 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.679920 -562.7292 + 1 1.0000 -20.633984 -561.4792 + 2 1.0000 -15.805709 -430.0952 + 3 1.0000 -1.610532 -43.8248 + 4 1.0000 -1.389619 -37.8135 + 5 1.0000 -0.961529 -26.1645 + 6 1.0000 -0.771400 -20.9909 + 7 1.0000 -0.738249 -20.0888 + 8 1.0000 -0.693176 -18.8623 + 9 1.0000 -0.608195 -16.5498 + 10 1.0000 -0.533130 -14.5072 + 11 1.0000 -0.468859 -12.7583 + 12 0.0000 0.031417 0.8549 + 13 0.0000 0.069621 1.8945 + 14 0.0000 0.093780 2.5519 + 15 0.0000 0.110482 3.0064 + 16 0.0000 0.117165 3.1882 + 17 0.0000 0.151509 4.1228 + 18 0.0000 0.157759 4.2929 + 19 0.0000 0.170028 4.6267 + 20 0.0000 0.181660 4.9432 + 21 0.0000 0.193035 5.2528 + 22 0.0000 0.202866 5.5203 + 23 0.0000 0.233887 6.3644 + 24 0.0000 0.262402 7.1403 + 25 0.0000 0.289658 7.8820 + 26 0.0000 0.308638 8.3985 + 27 0.0000 0.337873 9.1940 + 28 0.0000 0.345460 9.4005 + 29 0.0000 0.378211 10.2916 + 30 0.0000 0.422010 11.4835 + 31 0.0000 0.514086 13.9890 + 32 0.0000 0.528373 14.3778 + 33 0.0000 0.534030 14.5317 + 34 0.0000 0.561824 15.2880 + 35 0.0000 0.611120 16.6294 + 36 0.0000 0.633320 17.2335 + 37 0.0000 0.650330 17.6964 + 38 0.0000 0.692476 18.8432 + 39 0.0000 0.705924 19.2092 + 40 0.0000 0.735289 20.0082 + 41 0.0000 0.744288 20.2531 + 42 0.0000 0.766605 20.8604 + 43 0.0000 0.783689 21.3253 + 44 0.0000 0.812162 22.1001 + 45 0.0000 0.833026 22.6678 + 46 0.0000 0.848350 23.0848 + 47 0.0000 0.879529 23.9332 + 48 0.0000 0.919192 25.0125 + 49 0.0000 0.942068 25.6350 + 50 0.0000 0.969244 26.3745 + 51 0.0000 0.982429 26.7333 + 52 0.0000 1.018061 27.7028 + 53 0.0000 1.026238 27.9254 + 54 0.0000 1.060534 28.8586 + 55 0.0000 1.086654 29.5693 + 56 0.0000 1.165420 31.7127 + 57 0.0000 1.197609 32.5886 + 58 0.0000 1.233072 33.5536 + 59 0.0000 1.278399 34.7870 + 60 0.0000 1.361649 37.0524 + 61 0.0000 1.411282 38.4029 + 62 0.0000 1.442379 39.2491 + 63 0.0000 1.525090 41.4998 + 64 0.0000 1.531333 41.6697 + 65 0.0000 1.542436 41.9718 + 66 0.0000 1.609442 43.7951 + 67 0.0000 1.629283 44.3351 + 68 0.0000 1.653918 45.0054 + 69 0.0000 1.729469 47.0612 + 70 0.0000 1.768316 48.1183 + 71 0.0000 1.800938 49.0060 + 72 0.0000 1.905855 51.8609 + 73 0.0000 1.957857 53.2760 + 74 0.0000 1.970170 53.6111 + 75 0.0000 2.010218 54.7008 + 76 0.0000 2.040455 55.5236 + 77 0.0000 2.074422 56.4479 + 78 0.0000 2.158912 58.7470 + 79 0.0000 2.172649 59.1208 + 80 0.0000 2.250196 61.2310 + 81 0.0000 2.305775 62.7433 + 82 0.0000 2.349934 63.9450 + 83 0.0000 2.396326 65.2073 + 84 0.0000 2.414504 65.7020 + 85 0.0000 2.447785 66.6076 + 86 0.0000 2.471322 67.2481 + 87 0.0000 2.500146 68.0324 + 88 0.0000 2.530803 68.8667 + 89 0.0000 2.555705 69.5443 + 90 0.0000 2.577346 70.1332 + 91 0.0000 2.616302 71.1932 + 92 0.0000 2.648898 72.0802 + 93 0.0000 2.692260 73.2601 + 94 0.0000 2.756305 75.0029 + 95 0.0000 2.798556 76.1526 + 96 0.0000 2.830445 77.0203 + 97 0.0000 2.930073 79.7313 + 98 0.0000 2.966941 80.7346 + 99 0.0000 3.004725 81.7627 + 100 0.0000 3.129655 85.1623 + 101 0.0000 3.172061 86.3162 + 102 0.0000 3.227030 87.8119 + 103 0.0000 3.502709 95.3136 + 104 0.0000 3.691217 100.4431 + 105 0.0000 3.873994 105.4167 + 106 0.0000 4.016348 109.2904 + 107 0.0000 4.151174 112.9592 + 108 0.0000 4.183833 113.8479 + 109 0.0000 4.321326 117.5892 + 110 0.0000 4.377061 119.1059 + 111 0.0000 4.384869 119.3183 + 112 0.0000 4.533553 123.3642 + 113 0.0000 4.579930 124.6262 + 114 0.0000 4.671049 127.1057 + 115 0.0000 4.791336 130.3789 + 116 0.0000 4.819991 131.1586 + 117 0.0000 4.866684 132.4292 + 118 0.0000 4.962067 135.0247 + 119 0.0000 4.993193 135.8717 + 120 0.0000 5.070431 137.9735 + 121 0.0000 5.103488 138.8730 + 122 0.0000 5.183119 141.0398 + 123 0.0000 5.229094 142.2909 + 124 0.0000 5.247395 142.7889 + 125 0.0000 5.278592 143.6378 + 126 0.0000 5.376640 146.3058 + 127 0.0000 5.459630 148.5641 + 128 0.0000 5.529588 150.4677 + 129 0.0000 5.696860 155.0194 + 130 0.0000 5.771808 157.0589 + 131 0.0000 5.947633 161.8433 + 132 0.0000 6.160605 167.6386 + 133 0.0000 6.394550 174.0046 + 134 0.0000 6.492372 176.6664 + 135 0.0000 6.525154 177.5585 + 136 0.0000 6.685141 181.9119 + 137 0.0000 6.721141 182.8915 + 138 0.0000 6.777423 184.4231 + 139 0.0000 6.798946 185.0087 + 140 0.0000 6.887718 187.4243 + 141 0.0000 7.090342 192.9380 + 142 0.0000 7.123908 193.8514 + 143 0.0000 7.163535 194.9297 + 144 0.0000 7.195148 195.7899 + 145 0.0000 7.243323 197.1008 + 146 0.0000 7.257493 197.4864 + 147 0.0000 7.316101 199.0812 + 148 0.0000 7.390356 201.1018 + 149 0.0000 7.459046 202.9710 + 150 0.0000 7.496746 203.9968 + 151 0.0000 7.524112 204.7415 + 152 0.0000 7.548451 205.4038 + 153 0.0000 7.657340 208.3668 + 154 0.0000 7.760478 211.1733 + 155 0.0000 7.883695 214.5263 + 156 0.0000 8.104999 220.5482 + 157 0.0000 8.345121 227.0823 + 158 0.0000 14.017143 381.4258 + 159 0.0000 15.001223 408.2040 + 160 0.0000 15.799130 429.9162 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.332525 0.000000 + 1 N : 0.354131 0.000000 + 2 O : -0.271804 0.000000 + 3 H : 0.250198 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.829788 s : 3.829788 + pz : 1.712174 p : 4.465346 + px : 1.334227 + py : 1.418944 + dz2 : 0.005311 d : 0.032590 + dxz : 0.007261 + dyz : 0.000657 + dx2y2 : 0.014911 + dxy : 0.004449 + f0 : 0.000611 f : 0.004801 + f+1 : 0.001048 + f-1 : 0.000193 + f+2 : 0.000601 + f-2 : 0.000562 + f+3 : 0.000835 + f-3 : 0.000949 + 1 N s : 3.843643 s : 3.843643 + pz : 0.750033 p : 2.628719 + px : 0.759338 + py : 1.119348 + dz2 : 0.030980 d : 0.141310 + dxz : 0.029461 + dyz : 0.022185 + dx2y2 : 0.037951 + dxy : 0.020734 + f0 : 0.001564 f : 0.032199 + f+1 : 0.004516 + f-1 : 0.004971 + f+2 : 0.003323 + f-2 : 0.005016 + f+3 : 0.005902 + f-3 : 0.006907 + 2 O s : 3.868605 s : 3.868605 + pz : 1.260976 p : 4.333827 + px : 1.699157 + py : 1.373694 + dz2 : 0.018368 d : 0.061823 + dxz : 0.004904 + dyz : 0.013185 + dx2y2 : 0.009099 + dxy : 0.016267 + f0 : 0.000496 f : 0.007549 + f+1 : 0.000169 + f-1 : 0.002086 + f+2 : 0.001363 + f-2 : 0.001107 + f+3 : 0.001211 + f-3 : 0.001118 + 3 H s : 0.641912 s : 0.641912 + pz : 0.039958 p : 0.086986 + px : 0.026158 + py : 0.020870 + dz2 : 0.002144 d : 0.020904 + dxz : -0.000014 + dyz : 0.007121 + dx2y2 : 0.001450 + dxy : 0.010204 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.587003 0.000000 + 1 N : -0.256383 0.000000 + 2 O : 0.244415 0.000000 + 3 H : -0.575035 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.122864 s : 3.122864 + pz : 1.386910 p : 3.930288 + px : 1.225736 + py : 1.317642 + dz2 : 0.036632 d : 0.276822 + dxz : 0.070372 + dyz : 0.028913 + dx2y2 : 0.078142 + dxy : 0.062763 + f0 : 0.007998 f : 0.083023 + f+1 : 0.015247 + f-1 : 0.000892 + f+2 : 0.013999 + f-2 : 0.011671 + f+3 : 0.010259 + f-3 : 0.022955 + 1 N s : 3.022212 s : 3.022212 + pz : 0.797691 p : 2.831669 + px : 0.839343 + py : 1.194635 + dz2 : 0.158747 d : 0.946938 + dxz : 0.211465 + dyz : 0.163646 + dx2y2 : 0.238041 + dxy : 0.175039 + f0 : 0.031203 f : 0.455565 + f+1 : 0.052211 + f-1 : 0.054946 + f+2 : 0.077862 + f-2 : 0.081832 + f+3 : 0.071954 + f-3 : 0.085556 + 2 O s : 3.306311 s : 3.306311 + pz : 1.193426 p : 4.008090 + px : 1.407905 + py : 1.406759 + dz2 : 0.038710 d : 0.325125 + dxz : 0.050265 + dyz : 0.091320 + dx2y2 : 0.097520 + dxy : 0.047310 + f0 : 0.009703 f : 0.116060 + f+1 : 0.005267 + f-1 : 0.018837 + f+2 : 0.028231 + f-2 : 0.020482 + f+3 : 0.010261 + f-3 : 0.023280 + 3 H s : 0.618660 s : 0.618660 + pz : 0.161596 p : 0.557930 + px : 0.137202 + py : 0.259132 + dz2 : 0.050815 d : 0.398445 + dxz : 0.030373 + dyz : 0.112506 + dx2y2 : 0.096748 + dxy : 0.108003 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3325 8.0000 -0.3325 1.8214 1.8214 0.0000 + 1 N 6.6459 7.0000 0.3541 2.5475 2.5475 0.0000 + 2 O 8.2718 8.0000 -0.2718 1.7382 1.7382 0.0000 + 3 H 0.7498 1.0000 0.2502 1.0097 1.0097 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8164 B( 0-O , 3-H ) : 0.9436 B( 1-N , 2-O ) : 1.6709 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.472 sec +Sum of individual times .... 2.246 sec ( 90.8%) + +Fock matrix formation .... 1.847 sec ( 74.7%) +Diagonalization .... 0.185 sec ( 7.5%) +Density matrix formation .... 0.014 sec ( 0.5%) +Population analysis .... 0.034 sec ( 1.4%) +Initial guess .... 0.010 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.2%) +DIIS solution .... 0.156 sec ( 6.3%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.228 sec +Reference energy ... -204.714074482 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.344 sec +AO-integral generation ... 0.142 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.347 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.024 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.028 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.338 sec +AO-integral generation ... 0.236 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.048 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.161 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.250 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090418738 +EMP2(bb)= -0.090418738 +EMP2(ab)= -0.516582025 + +Initial guess performed in 0.132 sec +E(0) ... -204.714074482 +E(MP2) ... -0.697419501 +Initial E(tot) ... -205.411493982 + ... 0.188578980 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.411493982 -0.697419501 -0.000000000 0.024534277 2.77 0.000002719 + *** Turning on DIIS *** + 1 -205.382513608 -0.668439127 0.028980374 0.010203486 2.77 0.057839481 + 2 -205.402120978 -0.688046496 -0.019607369 0.005372665 2.84 0.060914416 + 3 -205.405902861 -0.691828380 -0.003781884 0.001916207 2.87 0.075299941 + 4 -205.407498579 -0.693424097 -0.001595717 0.001629838 2.87 0.082228252 + 5 -205.408067961 -0.693993479 -0.000569382 0.000962503 2.99 0.088013081 + 6 -205.408182640 -0.694108158 -0.000114680 0.000589831 2.93 0.090978662 + 7 -205.408232767 -0.694158286 -0.000050127 0.000263997 2.94 0.092398699 + 8 -205.408245837 -0.694171355 -0.000013069 0.000127930 3.02 0.092975326 + 9 -205.408241470 -0.694166989 0.000004366 0.000047696 2.92 0.093148740 + 10 -205.408247279 -0.694172798 -0.000005809 0.000029876 3.05 0.093219132 + 11 -205.408244075 -0.694169593 0.000003204 0.000021422 4.45 0.093207329 + 12 -205.408245472 -0.694170990 -0.000001397 0.000014404 3.93 0.093222723 + 13 -205.408245305 -0.694170824 0.000000167 0.000008884 3.18 0.093218562 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.714074482 +E(CORR) ... -0.694170824 +E(TOT) ... -205.408245305 +Singles norm **1/2 ... 0.093218562 ( 0.046609281, 0.046609281) +T1 diagnostic ... 0.021971826 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.060073 + 8b-> 13b -1b-> -1b 0.040211 + 8a-> 13a -1a-> -1a 0.040211 + 9a-> 13a 9b-> 13b 0.035907 + 8a-> 13a 9b-> 13b 0.032527 + 9a-> 13a 8b-> 13b 0.032527 + 10a-> 13a 10b-> 13b 0.032493 + 10a-> 13a -1a-> -1a 0.032258 + 10b-> 13b -1b-> -1b 0.032258 + 11a-> 13a 11b-> 13b 0.029597 + 5a-> 13a 5b-> 13b 0.027646 + 8a-> 13a 10b-> 13b 0.026305 + 10a-> 13a 8b-> 13b 0.026305 + 11a-> 25a 11b-> 25b 0.026018 + 11a-> 25a -1a-> -1a 0.025037 + 11b-> 25b -1b-> -1b 0.025037 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034835223 + alpha-alpha-alpha ... -0.000897988 ( 2.6%) + alpha-alpha-beta ... -0.016519623 ( 47.4%) + alpha-beta -beta ... -0.016519623 ( 47.4%) + beta -beta -beta ... -0.000897988 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034835223 + +Final correlation energy ... -0.729006046 +E(CCSD) ... -205.408245305 +E(CCSD(T)) ... -205.443080528 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.211233247 sqrt= 1.100560424 +W(HF) = 0.825604815 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.254617 0.000000 + 1 N : 0.166679 0.000000 + 2 O : -0.148836 -0.000000 + 3 H : 0.236774 -0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.814672 s : 3.814672 + pz : 1.660036 p : 4.368580 + px : 1.314375 + py : 1.394168 + dz2 : 0.012215 d : 0.062871 + dxz : 0.012795 + dyz : 0.007539 + dx2y2 : 0.018466 + dxy : 0.011855 + f0 : 0.001116 f : 0.008494 + f+1 : 0.001626 + f-1 : 0.000840 + f+2 : 0.000996 + f-2 : 0.001132 + f+3 : 0.001299 + f-3 : 0.001485 + 1 N s : 3.895741 s : 3.895741 + pz : 0.832401 p : 2.736424 + px : 0.811778 + py : 1.092246 + dz2 : 0.035417 d : 0.169931 + dxz : 0.037870 + dyz : 0.025684 + dx2y2 : 0.044799 + dxy : 0.026160 + f0 : 0.001842 f : 0.031225 + f+1 : 0.004588 + f-1 : 0.004287 + f+2 : 0.003115 + f-2 : 0.004984 + f+3 : 0.005509 + f-3 : 0.006899 + 2 O s : 3.855736 s : 3.855736 + pz : 1.227177 p : 4.199121 + px : 1.628459 + py : 1.343485 + dz2 : 0.021202 d : 0.083919 + dxz : 0.011614 + dyz : 0.015439 + dx2y2 : 0.015511 + dxy : 0.020153 + f0 : 0.000938 f : 0.010060 + f+1 : 0.000737 + f-1 : 0.002041 + f+2 : 0.001683 + f-2 : 0.001517 + f+3 : 0.001585 + f-3 : 0.001560 + 3 H s : 0.654230 s : 0.654230 + pz : 0.044877 p : 0.090385 + px : 0.029723 + py : 0.015785 + dz2 : 0.001973 d : 0.018611 + dxz : 0.000365 + dyz : 0.006204 + dx2y2 : 0.000735 + dxy : 0.009333 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.599966 0.000000 + 1 N : -0.304631 -0.000000 + 2 O : 0.282200 0.000000 + 3 H : -0.577536 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.130030 s : 3.130030 + pz : 1.351378 p : 3.871298 + px : 1.219294 + py : 1.300626 + dz2 : 0.042871 d : 0.308435 + dxz : 0.077272 + dyz : 0.035715 + dx2y2 : 0.084872 + dxy : 0.067706 + f0 : 0.008963 f : 0.090270 + f+1 : 0.016486 + f-1 : 0.001666 + f+2 : 0.015542 + f-2 : 0.012466 + f+3 : 0.011777 + f-3 : 0.023371 + 1 N s : 3.027583 s : 3.027583 + pz : 0.847056 p : 2.879494 + px : 0.862626 + py : 1.169812 + dz2 : 0.157496 d : 0.952685 + dxz : 0.215909 + dyz : 0.168966 + dx2y2 : 0.240586 + dxy : 0.169726 + f0 : 0.032102 f : 0.444869 + f+1 : 0.047463 + f-1 : 0.054230 + f+2 : 0.076895 + f-2 : 0.079160 + f+3 : 0.072187 + f-3 : 0.082832 + 2 O s : 3.308403 s : 3.308403 + pz : 1.174862 p : 3.927614 + px : 1.364922 + py : 1.387829 + dz2 : 0.049719 d : 0.356988 + dxz : 0.054806 + dyz : 0.096926 + dx2y2 : 0.101565 + dxy : 0.053972 + f0 : 0.010871 f : 0.124795 + f+1 : 0.006188 + f-1 : 0.023066 + f+2 : 0.028373 + f-2 : 0.021153 + f+3 : 0.012177 + f-3 : 0.022966 + 3 H s : 0.621756 s : 0.621756 + pz : 0.166288 p : 0.568115 + px : 0.137707 + py : 0.264120 + dz2 : 0.049845 d : 0.387665 + dxz : 0.029759 + dyz : 0.107934 + dx2y2 : 0.095679 + dxy : 0.104448 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2546 8.0000 -0.2546 2.1953 1.7374 0.4579 + 1 N 6.8333 7.0000 0.1667 2.8278 2.3459 0.4819 + 2 O 8.1488 8.0000 -0.1488 2.1344 1.6355 0.4989 + 3 H 0.7632 1.0000 0.2368 1.0267 0.9521 0.0746 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7610 B( 0-O , 2-O ) : 0.1020 B( 0-O , 3-H ) : 0.8744 +B( 1-N , 2-O ) : 1.5203 + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 59.135 sec + +Fock Matrix Formation ... 0.228 sec ( 0.4%) +Initial Guess ... 0.132 sec ( 0.2%) +DIIS Solver ... 2.316 sec ( 3.9%) +State Vector Update ... 0.101 sec ( 0.2%) +Sigma-vector construction ... 41.116 sec ( 69.5%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (0-ext) ... 0.072 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (2-ext) ... 0.966 sec ( 2.3% of sigma) + (4-ext) ... 23.372 sec ( 56.8% of sigma) + ... 1.615 sec ( 3.9% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.116 sec ( 0.3% of sigma) + Fock-dressing ... 2.130 sec ( 5.2% of sigma) + (ik|jl)-dressing ... 0.078 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.046 sec ( 24.4% of sigma) + Pair energies ... 0.007 sec ( 0.0% of sigma) +Total Time for computing (T) ... 7.252 sec ( 12.3% of ALL) + I/O of integral and amplitudes ... 0.986 sec ( 13.6% of (T)) + External N**7 contributions ... 4.067 sec ( 56.1% of (T)) + Internal N**7 contributions ... 0.334 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.741 sec ( 24.0% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.443080527830 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.009268066 0.002576146 -0.010807929 + 2 N : 0.010090253 0.001035040 0.008874911 + 3 O : -0.004525398 -0.001979796 -0.006939857 + 4 H : 0.003703210 -0.001631391 0.008872875 + +Norm of the cartesian gradient ... 0.023635926 +RMS gradient ... 0.006823104 +MAX gradient ... 0.010807929 + +------- +TIMINGS +------- + +Total numerical gradient time ... 367.468 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 110.28 cm**-1 + 7: 610.44 cm**-1 + 8: 798.53 cm**-1 + 9: 1266.31 cm**-1 + 10: 1673.69 cm**-1 + 11: 3666.83 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 0.110449 -0.267104 -0.177344 0.053642 -0.041739 -0.001721 + 1 -0.013052 -0.113151 0.112866 0.069962 0.051631 -0.059263 + 2 0.027636 0.297128 0.058522 -0.020221 0.017095 -0.019303 + 3 -0.104991 0.047497 0.356501 0.057480 -0.067803 0.001042 + 4 -0.034796 0.117095 -0.204966 -0.039916 -0.563946 -0.000487 + 5 -0.030144 -0.174368 -0.141739 -0.056298 0.309778 -0.000597 + 6 0.001561 0.275685 -0.160267 -0.046435 0.129795 -0.000507 + 7 0.025000 0.006368 0.046091 -0.032453 0.442888 -0.000109 + 8 0.054473 -0.130438 0.108029 0.045686 -0.304189 0.000424 + 9 -0.318881 -0.796207 0.404680 -0.913138 -0.455463 0.020881 + 10 0.293872 0.067731 0.325211 -0.040674 -0.012515 0.949128 + 11 -0.884355 -0.222725 -0.673931 0.378127 0.252139 0.307944 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 110.28 0.022371 113.05 0.063304 (-0.240120 0.023487 -0.071374) + 7: 610.44 0.010408 52.60 0.005321 ( 0.025851 0.026170 -0.062989) + 8: 798.53 0.047448 239.78 0.018543 ( 0.102775 0.000062 -0.089331) + 9: 1266.31 0.001701 8.59 0.000419 (-0.012091 0.016168 0.003393) + 10: 1673.69 0.032174 162.59 0.005999 (-0.056300 -0.019160 0.049619) + 11: 3666.83 0.008954 45.25 0.000762 (-0.010410 0.019065 0.017034) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 110.28 E(vib) ... 0.45 +freq. 610.44 E(vib) ... 0.10 +freq. 798.53 E(vib) ... 0.05 +freq. 1266.31 E(vib) ... 0.01 +freq. 1673.69 E(vib) ... 0.00 +freq. 3666.83 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.44308053 Eh +Zero point energy ... 0.01851258 Eh 11.62 kcal/mol +Thermal vibrational correction ... 0.00096350 Eh 0.60 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42077190 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00379604 Eh 2.38 kcal/mol +Non-thermal (ZPE) correction 0.01851258 Eh 11.62 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02230862 Eh 14.00 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42077190 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.41982769 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.719290 0.419112 0.368078 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00177609 Eh 1.11 kcal/mol +Rotational entropy ... 0.00992092 Eh 6.23 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02949933 Eh 18.51 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00992092 Eh 6.23 kcal/mol| +| sn= 2 | S(rot)= 0.00926646 Eh 5.81 kcal/mol| +| sn= 3 | S(rot)= 0.00888363 Eh 5.57 kcal/mol| +| sn= 4 | S(rot)= 0.00861201 Eh 5.40 kcal/mol| +| sn= 5 | S(rot)= 0.00840132 Eh 5.27 kcal/mol| +| sn= 6 | S(rot)= 0.00822917 Eh 5.16 kcal/mol| +| sn= 7 | S(rot)= 0.00808363 Eh 5.07 kcal/mol| +| sn= 8 | S(rot)= 0.00795755 Eh 4.99 kcal/mol| +| sn= 9 | S(rot)= 0.00784634 Eh 4.92 kcal/mol| +| sn=10 | S(rot)= 0.00774686 Eh 4.86 kcal/mol| +| sn=11 | S(rot)= 0.00765687 Eh 4.80 kcal/mol| +| sn=12 | S(rot)= 0.00757472 Eh 4.75 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.41982769 Eh +Total entropy correction ... -0.02949933 Eh -18.51 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44932702 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00624649 Eh -3.92 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.443080527 Eh +Current gradient norm .... 0.023635958 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.000890732 0.113249465 0.188015990 0.477336991 0.513413713 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999410770 +Lowest eigenvalues of augmented Hessian: + -0.000150162 0.107125270 0.187173402 0.477216590 0.513197940 +Length of the computed step .... 0.034343889 +The final length of the internal step .... 0.034343889 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0140208338 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0069847286 RMS(Int)= 0.0140216505 + Iter 1: RMS(Cart)= 0.0000140966 RMS(Int)= 0.0000267124 + Iter 2: RMS(Cart)= 0.0000001226 RMS(Int)= 0.0000001024 + Iter 3: RMS(Cart)= 0.0000000007 RMS(Int)= 0.0000000013 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000007 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0020771969 0.0001000000 NO + MAX gradient 0.0041608475 0.0003000000 NO + RMS step 0.0140208338 0.0020000000 NO + MAX step 0.0328183612 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0174 Max(Angles) 0.40 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4538 0.004161 -0.0174 1.4365 + 2. B(O 2,N 1) 1.1771 0.001089 0.0016 1.1787 + 3. B(H 3,O 0) 0.9744 0.001272 -0.0011 0.9734 + 4. A(N 1,O 0,H 3) 104.70 0.000368 0.36 105.06 + 5. A(O 0,N 1,O 2) 112.56 -0.002374 0.40 112.96 + 6. D(O 2,N 1,O 0,H 3) -40.91 -0.017217 0.00 -40.91 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.719579 -0.358445 0.414429 + N 0.545385 -0.562927 -0.234797 + O 0.876298 0.354776 -0.896394 + H -0.702103 0.566597 0.716761 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.359807 -0.677363 0.783158 + 1 N 7.0000 0 14.007 1.030629 -1.063778 -0.443701 + 2 O 8.0000 0 15.999 1.655963 0.670429 -1.693939 + 3 H 1.0000 0 1.008 -1.326783 1.070713 1.354482 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.436468067788 0.00000000 0.00000000 + O 2 1 0 1.178724579962 112.95880000 0.00000000 + H 1 2 3 0.973351192068 105.06161474 319.09090911 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.714531248243 0.00000000 0.00000000 + O 2 1 0 2.227466643450 112.95880000 0.00000000 + H 1 2 3 1.839367185135 105.06161474 319.09090911 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2242 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2715 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 542 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.403991326646 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.556e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7153034878 0.000000000000 0.00051664 0.00001363 0.0028571 0.7000 + 1 -204.7153458661 -0.000042378248 0.00042485 0.00001141 0.0022148 0.7000 + ***Turning on DIIS*** + 2 -204.7153810810 -0.000035214965 0.00108657 0.00002963 0.0016980 0.0000 + 3 -204.7150479886 0.000333092400 0.00039765 0.00001344 0.0004575 0.0000 + 4 -204.7157406820 -0.000692693359 0.00017252 0.00000418 0.0001470 0.0000 + 5 -204.7156156184 0.000125063555 0.00003656 0.00000128 0.0000520 0.0000 + 6 -204.7152598094 0.000355809035 0.00002443 0.00000069 0.0000475 0.0000 + 7 -204.7155089993 -0.000249189878 0.00000859 0.00000032 0.0000171 0.0000 + 8 -204.7154937802 0.000015219096 0.00000697 0.00000022 0.0000100 0.0000 + 9 -204.7154750398 0.000018740388 0.00000424 0.00000017 0.0000056 0.0000 + 10 -204.7155072822 -0.000032242373 0.00000208 0.00000009 0.0000019 0.0000 + 11 -204.7154927098 0.000014572408 0.00000139 0.00000006 0.0000013 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + +Total Energy : -204.71549678 Eh -5570.59187 eV + Last Energy change ... -4.0749e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.7488e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.201 sec +Reference energy ... -204.715495826 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.330 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.077 sec +K-integral sorting ... 5.336 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.024 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.027 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.031 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.345 sec +AO-integral generation ... 0.242 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.049 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.163 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.249 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090283636 +EMP2(bb)= -0.090283636 +EMP2(ab)= -0.515519875 + +Initial guess performed in 0.134 sec +E(0) ... -204.715495826 +E(MP2) ... -0.696087147 +Initial E(tot) ... -205.411582973 + ... 0.187285152 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.411582973 -0.696087148 -0.000000000 0.024792700 2.70 0.000001523 + *** Turning on DIIS *** + 1 -205.383181948 -0.667686122 0.028401026 0.009859536 2.69 0.057288848 + 2 -205.402573618 -0.687077792 -0.019391670 0.005459563 2.78 0.060487444 + 3 -205.406314682 -0.690818856 -0.003741064 0.001803860 2.81 0.074696468 + 4 -205.407887589 -0.692391763 -0.001572907 0.001520104 2.79 0.081541274 + 5 -205.408440090 -0.692944264 -0.000552501 0.000901220 2.89 0.087143705 + 6 -205.408549601 -0.693053775 -0.000109511 0.000551041 2.80 0.089949276 + 7 -205.408596101 -0.693100275 -0.000046500 0.000250695 2.82 0.091243698 + 8 -205.408607604 -0.693111779 -0.000011503 0.000120075 3.04 0.091768137 + 9 -205.408603543 -0.693107717 0.000004062 0.000049430 2.83 0.091928558 + 10 -205.408608815 -0.693112989 -0.000005272 0.000030668 2.77 0.091992774 + 11 -205.408605818 -0.693109993 0.000002996 0.000022044 2.91 0.091981850 + 12 -205.408607195 -0.693111370 -0.000001377 0.000014584 2.83 0.091996084 + 13 -205.408607026 -0.693111200 0.000000169 0.000008582 2.91 0.091992241 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.715495826 +E(CORR) ... -0.693111200 +E(TOT) ... -205.408607026 +Singles norm **1/2 ... 0.091992241 ( 0.045996120, 0.045996120) +T1 diagnostic ... 0.021682779 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.057631 + 8b-> 13b -1b-> -1b 0.040820 + 8a-> 13a -1a-> -1a 0.040820 + 9a-> 13a 9b-> 13b 0.036016 + 10a-> 13a 10b-> 13b 0.034682 + 9a-> 13a 8b-> 13b 0.031549 + 8a-> 13a 9b-> 13b 0.031549 + 11a-> 13a 11b-> 13b 0.030353 + 10b-> 13b -1b-> -1b 0.029650 + 10a-> 13a -1a-> -1a 0.029650 + 5a-> 13a 5b-> 13b 0.026891 + 10a-> 13a 8b-> 13b 0.026642 + 8a-> 13a 10b-> 13b 0.026642 + 10a-> 13a 9b-> 13b 0.025258 + 9a-> 13a 10b-> 13b 0.025258 + 8a-> 13a 8b-> 22b 0.021595 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034545699 + alpha-alpha-alpha ... -0.000894850 ( 2.6%) + alpha-alpha-beta ... -0.016378000 ( 47.4%) + alpha-beta -beta ... -0.016378000 ( 47.4%) + beta -beta -beta ... -0.000894850 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034545699 + +Final correlation energy ... -0.727656900 +E(CCSD) ... -205.408607026 +E(CCSD(T)) ... -205.443152725 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209503703 sqrt= 1.099774387 +W(HF) = 0.826785398 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 54.841 sec + +Fock Matrix Formation ... 0.201 sec ( 0.4%) +Initial Guess ... 0.134 sec ( 0.2%) +DIIS Solver ... 1.650 sec ( 3.0%) +State Vector Update ... 0.085 sec ( 0.2%) +Sigma-vector construction ... 37.840 sec ( 69.0%) + <0|H|D> ... 0.003 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.022 sec ( 0.1% of sigma) + (0-ext) ... 0.071 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (2-ext) ... 0.938 sec ( 2.5% of sigma) + (4-ext) ... 20.968 sec ( 55.4% of sigma) + ... 1.294 sec ( 3.4% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.106 sec ( 0.3% of sigma) + Fock-dressing ... 2.094 sec ( 5.5% of sigma) + (ik|jl)-dressing ... 0.074 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.637 sec ( 25.5% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 7.133 sec ( 13.0% of ALL) + I/O of integral and amplitudes ... 0.944 sec ( 13.2% of (T)) + External N**7 contributions ... 4.016 sec ( 56.3% of (T)) + Internal N**7 contributions ... 0.335 sec ( 4.7% of (T)) + N**6 triples energy contributions ... 1.750 sec ( 24.5% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.443152725208 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.005872673 0.002361981 -0.012749358 + 2 N : 0.005933104 0.004202022 0.010852116 + 3 O : -0.004126819 -0.003546726 -0.006952338 + 4 H : 0.004066388 -0.003017276 0.008849581 + +Norm of the cartesian gradient ... 0.023561408 +RMS gradient ... 0.006801593 +MAX gradient ... 0.012749358 + +------- +TIMINGS +------- + +Total numerical gradient time ... 353.881 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.443152725 Eh +Current gradient norm .... 0.023561408 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999997791 +Lowest eigenvalues of augmented Hessian: + -0.000000545 0.112712090 0.188907142 0.477183088 0.512426592 +Length of the computed step .... 0.002101700 +The final length of the internal step .... 0.002101700 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0008580154 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0004326088 RMS(Int)= 0.0008580135 + Iter 1: RMS(Cart)= 0.0000000517 RMS(Int)= 0.0000000878 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000721985 0.0000050000 NO + RMS gradient 0.0001117707 0.0001000000 NO + MAX gradient 0.0002651968 0.0003000000 YES + RMS step 0.0008580154 0.0020000000 YES + MAX step 0.0020160772 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0011 Max(Angles) 0.03 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4365 -0.000265 0.0011 1.4375 + 2. B(O 2,N 1) 1.1787 -0.000017 -0.0001 1.1786 + 3. B(H 3,O 0) 0.9734 -0.000046 0.0000 0.9734 + 4. A(N 1,O 0,H 3) 105.06 0.000003 -0.03 105.03 + 5. A(O 0,N 1,O 2) 112.96 0.000047 -0.01 112.95 + 6. D(O 2,N 1,O 0,H 3) -40.91 -0.018108 -0.00 -40.91 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.720057 -0.358445 0.414684 + N 0.545843 -0.562992 -0.235058 + O 0.876421 0.354764 -0.896494 + H -0.702205 0.566673 0.716868 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.360711 -0.677362 0.783639 + 1 N 7.0000 0 14.007 1.031493 -1.063901 -0.444195 + 2 O 8.0000 0 15.999 1.656195 0.670406 -1.694129 + 3 H 1.0000 0 1.008 -1.326975 1.070857 1.354685 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.437534929880 0.00000000 0.00000000 + O 2 1 0 1.178582482862 112.94562438 0.00000000 + H 1 2 3 0.973384438065 105.03451907 319.09090911 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.716547325418 0.00000000 0.00000000 + O 2 1 0 2.227198118846 112.94562438 0.00000000 + H 1 2 3 1.839430010964 105.03451907 319.09090911 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2242 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2715 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 542 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.386085275021 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.558e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7154191341 0.000000000000 0.00003244 0.00000081 0.0001755 0.7000 + 1 -204.7154192901 -0.000000156036 0.00002670 0.00000068 0.0001364 0.7000 + ***Turning on DIIS*** + 2 -204.7154194199 -0.000000129813 0.00006939 0.00000182 0.0001050 0.0000 + 3 -204.7154334381 -0.000014018172 0.00002165 0.00000078 0.0000261 0.0000 + 4 -204.7154085179 0.000024920218 0.00000948 0.00000025 0.0000077 0.0000 + 5 -204.7154224742 -0.000013956320 0.00000272 0.00000009 0.0000027 0.0000 + 6 -204.7154269154 -0.000004441172 0.00000151 0.00000004 0.0000025 0.0000 + 7 -204.7154181485 0.000008766871 0.00000050 0.00000002 0.0000013 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + +Total Energy : -204.71542085 Eh -5570.58980 eV + Last Energy change ... -2.7019e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.2460e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.202 sec +Reference energy ... -204.715419848 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.344 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.343 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.024 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.027 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.031 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.030 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.346 sec +AO-integral generation ... 0.243 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.048 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.149 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.250 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090291048 +EMP2(bb)= -0.090291048 +EMP2(ab)= -0.515579658 + +Initial guess performed in 0.133 sec +E(0) ... -204.715419848 +E(MP2) ... -0.696161754 +Initial E(tot) ... -205.411581602 + ... 0.187357804 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.411581602 -0.696161754 -0.000000000 0.024776552 2.74 0.000001163 + *** Turning on DIIS *** + 1 -205.383148041 -0.667728193 0.028433561 0.009880091 2.74 0.057321323 + 2 -205.402551976 -0.687132128 -0.019403935 0.005454120 2.78 0.060512548 + 3 -205.406295382 -0.690875534 -0.003743406 0.001801453 2.80 0.074732330 + 4 -205.407869633 -0.692449785 -0.001574251 0.001527234 2.81 0.081582384 + 5 -205.408423180 -0.693003332 -0.000553547 0.000905125 2.85 0.087196387 + 6 -205.408533020 -0.693113173 -0.000109841 0.000553389 2.80 0.090012081 + 7 -205.408579741 -0.693159894 -0.000046721 0.000251468 2.88 0.091313968 + 8 -205.408591335 -0.693171487 -0.000011593 0.000120519 2.88 0.091841391 + 9 -205.408587254 -0.693167406 0.000004081 0.000049326 2.81 0.092002465 + 10 -205.408592557 -0.693172709 -0.000005303 0.000030625 2.76 0.092067038 + 11 -205.408589549 -0.693169701 0.000003008 0.000022011 2.78 0.092056051 + 12 -205.408590926 -0.693171078 -0.000001377 0.000014578 2.82 0.092070351 + 13 -205.408590757 -0.693170909 0.000000169 0.000008603 3.11 0.092066488 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.715419848 +E(CORR) ... -0.693170909 +E(TOT) ... -205.408590757 +Singles norm **1/2 ... 0.092066488 ( 0.046033244, 0.046033244) +T1 diagnostic ... 0.021700279 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.057778 + 8a-> 13a -1a-> -1a 0.040781 + 8b-> 13b -1b-> -1b 0.040781 + 9a-> 13a 9b-> 13b 0.036012 + 10a-> 13a 10b-> 13b 0.034536 + 9a-> 13a 8b-> 13b 0.031612 + 8a-> 13a 9b-> 13b 0.031612 + 11a-> 13a 11b-> 13b 0.030314 + 10b-> 13b -1b-> -1b 0.029819 + 10a-> 13a -1a-> -1a 0.029819 + 5a-> 13a 5b-> 13b 0.026937 + 10a-> 13a 8b-> 13b 0.026617 + 8a-> 13a 10b-> 13b 0.026617 + 9a-> 13a 10b-> 13b 0.025187 + 10a-> 13a 9b-> 13b 0.025187 + 8a-> 13a 8b-> 22b 0.021644 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034562216 + alpha-alpha-alpha ... -0.000895037 ( 2.6%) + alpha-alpha-beta ... -0.016386071 ( 47.4%) + alpha-beta -beta ... -0.016386071 ( 47.4%) + beta -beta -beta ... -0.000895037 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034562216 + +Final correlation energy ... -0.727733125 +E(CCSD) ... -205.408590757 +E(CCSD(T)) ... -205.443152973 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209603169 sqrt= 1.099819607 +W(HF) = 0.826717411 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 55.081 sec + +Fock Matrix Formation ... 0.202 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 1.710 sec ( 3.1%) +State Vector Update ... 0.083 sec ( 0.2%) +Sigma-vector construction ... 37.770 sec ( 68.6%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.025 sec ( 0.1% of sigma) + (0-ext) ... 0.070 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.025 sec ( 0.1% of sigma) + (2-ext) ... 0.933 sec ( 2.5% of sigma) + (4-ext) ... 20.941 sec ( 55.4% of sigma) + ... 1.431 sec ( 3.8% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.108 sec ( 0.3% of sigma) + Fock-dressing ... 2.047 sec ( 5.4% of sigma) + (ik|jl)-dressing ... 0.074 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.483 sec ( 25.1% of sigma) + Pair energies ... 0.006 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.908 sec ( 12.5% of ALL) + I/O of integral and amplitudes ... 0.808 sec ( 11.7% of (T)) + External N**7 contributions ... 3.903 sec ( 56.5% of (T)) + Internal N**7 contributions ... 0.319 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.691 sec ( 24.5% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.443152973382 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.006102098 0.002365383 -0.012595834 + 2 N : 0.006173063 0.004109479 0.010697467 + 3 O : -0.004126217 -0.003511321 -0.006937014 + 4 H : 0.004055251 -0.002963541 0.008835381 + +Norm of the cartesian gradient ... 0.023487971 +RMS gradient ... 0.006780393 +MAX gradient ... 0.012595834 + +------- +TIMINGS +------- + +Total numerical gradient time ... 357.858 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.443152973 Eh +Current gradient norm .... 0.023487971 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999992 +Lowest eigenvalues of augmented Hessian: + -0.000000002 0.117601816 0.192362114 0.477184822 0.511993921 +Length of the computed step .... 0.000122845 +The final length of the internal step .... 0.000122845 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0000501512 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0000288402 RMS(Int)= 0.0000501512 + Iter 1: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000002 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000002482 0.0000050000 YES + RMS gradient 0.0000073137 0.0001000000 YES + MAX gradient 0.0000176882 0.0003000000 YES + RMS step 0.0000501512 0.0020000000 YES + MAX step 0.0001207649 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4375 0.000018 -0.0001 1.4375 + 2. B(O 2,N 1) 1.1786 0.000002 0.0000 1.1786 + 3. B(H 3,O 0) 0.9734 0.000000 0.0000 0.9734 + 4. A(N 1,O 0,H 3) 105.03 0.000002 0.00 105.04 + 5. A(O 0,N 1,O 2) 112.95 0.000001 0.00 112.95 + 6. D(O 2,N 1,O 0,H 3) -40.91 -0.018054 0.00 -40.91 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.720031 -0.358448 0.414667 + N 0.545815 -0.562990 -0.235040 + O 0.876407 0.354768 -0.896483 + H -0.702190 0.566670 0.716856 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.360661 -0.677368 0.783607 + 1 N 7.0000 0 14.007 1.031442 -1.063897 -0.444161 + 2 O 8.0000 0 15.999 1.656169 0.670414 -1.694108 + 3 H 1.0000 0 1.008 -1.326948 1.070851 1.354661 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.437471023863 0.00000000 0.00000000 + O 2 1 0 1.178591001336 112.94595042 0.00000000 + H 1 2 3 0.973385154345 105.03535601 319.09090911 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.716426560548 0.00000000 0.00000000 + O 2 1 0 2.227214216428 112.94595042 0.00000000 + H 1 2 3 1.839431364536 105.03535601 319.09090911 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2242 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2715 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 542 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.387208989773 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.3872089898 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.557e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7154242769 0.000000000000 0.00000193 0.00000005 0.0000107 0.7000 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 1 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71542428 Eh -5570.58990 eV + +Components: +Nuclear Repulsion : 69.38720899 Eh 1888.12195 eV +Electronic Energy : -274.10263327 Eh -7458.71184 eV +One Electron Energy: -418.40330601 Eh -11385.33278 eV +Two Electron Energy: 144.30067274 Eh 3926.62093 eV + +Virial components: +Potential Energy : -408.95525211 Eh -11128.23816 eV +Kinetic Energy : 204.23982783 Eh 5557.64826 eV +Virial Ratio : 2.00232862 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -7.5693e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.5885e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.0160e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.3318e-06 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.676675 -562.6409 + 1 1.0000 -20.636700 -561.5532 + 2 1.0000 -15.803565 -430.0369 + 3 1.0000 -1.609675 -43.8015 + 4 1.0000 -1.395176 -37.9647 + 5 1.0000 -0.962158 -26.1817 + 6 1.0000 -0.773677 -21.0528 + 7 1.0000 -0.738677 -20.1004 + 8 1.0000 -0.694426 -18.8963 + 9 1.0000 -0.606716 -16.5096 + 10 1.0000 -0.534103 -14.5337 + 11 1.0000 -0.469435 -12.7740 + 12 0.0000 0.031087 0.8459 + 13 0.0000 0.070978 1.9314 + 14 0.0000 0.094156 2.5621 + 15 0.0000 0.110876 3.0171 + 16 0.0000 0.116874 3.1803 + 17 0.0000 0.151344 4.1183 + 18 0.0000 0.157249 4.2790 + 19 0.0000 0.170470 4.6387 + 20 0.0000 0.181348 4.9347 + 21 0.0000 0.193347 5.2612 + 22 0.0000 0.203405 5.5349 + 23 0.0000 0.234320 6.3762 + 24 0.0000 0.262399 7.1402 + 25 0.0000 0.293946 7.9987 + 26 0.0000 0.310552 8.4506 + 27 0.0000 0.340005 9.2520 + 28 0.0000 0.345775 9.4090 + 29 0.0000 0.379132 10.3167 + 30 0.0000 0.422137 11.4869 + 31 0.0000 0.514843 14.0096 + 32 0.0000 0.528544 14.3824 + 33 0.0000 0.534201 14.5363 + 34 0.0000 0.562606 15.3093 + 35 0.0000 0.611355 16.6358 + 36 0.0000 0.633891 17.2491 + 37 0.0000 0.650636 17.7047 + 38 0.0000 0.692751 18.8507 + 39 0.0000 0.706412 19.2224 + 40 0.0000 0.733701 19.9650 + 41 0.0000 0.744141 20.2491 + 42 0.0000 0.766510 20.8578 + 43 0.0000 0.784102 21.3365 + 44 0.0000 0.811195 22.0737 + 45 0.0000 0.834393 22.7050 + 46 0.0000 0.849322 23.1112 + 47 0.0000 0.880055 23.9475 + 48 0.0000 0.919489 25.0206 + 49 0.0000 0.941856 25.6292 + 50 0.0000 0.968475 26.3536 + 51 0.0000 0.982079 26.7237 + 52 0.0000 1.017441 27.6860 + 53 0.0000 1.026008 27.9191 + 54 0.0000 1.061621 28.8882 + 55 0.0000 1.086907 29.5762 + 56 0.0000 1.166633 31.7457 + 57 0.0000 1.198665 32.6173 + 58 0.0000 1.235281 33.6137 + 59 0.0000 1.278743 34.7964 + 60 0.0000 1.359279 36.9879 + 61 0.0000 1.411669 38.4135 + 62 0.0000 1.440534 39.1989 + 63 0.0000 1.525772 41.5184 + 64 0.0000 1.530988 41.6603 + 65 0.0000 1.546873 42.0926 + 66 0.0000 1.612858 43.8881 + 67 0.0000 1.631782 44.4030 + 68 0.0000 1.654193 45.0129 + 69 0.0000 1.732684 47.1487 + 70 0.0000 1.770817 48.1864 + 71 0.0000 1.803346 49.0715 + 72 0.0000 1.905344 51.8471 + 73 0.0000 1.961116 53.3647 + 74 0.0000 1.974843 53.7382 + 75 0.0000 2.014202 54.8092 + 76 0.0000 2.042153 55.5698 + 77 0.0000 2.078649 56.5629 + 78 0.0000 2.157938 58.7205 + 79 0.0000 2.173768 59.1512 + 80 0.0000 2.253405 61.3183 + 81 0.0000 2.306559 62.7647 + 82 0.0000 2.352301 64.0094 + 83 0.0000 2.395195 65.1766 + 84 0.0000 2.416277 65.7502 + 85 0.0000 2.449094 66.6432 + 86 0.0000 2.469706 67.2041 + 87 0.0000 2.505801 68.1863 + 88 0.0000 2.532098 68.9019 + 89 0.0000 2.557182 69.5845 + 90 0.0000 2.575641 70.0868 + 91 0.0000 2.618430 71.2511 + 92 0.0000 2.651825 72.1598 + 93 0.0000 2.693292 73.2882 + 94 0.0000 2.761594 75.1468 + 95 0.0000 2.802750 76.2667 + 96 0.0000 2.835138 77.1480 + 97 0.0000 2.942130 80.0594 + 98 0.0000 2.974850 80.9498 + 99 0.0000 3.014633 82.0323 + 100 0.0000 3.139633 85.4338 + 101 0.0000 3.170408 86.2712 + 102 0.0000 3.227965 87.8374 + 103 0.0000 3.512687 95.5851 + 104 0.0000 3.693027 100.4924 + 105 0.0000 3.880942 105.6058 + 106 0.0000 4.016828 109.3034 + 107 0.0000 4.151887 112.9786 + 108 0.0000 4.184950 113.8783 + 109 0.0000 4.326857 117.7398 + 110 0.0000 4.380976 119.2124 + 111 0.0000 4.387872 119.4001 + 112 0.0000 4.533414 123.3605 + 113 0.0000 4.582271 124.6899 + 114 0.0000 4.678525 127.3091 + 115 0.0000 4.796030 130.5066 + 116 0.0000 4.821974 131.2126 + 117 0.0000 4.867856 132.4611 + 118 0.0000 4.967619 135.1758 + 119 0.0000 4.999033 136.0306 + 120 0.0000 5.073540 138.0580 + 121 0.0000 5.107294 138.9765 + 122 0.0000 5.185649 141.1087 + 123 0.0000 5.233254 142.4041 + 124 0.0000 5.248639 142.8227 + 125 0.0000 5.278536 143.6363 + 126 0.0000 5.382845 146.4747 + 127 0.0000 5.472952 148.9266 + 128 0.0000 5.533839 150.5834 + 129 0.0000 5.699052 155.0791 + 130 0.0000 5.775880 157.1697 + 131 0.0000 5.952664 161.9802 + 132 0.0000 6.164638 167.7483 + 133 0.0000 6.402839 174.2301 + 134 0.0000 6.495164 176.7424 + 135 0.0000 6.527378 177.6190 + 136 0.0000 6.686172 181.9400 + 137 0.0000 6.721688 182.9064 + 138 0.0000 6.778349 184.4483 + 139 0.0000 6.799600 185.0265 + 140 0.0000 6.895343 187.6318 + 141 0.0000 7.096934 193.1174 + 142 0.0000 7.127100 193.9383 + 143 0.0000 7.170481 195.1187 + 144 0.0000 7.197701 195.8594 + 145 0.0000 7.246209 197.1794 + 146 0.0000 7.265336 197.6998 + 147 0.0000 7.316038 199.0795 + 148 0.0000 7.393272 201.1812 + 149 0.0000 7.462444 203.0634 + 150 0.0000 7.507937 204.3014 + 151 0.0000 7.534489 205.0239 + 152 0.0000 7.552419 205.5118 + 153 0.0000 7.664386 208.5585 + 154 0.0000 7.779827 211.6998 + 155 0.0000 7.890083 214.7001 + 156 0.0000 8.136660 221.4098 + 157 0.0000 8.349959 227.2139 + 158 0.0000 14.047102 382.2411 + 159 0.0000 15.109662 411.1548 + 160 0.0000 15.783010 429.4775 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.676675 -562.6409 + 1 1.0000 -20.636700 -561.5532 + 2 1.0000 -15.803565 -430.0369 + 3 1.0000 -1.609675 -43.8015 + 4 1.0000 -1.395176 -37.9647 + 5 1.0000 -0.962158 -26.1817 + 6 1.0000 -0.773677 -21.0528 + 7 1.0000 -0.738677 -20.1004 + 8 1.0000 -0.694426 -18.8963 + 9 1.0000 -0.606716 -16.5096 + 10 1.0000 -0.534103 -14.5337 + 11 1.0000 -0.469435 -12.7740 + 12 0.0000 0.031087 0.8459 + 13 0.0000 0.070978 1.9314 + 14 0.0000 0.094156 2.5621 + 15 0.0000 0.110876 3.0171 + 16 0.0000 0.116874 3.1803 + 17 0.0000 0.151344 4.1183 + 18 0.0000 0.157249 4.2790 + 19 0.0000 0.170470 4.6387 + 20 0.0000 0.181348 4.9347 + 21 0.0000 0.193347 5.2612 + 22 0.0000 0.203405 5.5349 + 23 0.0000 0.234320 6.3762 + 24 0.0000 0.262399 7.1402 + 25 0.0000 0.293946 7.9987 + 26 0.0000 0.310552 8.4506 + 27 0.0000 0.340005 9.2520 + 28 0.0000 0.345775 9.4090 + 29 0.0000 0.379132 10.3167 + 30 0.0000 0.422137 11.4869 + 31 0.0000 0.514843 14.0096 + 32 0.0000 0.528544 14.3824 + 33 0.0000 0.534201 14.5363 + 34 0.0000 0.562606 15.3093 + 35 0.0000 0.611355 16.6358 + 36 0.0000 0.633891 17.2491 + 37 0.0000 0.650636 17.7047 + 38 0.0000 0.692751 18.8507 + 39 0.0000 0.706412 19.2224 + 40 0.0000 0.733701 19.9650 + 41 0.0000 0.744141 20.2491 + 42 0.0000 0.766510 20.8578 + 43 0.0000 0.784102 21.3365 + 44 0.0000 0.811195 22.0737 + 45 0.0000 0.834393 22.7050 + 46 0.0000 0.849322 23.1112 + 47 0.0000 0.880055 23.9475 + 48 0.0000 0.919489 25.0206 + 49 0.0000 0.941856 25.6292 + 50 0.0000 0.968475 26.3536 + 51 0.0000 0.982079 26.7237 + 52 0.0000 1.017441 27.6860 + 53 0.0000 1.026008 27.9191 + 54 0.0000 1.061621 28.8882 + 55 0.0000 1.086907 29.5762 + 56 0.0000 1.166633 31.7457 + 57 0.0000 1.198665 32.6173 + 58 0.0000 1.235281 33.6137 + 59 0.0000 1.278743 34.7964 + 60 0.0000 1.359279 36.9879 + 61 0.0000 1.411669 38.4135 + 62 0.0000 1.440534 39.1989 + 63 0.0000 1.525772 41.5184 + 64 0.0000 1.530988 41.6603 + 65 0.0000 1.546873 42.0926 + 66 0.0000 1.612858 43.8881 + 67 0.0000 1.631782 44.4030 + 68 0.0000 1.654193 45.0129 + 69 0.0000 1.732684 47.1487 + 70 0.0000 1.770817 48.1864 + 71 0.0000 1.803346 49.0715 + 72 0.0000 1.905344 51.8471 + 73 0.0000 1.961116 53.3647 + 74 0.0000 1.974843 53.7382 + 75 0.0000 2.014202 54.8092 + 76 0.0000 2.042153 55.5698 + 77 0.0000 2.078649 56.5629 + 78 0.0000 2.157938 58.7205 + 79 0.0000 2.173768 59.1512 + 80 0.0000 2.253405 61.3183 + 81 0.0000 2.306559 62.7647 + 82 0.0000 2.352301 64.0094 + 83 0.0000 2.395195 65.1766 + 84 0.0000 2.416277 65.7502 + 85 0.0000 2.449094 66.6432 + 86 0.0000 2.469706 67.2041 + 87 0.0000 2.505801 68.1863 + 88 0.0000 2.532098 68.9019 + 89 0.0000 2.557182 69.5845 + 90 0.0000 2.575641 70.0868 + 91 0.0000 2.618430 71.2511 + 92 0.0000 2.651825 72.1598 + 93 0.0000 2.693292 73.2882 + 94 0.0000 2.761594 75.1468 + 95 0.0000 2.802750 76.2667 + 96 0.0000 2.835138 77.1480 + 97 0.0000 2.942130 80.0594 + 98 0.0000 2.974850 80.9498 + 99 0.0000 3.014633 82.0323 + 100 0.0000 3.139633 85.4338 + 101 0.0000 3.170408 86.2712 + 102 0.0000 3.227965 87.8374 + 103 0.0000 3.512687 95.5851 + 104 0.0000 3.693027 100.4924 + 105 0.0000 3.880942 105.6058 + 106 0.0000 4.016828 109.3034 + 107 0.0000 4.151887 112.9786 + 108 0.0000 4.184950 113.8783 + 109 0.0000 4.326857 117.7398 + 110 0.0000 4.380976 119.2124 + 111 0.0000 4.387872 119.4001 + 112 0.0000 4.533414 123.3605 + 113 0.0000 4.582271 124.6899 + 114 0.0000 4.678525 127.3091 + 115 0.0000 4.796030 130.5066 + 116 0.0000 4.821974 131.2126 + 117 0.0000 4.867856 132.4611 + 118 0.0000 4.967619 135.1758 + 119 0.0000 4.999033 136.0306 + 120 0.0000 5.073540 138.0580 + 121 0.0000 5.107294 138.9765 + 122 0.0000 5.185649 141.1087 + 123 0.0000 5.233254 142.4041 + 124 0.0000 5.248639 142.8227 + 125 0.0000 5.278536 143.6363 + 126 0.0000 5.382845 146.4747 + 127 0.0000 5.472952 148.9266 + 128 0.0000 5.533839 150.5834 + 129 0.0000 5.699052 155.0791 + 130 0.0000 5.775880 157.1697 + 131 0.0000 5.952664 161.9802 + 132 0.0000 6.164638 167.7483 + 133 0.0000 6.402839 174.2301 + 134 0.0000 6.495164 176.7424 + 135 0.0000 6.527378 177.6190 + 136 0.0000 6.686172 181.9400 + 137 0.0000 6.721688 182.9064 + 138 0.0000 6.778349 184.4483 + 139 0.0000 6.799600 185.0265 + 140 0.0000 6.895343 187.6318 + 141 0.0000 7.096934 193.1174 + 142 0.0000 7.127100 193.9383 + 143 0.0000 7.170481 195.1187 + 144 0.0000 7.197701 195.8594 + 145 0.0000 7.246209 197.1794 + 146 0.0000 7.265336 197.6998 + 147 0.0000 7.316038 199.0795 + 148 0.0000 7.393272 201.1812 + 149 0.0000 7.462444 203.0634 + 150 0.0000 7.507937 204.3014 + 151 0.0000 7.534489 205.0239 + 152 0.0000 7.552419 205.5118 + 153 0.0000 7.664386 208.5585 + 154 0.0000 7.779827 211.6998 + 155 0.0000 7.890083 214.7001 + 156 0.0000 8.136660 221.4098 + 157 0.0000 8.349959 227.2139 + 158 0.0000 14.047102 382.2411 + 159 0.0000 15.109662 411.1548 + 160 0.0000 15.783010 429.4775 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.320811 0.000000 + 1 N : 0.348741 0.000000 + 2 O : -0.276967 0.000000 + 3 H : 0.249037 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.824674 s : 3.824674 + pz : 1.707769 p : 4.458136 + px : 1.330833 + py : 1.419534 + dz2 : 0.005565 d : 0.033098 + dxz : 0.007282 + dyz : 0.000671 + dx2y2 : 0.014828 + dxy : 0.004752 + f0 : 0.000603 f : 0.004903 + f+1 : 0.001084 + f-1 : 0.000187 + f+2 : 0.000601 + f-2 : 0.000590 + f+3 : 0.000848 + f-3 : 0.000991 + 1 N s : 3.844059 s : 3.844059 + pz : 0.749233 p : 2.632542 + px : 0.758548 + py : 1.124761 + dz2 : 0.031592 d : 0.142135 + dxz : 0.029365 + dyz : 0.022347 + dx2y2 : 0.038059 + dxy : 0.020771 + f0 : 0.001536 f : 0.032523 + f+1 : 0.004670 + f-1 : 0.005008 + f+2 : 0.003392 + f-2 : 0.005023 + f+3 : 0.005902 + f-3 : 0.006993 + 2 O s : 3.868490 s : 3.868490 + pz : 1.260886 p : 4.339758 + px : 1.700978 + py : 1.377893 + dz2 : 0.018269 d : 0.061225 + dxz : 0.004881 + dyz : 0.013020 + dx2y2 : 0.008986 + dxy : 0.016069 + f0 : 0.000499 f : 0.007494 + f+1 : 0.000173 + f-1 : 0.002062 + f+2 : 0.001370 + f-2 : 0.001090 + f+3 : 0.001188 + f-3 : 0.001111 + 3 H s : 0.641998 s : 0.641998 + pz : 0.040209 p : 0.087697 + px : 0.026390 + py : 0.021098 + dz2 : 0.002203 d : 0.021268 + dxz : 0.000050 + dyz : 0.007204 + dx2y2 : 0.001456 + dxy : 0.010355 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.592195 0.000000 + 1 N : -0.267331 0.000000 + 2 O : 0.244534 0.000000 + 3 H : -0.569397 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.116188 s : 3.116188 + pz : 1.381371 p : 3.922086 + px : 1.226431 + py : 1.314285 + dz2 : 0.037880 d : 0.283517 + dxz : 0.071509 + dyz : 0.029806 + dx2y2 : 0.079034 + dxy : 0.065289 + f0 : 0.008148 f : 0.086014 + f+1 : 0.015990 + f-1 : 0.000881 + f+2 : 0.014333 + f-2 : 0.012251 + f+3 : 0.010487 + f-3 : 0.023924 + 1 N s : 3.014752 s : 3.014752 + pz : 0.796447 p : 2.833736 + px : 0.844161 + py : 1.193128 + dz2 : 0.162227 d : 0.958096 + dxz : 0.214407 + dyz : 0.164250 + dx2y2 : 0.239590 + dxy : 0.177622 + f0 : 0.031456 f : 0.460748 + f+1 : 0.053765 + f-1 : 0.055034 + f+2 : 0.078916 + f-2 : 0.082591 + f+3 : 0.072332 + f-3 : 0.086654 + 2 O s : 3.306081 s : 3.306081 + pz : 1.193239 p : 4.009733 + px : 1.409537 + py : 1.406957 + dz2 : 0.038701 d : 0.323533 + dxz : 0.050337 + dyz : 0.090693 + dx2y2 : 0.096862 + dxy : 0.046941 + f0 : 0.009722 f : 0.116119 + f+1 : 0.005449 + f-1 : 0.018671 + f+2 : 0.028292 + f-2 : 0.020535 + f+3 : 0.010172 + f-3 : 0.023280 + 3 H s : 0.616961 s : 0.616961 + pz : 0.160620 p : 0.555064 + px : 0.136153 + py : 0.258290 + dz2 : 0.050924 d : 0.397372 + dxz : 0.030543 + dyz : 0.111896 + dx2y2 : 0.096514 + dxy : 0.107495 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3208 8.0000 -0.3208 1.8191 1.8191 0.0000 + 1 N 6.6513 7.0000 0.3487 2.5391 2.5391 0.0000 + 2 O 8.2770 8.0000 -0.2770 1.7282 1.7282 0.0000 + 3 H 0.7510 1.0000 0.2490 1.0122 1.0122 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8152 B( 0-O , 3-H ) : 0.9434 B( 1-N , 2-O ) : 1.6614 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.499 sec +Sum of individual times .... 0.307 sec ( 61.5%) + +Fock matrix formation .... 0.225 sec ( 45.2%) +Diagonalization .... 0.023 sec ( 4.5%) +Density matrix formation .... 0.002 sec ( 0.4%) +Population analysis .... 0.035 sec ( 7.0%) +Initial guess .... 0.009 sec ( 1.9%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 1.0%) +DIIS solution .... 0.012 sec ( 2.4%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.203 sec +Reference energy ... -204.715424279 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.339 sec +AO-integral generation ... 0.142 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.342 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.025 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.031 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.030 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.348 sec +AO-integral generation ... 0.244 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.049 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.165 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.251 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090290738 +EMP2(bb)= -0.090290738 +EMP2(ab)= -0.515576621 + +Initial guess performed in 0.133 sec +E(0) ... -204.715424279 +E(MP2) ... -0.696158097 +Initial E(tot) ... -205.411582376 + ... 0.187353876 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.411582376 -0.696158097 -0.000000000 0.024777216 2.75 0.000008803 + *** Turning on DIIS *** + 1 -205.383150094 -0.667725815 0.028432282 0.009878856 2.72 0.057317778 + 2 -205.402553353 -0.687129074 -0.019403259 0.005454467 2.77 0.060509081 + 3 -205.406296553 -0.690872274 -0.003743199 0.001801368 2.83 0.074727847 + 4 -205.407870678 -0.692446399 -0.001574125 0.001527038 2.78 0.081577442 + 5 -205.408424148 -0.692999869 -0.000553470 0.000905035 2.91 0.087190794 + 6 -205.408533975 -0.693109696 -0.000109827 0.000553295 2.82 0.090006175 + 7 -205.408580687 -0.693156408 -0.000046712 0.000251428 2.88 0.091307832 + 8 -205.408592276 -0.693167997 -0.000011590 0.000120476 3.00 0.091835192 + 9 -205.408588196 -0.693163917 0.000004080 0.000049336 2.91 0.091996237 + 10 -205.408593498 -0.693169218 -0.000005301 0.000030630 2.83 0.092060800 + 11 -205.408590490 -0.693166211 0.000003008 0.000022016 2.78 0.092049814 + 12 -205.408591867 -0.693167588 -0.000001377 0.000014580 2.87 0.092064113 + 13 -205.408591698 -0.693167419 0.000000169 0.000008602 2.87 0.092060250 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.715424279 +E(CORR) ... -0.693167419 +E(TOT) ... -205.408591698 +Singles norm **1/2 ... 0.092060250 ( 0.046030125, 0.046030125) +T1 diagnostic ... 0.021698809 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.057770 + 8a-> 13a -1a-> -1a 0.040785 + 8b-> 13b -1b-> -1b 0.040785 + 9a-> 13a 9b-> 13b 0.036012 + 10a-> 13a 10b-> 13b 0.034544 + 8a-> 13a 9b-> 13b 0.031609 + 9a-> 13a 8b-> 13b 0.031609 + 11a-> 13a 11b-> 13b 0.030316 + 10a-> 13a -1a-> -1a 0.029817 + 10b-> 13b -1b-> -1b 0.029817 + 5a-> 13a 5b-> 13b 0.026935 + 10a-> 13a 8b-> 13b 0.026619 + 8a-> 13a 10b-> 13b 0.026619 + 10a-> 13a 9b-> 13b 0.025191 + 9a-> 13a 10b-> 13b 0.025191 + 8a-> 22a 8b-> 13b 0.021641 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034561288 + alpha-alpha-alpha ... -0.000895028 ( 2.6%) + alpha-alpha-beta ... -0.016385616 ( 47.4%) + alpha-beta -beta ... -0.016385616 ( 47.4%) + beta -beta -beta ... -0.000895028 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034561288 + +Final correlation energy ... -0.727728707 +E(CCSD) ... -205.408591698 +E(CCSD(T)) ... -205.443152986 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209596584 sqrt= 1.099816614 +W(HF) = 0.826721911 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.242779 -0.000000 + 1 N : 0.161623 0.000000 + 2 O : -0.154737 0.000000 + 3 H : 0.235893 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.809428 s : 3.809428 + pz : 1.655548 p : 4.361442 + px : 1.311074 + py : 1.394821 + dz2 : 0.012458 d : 0.063332 + dxz : 0.012770 + dyz : 0.007559 + dx2y2 : 0.018368 + dxy : 0.012178 + f0 : 0.001110 f : 0.008577 + f+1 : 0.001649 + f-1 : 0.000833 + f+2 : 0.000999 + f-2 : 0.001152 + f+3 : 0.001315 + f-3 : 0.001518 + 1 N s : 3.896753 s : 3.896753 + pz : 0.832165 p : 2.739231 + px : 0.809335 + py : 1.097732 + dz2 : 0.035877 d : 0.170883 + dxz : 0.037872 + dyz : 0.025901 + dx2y2 : 0.045077 + dxy : 0.026157 + f0 : 0.001816 f : 0.031510 + f+1 : 0.004718 + f-1 : 0.004320 + f+2 : 0.003169 + f-2 : 0.004994 + f+3 : 0.005506 + f-3 : 0.006988 + 2 O s : 3.855524 s : 3.855524 + pz : 1.226539 p : 4.205695 + px : 1.631676 + py : 1.347481 + dz2 : 0.021139 d : 0.083479 + dxz : 0.011573 + dyz : 0.015337 + dx2y2 : 0.015459 + dxy : 0.019971 + f0 : 0.000941 f : 0.010038 + f+1 : 0.000741 + f-1 : 0.002031 + f+2 : 0.001694 + f-2 : 0.001504 + f+3 : 0.001569 + f-3 : 0.001558 + 3 H s : 0.654324 s : 0.654324 + pz : 0.044930 p : 0.090779 + px : 0.029864 + py : 0.015985 + dz2 : 0.002027 d : 0.019004 + dxz : 0.000428 + dyz : 0.006298 + dx2y2 : 0.000756 + dxy : 0.009495 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.604988 -0.000000 + 1 N : -0.314717 0.000000 + 2 O : 0.282039 0.000000 + 3 H : -0.572310 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.123568 s : 3.123568 + pz : 1.346099 p : 3.863121 + px : 1.219594 + py : 1.297428 + dz2 : 0.044118 d : 0.315044 + dxz : 0.078366 + dyz : 0.036643 + dx2y2 : 0.085734 + dxy : 0.070182 + f0 : 0.009094 f : 0.093279 + f+1 : 0.017305 + f-1 : 0.001661 + f+2 : 0.015849 + f-2 : 0.013048 + f+3 : 0.012028 + f-3 : 0.024295 + 1 N s : 3.020262 s : 3.020262 + pz : 0.846079 p : 2.880750 + px : 0.866077 + py : 1.168595 + dz2 : 0.160435 d : 0.963909 + dxz : 0.219152 + dyz : 0.169561 + dx2y2 : 0.242412 + dxy : 0.172349 + f0 : 0.032340 f : 0.449796 + f+1 : 0.048904 + f-1 : 0.054266 + f+2 : 0.077805 + f-2 : 0.079996 + f+3 : 0.072546 + f-3 : 0.083939 + 2 O s : 3.308204 s : 3.308204 + pz : 1.174183 p : 3.929416 + px : 1.367406 + py : 1.387827 + dz2 : 0.049728 d : 0.355540 + dxz : 0.054925 + dyz : 0.096283 + dx2y2 : 0.100963 + dxy : 0.053641 + f0 : 0.010903 f : 0.124801 + f+1 : 0.006383 + f-1 : 0.022896 + f+2 : 0.028417 + f-2 : 0.021183 + f+3 : 0.012070 + f-3 : 0.022948 + 3 H s : 0.620322 s : 0.620322 + pz : 0.165088 p : 0.565118 + px : 0.136793 + py : 0.263237 + dz2 : 0.049963 d : 0.386870 + dxz : 0.029942 + dyz : 0.107443 + dx2y2 : 0.095460 + dxy : 0.104062 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2428 8.0000 -0.2428 2.1896 1.7365 0.4531 + 1 N 6.8384 7.0000 0.1616 2.8188 2.3401 0.4786 + 2 O 8.1547 8.0000 -0.1547 2.1238 1.6253 0.4985 + 3 H 0.7641 1.0000 0.2359 1.0289 0.9547 0.0742 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7622 B( 0-O , 2-O ) : 0.1005 B( 0-O , 3-H ) : 0.8738 +B( 1-N , 2-O ) : 1.5110 + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 54.801 sec + +Fock Matrix Formation ... 0.203 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 1.810 sec ( 3.3%) +State Vector Update ... 0.085 sec ( 0.2%) +Sigma-vector construction ... 37.836 sec ( 69.0%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.024 sec ( 0.1% of sigma) + (0-ext) ... 0.070 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (2-ext) ... 0.934 sec ( 2.5% of sigma) + (4-ext) ... 21.027 sec ( 55.6% of sigma) + ... 1.359 sec ( 3.6% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.109 sec ( 0.3% of sigma) + Fock-dressing ... 2.102 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.078 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.483 sec ( 25.1% of sigma) + Pair energies ... 0.006 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.866 sec ( 12.5% of ALL) + I/O of integral and amplitudes ... 0.763 sec ( 11.1% of (T)) + External N**7 contributions ... 3.889 sec ( 56.6% of (T)) + Internal N**7 contributions ... 0.308 sec ( 4.5% of (T)) + N**6 triples energy contributions ... 1.594 sec ( 23.2% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.443152986278 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.018.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.018.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.379420, -0.296383 -0.413140) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.79397 -0.20409 -0.54921 +Nuclear contribution : -0.84887 0.68113 0.87690 + ----------------------------------------- +Total Dipole Moment : -0.05490 0.47704 0.32769 + ----------------------------------------- +Magnitude (a.u.) : 0.58134 +Magnitude (Debye) : 1.47765 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.757471 0.422676 0.371484 +Rotational constants in MHz : 82666.892510 12671.512373 11136.807348 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.111413 -0.425090 0.380584 +x,y,z [Debye]: 0.283190 -1.080493 0.967367 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.379420, -0.296383 -0.413140) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.81115 -0.13096 -0.64156 +Nuclear contribution : -0.84887 0.68113 0.87690 + ----------------------------------------- +Total Dipole Moment : -0.03772 0.55017 0.23534 + ----------------------------------------- +Magnitude (a.u.) : 0.59958 +Magnitude (Debye) : 1.52400 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.757471 0.422676 0.371484 +Rotational constants in MHz : 82666.892510 12671.512373 11136.807348 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.023229 -0.493680 0.339459 +x,y,z [Debye]: 0.059044 -1.254836 0.862837 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 19 * + * * + * Dihedral ( 2, 1, 0, 3) : -32.72727273 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0340123301 RMS(Int)= 0.0008899342 + Iter 1: RMS(Cart)= 0.0002119664 RMS(Int)= 0.0000133735 + Iter 2: RMS(Cart)= 0.0000031853 RMS(Int)= 0.0000002019 + Iter 3: RMS(Cart)= 0.0000000481 RMS(Int)= 0.0000000030 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4387 0.000000 + 2. B(O 2,N 1) 1.1800 0.000000 + 3. B(H 3,O 0) 0.9755 0.000000 + 4. A(N 1,O 0,H 3) 104.8525 0.000000 + 5. A(O 0,N 1,O 2) 112.7878 0.000000 + 6. D(O 2,N 1,O 0,H 3) -32.7273 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.707102 -0.368043 0.443293 + N 0.531541 -0.578027 -0.257701 + O 0.875679 0.369283 -0.871368 + H -0.700117 0.576787 0.685776 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.336229 -0.695500 0.837703 + 1 N 7.0000 0 14.007 1.004467 -1.092313 -0.486984 + 2 O 8.0000 0 15.999 1.654794 0.697844 -1.646647 + 3 H 1.0000 0 1.008 -1.323030 1.089969 1.295928 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.437471023863 0.00000000 0.00000000 + O 2 1 0 1.178591001336 112.94595042 0.00000000 + H 1 2 3 0.973385154345 105.03535601 319.09090911 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.716426560548 0.00000000 0.00000000 + O 2 1 0 2.227214216428 112.94595042 0.00000000 + H 1 2 3 1.839431364536 105.03535601 319.09090911 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2243 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2716 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.364551369099 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.3645513691 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.540e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7128623353 0.000000000000 0.00193246 0.00005209 0.0156239 0.7000 + 1 -204.7136304140 -0.000768078737 0.00173516 0.00004833 0.0130160 0.7000 + ***Turning on DIIS*** + 2 -204.7142980217 -0.000667607619 0.00462837 0.00013360 0.0106528 0.0000 + 3 -204.7178050686 -0.003507046951 0.00209691 0.00006121 0.0045715 0.0000 + 4 -204.7158337022 0.001971366445 0.00098579 0.00003162 0.0018644 0.0000 + 5 -204.7176641210 -0.001830418805 0.00063097 0.00002620 0.0010233 0.0000 + 6 -204.7168914137 0.000772707228 0.00072019 0.00003163 0.0006813 0.0000 + 7 -204.7165465230 0.000344890736 0.00037386 0.00001688 0.0002989 0.0000 + 8 -204.7172607787 -0.000714255738 0.00018464 0.00000921 0.0001862 0.0000 + 9 -204.7168101256 0.000450653166 0.00014694 0.00000479 0.0001176 0.0000 + 10 -204.7169039268 -0.000093801229 0.00005009 0.00000178 0.0000658 0.0000 + 11 -204.7170006229 -0.000096696114 0.00002844 0.00000079 0.0000294 0.0000 + 12 -204.7169472165 0.000053406403 0.00000805 0.00000023 0.0000082 0.0000 + 13 -204.7169620309 -0.000014814419 0.00000222 0.00000008 0.0000030 0.0000 + 14 -204.7169597163 0.000002314652 0.00000101 0.00000004 0.0000015 0.0000 + 15 -204.7169598829 -0.000000166603 0.00000065 0.00000003 0.0000016 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 16 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71696071 Eh -5570.63171 eV + +Components: +Nuclear Repulsion : 69.36455137 Eh 1887.50540 eV +Electronic Energy : -274.08151208 Eh -7458.13711 eV +One Electron Energy: -418.35210921 Eh -11383.93964 eV +Two Electron Energy: 144.27059713 Eh 3925.80253 eV + +Virial components: +Potential Energy : -408.94035434 Eh -11127.83277 eV +Kinetic Energy : 204.22339363 Eh 5557.20106 eV +Virial Ratio : 2.00241680 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -8.2412e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.2977e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.2166e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.2316e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.676005 -562.6227 + 1 1.0000 -20.638925 -561.6137 + 2 1.0000 -15.805152 -430.0801 + 3 1.0000 -1.609155 -43.7873 + 4 1.0000 -1.394898 -37.9571 + 5 1.0000 -0.963054 -26.2060 + 6 1.0000 -0.772861 -21.0306 + 7 1.0000 -0.739475 -20.1221 + 8 1.0000 -0.691553 -18.8181 + 9 1.0000 -0.609989 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195.5111 + 145 0.0000 7.243347 197.1015 + 146 0.0000 7.256795 197.4674 + 147 0.0000 7.311782 198.9637 + 148 0.0000 7.392856 201.1698 + 149 0.0000 7.455616 202.8776 + 150 0.0000 7.495242 203.9559 + 151 0.0000 7.516868 204.5444 + 152 0.0000 7.561502 205.7589 + 153 0.0000 7.653444 208.2608 + 154 0.0000 7.812605 212.5918 + 155 0.0000 7.870370 214.1637 + 156 0.0000 8.164242 222.1603 + 157 0.0000 8.332220 226.7312 + 158 0.0000 14.049759 382.3134 + 159 0.0000 15.035161 409.1275 + 160 0.0000 15.718288 427.7164 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.676005 -562.6227 + 1 1.0000 -20.638925 -561.6137 + 2 1.0000 -15.805152 -430.0801 + 3 1.0000 -1.609155 -43.7873 + 4 1.0000 -1.394898 -37.9571 + 5 1.0000 -0.963054 -26.2060 + 6 1.0000 -0.772861 -21.0306 + 7 1.0000 -0.739475 -20.1221 + 8 1.0000 -0.691553 -18.8181 + 9 1.0000 -0.609989 -16.5987 + 10 1.0000 -0.533425 -14.5152 + 11 1.0000 -0.470965 -12.8156 + 12 0.0000 0.031512 0.8575 + 13 0.0000 0.071599 1.9483 + 14 0.0000 0.094232 2.5642 + 15 0.0000 0.111485 3.0337 + 16 0.0000 0.119268 3.2455 + 17 0.0000 0.149040 4.0556 + 18 0.0000 0.157821 4.2945 + 19 0.0000 0.169538 4.6134 + 20 0.0000 0.182635 4.9698 + 21 0.0000 0.193946 5.2775 + 22 0.0000 0.203441 5.5359 + 23 0.0000 0.233582 6.3561 + 24 0.0000 0.258567 7.0360 + 25 0.0000 0.294317 8.0088 + 26 0.0000 0.308519 8.3952 + 27 0.0000 0.339853 9.2479 + 28 0.0000 0.347244 9.4490 + 29 0.0000 0.387439 10.5427 + 30 0.0000 0.423291 11.5183 + 31 0.0000 0.514047 13.9879 + 32 0.0000 0.525500 14.2996 + 33 0.0000 0.533898 14.5281 + 34 0.0000 0.562650 15.3105 + 35 0.0000 0.614650 16.7255 + 36 0.0000 0.633390 17.2354 + 37 0.0000 0.653706 17.7882 + 38 0.0000 0.689859 18.7720 + 39 0.0000 0.702459 19.1149 + 40 0.0000 0.734958 19.9992 + 41 0.0000 0.748084 20.3564 + 42 0.0000 0.764099 20.7922 + 43 0.0000 0.786170 21.3928 + 44 0.0000 0.806959 21.9585 + 45 0.0000 0.838302 22.8114 + 46 0.0000 0.847319 23.0567 + 47 0.0000 0.877576 23.8801 + 48 0.0000 0.919901 25.0318 + 49 0.0000 0.941512 25.6198 + 50 0.0000 0.964945 26.2575 + 51 0.0000 0.988425 26.8964 + 52 0.0000 1.020048 27.7569 + 53 0.0000 1.040032 28.3007 + 54 0.0000 1.067639 29.0519 + 55 0.0000 1.086167 29.5561 + 56 0.0000 1.172025 31.8924 + 57 0.0000 1.194034 32.4913 + 58 0.0000 1.236418 33.6447 + 59 0.0000 1.278260 34.7832 + 60 0.0000 1.365204 37.1491 + 61 0.0000 1.409502 38.3545 + 62 0.0000 1.438899 39.1544 + 63 0.0000 1.513809 41.1928 + 64 0.0000 1.535765 41.7903 + 65 0.0000 1.547320 42.1047 + 66 0.0000 1.602490 43.6060 + 67 0.0000 1.628254 44.3071 + 68 0.0000 1.654780 45.0289 + 69 0.0000 1.734697 47.2035 + 70 0.0000 1.776466 48.3401 + 71 0.0000 1.810225 49.2587 + 72 0.0000 1.900713 51.7210 + 73 0.0000 1.950030 53.0630 + 74 0.0000 1.979052 53.8527 + 75 0.0000 2.017524 54.8996 + 76 0.0000 2.029798 55.2336 + 77 0.0000 2.082159 56.6584 + 78 0.0000 2.158474 58.7351 + 79 0.0000 2.176074 59.2140 + 80 0.0000 2.256572 61.4044 + 81 0.0000 2.306007 62.7496 + 82 0.0000 2.356716 64.1295 + 83 0.0000 2.394692 65.1629 + 84 0.0000 2.419855 65.8476 + 85 0.0000 2.444927 66.5298 + 86 0.0000 2.466163 67.1077 + 87 0.0000 2.510535 68.3151 + 88 0.0000 2.538704 69.0816 + 89 0.0000 2.555570 69.5406 + 90 0.0000 2.577738 70.1438 + 91 0.0000 2.618728 71.2592 + 92 0.0000 2.655523 72.2604 + 93 0.0000 2.683845 73.0311 + 94 0.0000 2.745618 74.7121 + 95 0.0000 2.800547 76.2067 + 96 0.0000 2.845488 77.4297 + 97 0.0000 2.944393 80.1210 + 98 0.0000 2.970310 80.8262 + 99 0.0000 3.021633 82.2228 + 100 0.0000 3.137162 85.3665 + 101 0.0000 3.171055 86.2888 + 102 0.0000 3.223665 87.7204 + 103 0.0000 3.506834 95.4258 + 104 0.0000 3.700024 100.6828 + 105 0.0000 3.875287 105.4519 + 106 0.0000 4.013511 109.2132 + 107 0.0000 4.149009 112.9003 + 108 0.0000 4.179432 113.7281 + 109 0.0000 4.299712 117.0011 + 110 0.0000 4.370853 118.9370 + 111 0.0000 4.406555 119.9084 + 112 0.0000 4.524573 123.1199 + 113 0.0000 4.565860 124.2434 + 114 0.0000 4.677030 127.2685 + 115 0.0000 4.807420 130.8166 + 116 0.0000 4.842812 131.7796 + 117 0.0000 4.869672 132.5105 + 118 0.0000 4.960542 134.9832 + 119 0.0000 4.998151 136.0066 + 120 0.0000 5.073102 138.0461 + 121 0.0000 5.104605 138.9034 + 122 0.0000 5.186338 141.1274 + 123 0.0000 5.230136 142.3192 + 124 0.0000 5.240767 142.6085 + 125 0.0000 5.283326 143.7666 + 126 0.0000 5.377731 146.3355 + 127 0.0000 5.464022 148.6836 + 128 0.0000 5.538145 150.7006 + 129 0.0000 5.691255 154.8669 + 130 0.0000 5.775972 157.1722 + 131 0.0000 5.941034 161.6638 + 132 0.0000 6.163473 167.7166 + 133 0.0000 6.398305 174.1067 + 134 0.0000 6.498554 176.8347 + 135 0.0000 6.532385 177.7552 + 136 0.0000 6.683557 181.8688 + 137 0.0000 6.723494 182.9556 + 138 0.0000 6.774624 184.3469 + 139 0.0000 6.798430 184.9947 + 140 0.0000 6.904349 187.8769 + 141 0.0000 7.097010 193.1195 + 142 0.0000 7.128918 193.9877 + 143 0.0000 7.166832 195.0194 + 144 0.0000 7.184901 195.5111 + 145 0.0000 7.243347 197.1015 + 146 0.0000 7.256795 197.4674 + 147 0.0000 7.311782 198.9637 + 148 0.0000 7.392856 201.1698 + 149 0.0000 7.455616 202.8776 + 150 0.0000 7.495242 203.9559 + 151 0.0000 7.516868 204.5444 + 152 0.0000 7.561502 205.7589 + 153 0.0000 7.653444 208.2608 + 154 0.0000 7.812605 212.5918 + 155 0.0000 7.870370 214.1637 + 156 0.0000 8.164242 222.1603 + 157 0.0000 8.332220 226.7312 + 158 0.0000 14.049759 382.3134 + 159 0.0000 15.035161 409.1275 + 160 0.0000 15.718288 427.7164 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.317517 0.000000 + 1 N : 0.350588 0.000000 + 2 O : -0.282874 0.000000 + 3 H : 0.249803 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.821202 s : 3.821202 + pz : 1.697752 p : 4.457285 + px : 1.356392 + py : 1.403142 + dz2 : 0.006621 d : 0.034008 + dxz : 0.007543 + dyz : 0.000396 + dx2y2 : 0.015365 + dxy : 0.004083 + f0 : 0.000526 f : 0.005022 + f+1 : 0.001145 + f-1 : 0.000235 + f+2 : 0.000642 + f-2 : 0.000742 + f+3 : 0.000766 + f-3 : 0.000965 + 1 N s : 3.850049 s : 3.850049 + pz : 0.735719 p : 2.624946 + px : 0.747288 + py : 1.141939 + dz2 : 0.030472 d : 0.141909 + dxz : 0.028939 + dyz : 0.023847 + dx2y2 : 0.037674 + dxy : 0.020977 + f0 : 0.001330 f : 0.032508 + f+1 : 0.004469 + f-1 : 0.005238 + f+2 : 0.003227 + f-2 : 0.005117 + f+3 : 0.005996 + f-3 : 0.007130 + 2 O s : 3.865194 s : 3.865194 + pz : 1.293183 p : 4.348636 + px : 1.676763 + py : 1.378690 + dz2 : 0.016628 d : 0.061502 + dxz : 0.004282 + dyz : 0.014247 + dx2y2 : 0.009341 + dxy : 0.017006 + f0 : 0.000380 f : 0.007542 + f+1 : 0.000142 + f-1 : 0.002087 + f+2 : 0.001360 + f-2 : 0.001053 + f+3 : 0.001263 + f-3 : 0.001257 + 3 H s : 0.643104 s : 0.643104 + pz : 0.039031 p : 0.086032 + px : 0.026769 + py : 0.020232 + dz2 : 0.001310 d : 0.021061 + dxz : -0.000416 + dyz : 0.008372 + dx2y2 : 0.001056 + dxy : 0.010739 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.591343 0.000000 + 1 N : -0.263874 0.000000 + 2 O : 0.243904 0.000000 + 3 H : -0.571373 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.118321 s : 3.118321 + pz : 1.376638 p : 3.920753 + px : 1.236681 + py : 1.307435 + dz2 : 0.038268 d : 0.283528 + dxz : 0.074387 + dyz : 0.030239 + dx2y2 : 0.076517 + dxy : 0.064117 + f0 : 0.008130 f : 0.086054 + f+1 : 0.015423 + f-1 : 0.001413 + f+2 : 0.014254 + f-2 : 0.014085 + f+3 : 0.009627 + f-3 : 0.023124 + 1 N s : 3.016268 s : 3.016268 + pz : 0.778893 p : 2.830804 + px : 0.832719 + py : 1.219192 + dz2 : 0.163498 d : 0.956118 + dxz : 0.208381 + dyz : 0.161425 + dx2y2 : 0.243764 + dxy : 0.179050 + f0 : 0.030098 f : 0.460684 + f+1 : 0.052200 + f-1 : 0.056320 + f+2 : 0.076024 + f-2 : 0.082724 + f+3 : 0.073697 + f-3 : 0.089621 + 2 O s : 3.304051 s : 3.304051 + pz : 1.198967 p : 4.012797 + px : 1.393791 + py : 1.420039 + dz2 : 0.039513 d : 0.323424 + dxz : 0.047637 + dyz : 0.083519 + dx2y2 : 0.103319 + dxy : 0.049435 + f0 : 0.009324 f : 0.115824 + f+1 : 0.004770 + f-1 : 0.018524 + f+2 : 0.025967 + f-2 : 0.020060 + f+3 : 0.011592 + f-3 : 0.025586 + 3 H s : 0.616260 s : 0.616260 + pz : 0.155045 p : 0.553050 + px : 0.136515 + py : 0.261490 + dz2 : 0.046589 d : 0.402062 + dxz : 0.028660 + dyz : 0.114946 + dx2y2 : 0.099866 + dxy : 0.112002 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3175 8.0000 -0.3175 1.8194 1.8194 -0.0000 + 1 N 6.6494 7.0000 0.3506 2.5350 2.5350 0.0000 + 2 O 8.2829 8.0000 -0.2829 1.7178 1.7178 -0.0000 + 3 H 0.7502 1.0000 0.2498 1.0121 1.0121 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8199 B( 0-O , 3-H ) : 0.9389 B( 1-N , 2-O ) : 1.6495 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.452 sec +Sum of individual times .... 2.228 sec ( 90.9%) + +Fock matrix formation .... 1.818 sec ( 74.1%) +Diagonalization .... 0.188 sec ( 7.7%) +Density matrix formation .... 0.014 sec ( 0.6%) +Population analysis .... 0.038 sec ( 1.5%) +Initial guess .... 0.009 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.2%) +DIIS solution .... 0.161 sec ( 6.6%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.231 sec +Reference energy ... -204.716960677 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.362 sec +AO-integral generation ... 0.144 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.364 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.025 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.024 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.031 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.345 sec +AO-integral generation ... 0.239 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.049 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.150 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.255 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090502288 +EMP2(bb)= -0.090502288 +EMP2(ab)= -0.516212066 + +Initial guess performed in 0.132 sec +E(0) ... -204.716960677 +E(MP2) ... -0.697216643 +Initial E(tot) ... -205.414177320 + ... 0.188115300 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.414177320 -0.697216643 -0.000000000 0.026272237 2.71 0.000002560 + *** Turning on DIIS *** + 1 -205.385112528 -0.668151851 0.029064792 0.010502456 2.71 0.058167663 + 2 -205.404693189 -0.687732511 -0.019580660 0.005836916 2.81 0.061291135 + 3 -205.408449777 -0.691489100 -0.003756589 0.002001110 2.88 0.075815072 + 4 -205.410049427 -0.693088750 -0.001599650 0.001588920 3.07 0.082856164 + 5 -205.410621539 -0.693660862 -0.000572112 0.000921517 2.87 0.088686465 + 6 -205.410734877 -0.693774199 -0.000113337 0.000566715 2.90 0.091574705 + 7 -205.410783001 -0.693822323 -0.000048124 0.000248062 3.09 0.092894158 + 8 -205.410795143 -0.693834466 -0.000012143 0.000123696 2.93 0.093406525 + 9 -205.410790737 -0.693830060 0.000004406 0.000036337 2.85 0.093557485 + 10 -205.410796202 -0.693835525 -0.000005465 0.000023145 2.83 0.093616683 + 11 -205.410793282 -0.693832605 0.000002920 0.000016763 2.89 0.093605494 + 12 -205.410794435 -0.693833758 -0.000001152 0.000011656 2.85 0.093617417 + 13 -205.410794285 -0.693833608 0.000000150 0.000007499 2.82 0.093614198 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.716960677 +E(CORR) ... -0.693833608 +E(TOT) ... -205.410794285 +Singles norm **1/2 ... 0.093614198 ( 0.046807099, 0.046807099) +T1 diagnostic ... 0.022065078 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.061492 + 8b-> 13b -1b-> -1b 0.043727 + 8a-> 13a -1a-> -1a 0.043727 + 10a-> 13a 10b-> 13b 0.040327 + 10a-> 13a -1a-> -1a 0.030958 + 10b-> 13b -1b-> -1b 0.030958 + 8a-> 13a 10b-> 13b 0.029948 + 10a-> 13a 8b-> 13b 0.029948 + 11a-> 13a 11b-> 13b 0.029526 + 9a-> 13a 9b-> 13b 0.028765 + 9a-> 13a 8b-> 13b 0.027542 + 8a-> 13a 9b-> 13b 0.027542 + 5a-> 13a 5b-> 13b 0.026959 + 8a-> 22a 8b-> 13b 0.023092 + 8a-> 13a 8b-> 22b 0.023092 + 9a-> 13a 10b-> 13b 0.022531 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034833292 + alpha-alpha-alpha ... -0.000904370 ( 2.6%) + alpha-alpha-beta ... -0.016512276 ( 47.4%) + alpha-beta -beta ... -0.016512276 ( 47.4%) + beta -beta -beta ... -0.000904370 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034833292 + +Final correlation energy ... -0.728666900 +E(CCSD) ... -205.410794285 +E(CCSD(T)) ... -205.445627577 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210530380 sqrt= 1.100241055 +W(HF) = 0.826084183 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.235152 -0.000000 + 1 N : 0.160500 0.000000 + 2 O : -0.160716 -0.000000 + 3 H : 0.235368 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.807047 s : 3.807047 + pz : 1.642635 p : 4.355312 + px : 1.333976 + py : 1.378701 + dz2 : 0.013432 d : 0.064097 + dxz : 0.012814 + dyz : 0.007413 + dx2y2 : 0.018875 + dxy : 0.011562 + f0 : 0.001038 f : 0.008696 + f+1 : 0.001723 + f-1 : 0.000879 + f+2 : 0.001010 + f-2 : 0.001276 + f+3 : 0.001262 + f-3 : 0.001509 + 1 N s : 3.901424 s : 3.901424 + pz : 0.825128 p : 2.736393 + px : 0.803404 + py : 1.107862 + dz2 : 0.035591 d : 0.170134 + dxz : 0.036822 + dyz : 0.026931 + dx2y2 : 0.044837 + dxy : 0.025953 + f0 : 0.001661 f : 0.031548 + f+1 : 0.004507 + f-1 : 0.004606 + f+2 : 0.002984 + f-2 : 0.005106 + f+3 : 0.005545 + f-3 : 0.007139 + 2 O s : 3.852593 s : 3.852593 + pz : 1.255686 p : 4.214078 + px : 1.609371 + py : 1.349021 + dz2 : 0.020088 d : 0.083941 + dxz : 0.010994 + dyz : 0.016287 + dx2y2 : 0.015943 + dxy : 0.020629 + f0 : 0.000853 f : 0.010103 + f+1 : 0.000708 + f-1 : 0.002086 + f+2 : 0.001678 + f-2 : 0.001479 + f+3 : 0.001617 + f-3 : 0.001681 + 3 H s : 0.656915 s : 0.656915 + pz : 0.043889 p : 0.088710 + px : 0.030371 + py : 0.014451 + dz2 : 0.001232 d : 0.019007 + dxz : 0.000066 + dyz : 0.007428 + dx2y2 : 0.000406 + dxy : 0.009875 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.605623 0.000000 + 1 N : -0.312830 -0.000000 + 2 O : 0.280790 0.000000 + 3 H : -0.573583 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.126109 s : 3.126109 + pz : 1.340350 p : 3.859709 + px : 1.228002 + py : 1.291358 + dz2 : 0.044779 d : 0.315188 + dxz : 0.081279 + dyz : 0.036821 + dx2y2 : 0.083344 + dxy : 0.068965 + f0 : 0.009014 f : 0.093371 + f+1 : 0.016983 + f-1 : 0.002300 + f+2 : 0.015718 + f-2 : 0.014716 + f+3 : 0.011084 + f-3 : 0.023556 + 1 N s : 3.021716 s : 3.021716 + pz : 0.832753 p : 2.880230 + px : 0.858469 + py : 1.189008 + dz2 : 0.161942 d : 0.961323 + dxz : 0.213686 + dyz : 0.165763 + dx2y2 : 0.246013 + dxy : 0.173918 + f0 : 0.030976 f : 0.449561 + f+1 : 0.047065 + f-1 : 0.055208 + f+2 : 0.075522 + f-2 : 0.080207 + f+3 : 0.073849 + f-3 : 0.086734 + 2 O s : 3.306059 s : 3.306059 + pz : 1.178419 p : 3.932406 + px : 1.353214 + py : 1.400772 + dz2 : 0.050319 d : 0.356093 + dxz : 0.052325 + dyz : 0.089759 + dx2y2 : 0.107197 + dxy : 0.056493 + f0 : 0.010235 f : 0.124652 + f+1 : 0.005766 + f-1 : 0.022754 + f+2 : 0.026459 + f-2 : 0.020630 + f+3 : 0.013618 + f-3 : 0.025190 + 3 H s : 0.620103 s : 0.620103 + pz : 0.158887 p : 0.562165 + px : 0.137188 + py : 0.266090 + dz2 : 0.045901 d : 0.391316 + dxz : 0.028321 + dyz : 0.109860 + dx2y2 : 0.098977 + dxy : 0.108258 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2352 8.0000 -0.2352 2.1964 1.7407 0.4557 + 1 N 6.8395 7.0000 0.1605 2.8189 2.3408 0.4780 + 2 O 8.1607 8.0000 -0.1607 2.1176 1.6189 0.4988 + 3 H 0.7646 1.0000 0.2354 1.0294 0.9549 0.0745 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7701 B( 0-O , 2-O ) : 0.1024 B( 0-O , 3-H ) : 0.8681 +B( 1-N , 2-O ) : 1.5002 + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 55.144 sec + +Fock Matrix Formation ... 0.231 sec ( 0.4%) +Initial Guess ... 0.132 sec ( 0.2%) +DIIS Solver ... 1.879 sec ( 3.4%) +State Vector Update ... 0.086 sec ( 0.2%) +Sigma-vector construction ... 38.229 sec ( 69.3%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.024 sec ( 0.1% of sigma) + (0-ext) ... 0.069 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (2-ext) ... 0.939 sec ( 2.5% of sigma) + (4-ext) ... 21.320 sec ( 55.8% of sigma) + ... 1.438 sec ( 3.8% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.108 sec ( 0.3% of sigma) + Fock-dressing ... 2.098 sec ( 5.5% of sigma) + (ik|jl)-dressing ... 0.074 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.533 sec ( 24.9% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.694 sec ( 12.1% of ALL) + I/O of integral and amplitudes ... 0.629 sec ( 9.4% of (T)) + External N**7 contributions ... 3.883 sec ( 58.0% of (T)) + Internal N**7 contributions ... 0.309 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.589 sec ( 23.7% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.445627577391 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.009532978 0.002086390 -0.010018152 + 2 N : 0.010092274 0.000332711 0.008297418 + 3 O : -0.004453604 -0.001345375 -0.006704372 + 4 H : 0.003894308 -0.001073726 0.008425106 + +Norm of the cartesian gradient ... 0.022810087 +RMS gradient ... 0.006584705 +MAX gradient ... 0.010092274 + +------- +TIMINGS +------- + +Total numerical gradient time ... 356.323 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 328.37 cm**-1 + 7: 630.23 cm**-1 + 8: 816.10 cm**-1 + 9: 1290.53 cm**-1 + 10: 1667.52 cm**-1 + 11: 3647.87 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 0.127401 -0.203440 -0.182740 0.055088 -0.033455 -0.000935 + 1 -0.004096 -0.107300 0.113231 0.072711 0.057344 -0.060219 + 2 0.012894 0.262783 0.089920 -0.025088 0.015215 -0.015420 + 3 -0.111522 0.009102 0.346108 0.058702 -0.070943 0.001405 + 4 -0.036922 0.115672 -0.204084 -0.033033 -0.551905 -0.000621 + 5 -0.022971 -0.146889 -0.174074 -0.060024 0.259413 -0.000798 + 6 -0.009120 0.247777 -0.142641 -0.050154 0.127731 -0.000501 + 7 0.021613 0.003884 0.046444 -0.041162 0.426675 -0.000117 + 8 0.063643 -0.116630 0.107165 0.051276 -0.261331 0.000380 + 9 -0.327651 -0.830187 0.354995 -0.894012 -0.510529 0.003261 + 10 0.235031 0.034063 0.301552 -0.041720 -0.013200 0.966291 + 11 -0.895579 -0.278608 -0.709235 0.418417 0.301594 0.249804 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 328.37 0.022274 112.56 0.021168 (-0.141143 0.000369 -0.035299) + 7: 630.23 0.008425 42.57 0.004172 ( 0.008097 0.025706 -0.058695) + 8: 816.10 0.050234 253.86 0.019209 ( 0.101726 0.001766 -0.094114) + 9: 1290.53 0.001591 8.04 0.000385 (-0.009449 0.017134 0.001340) + 10: 1667.52 0.031295 158.15 0.005857 (-0.055540 -0.019367 0.048956) + 11: 3647.87 0.008269 41.79 0.000707 (-0.010023 0.019157 0.015489) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 328.37 E(vib) ... 0.24 +freq. 630.23 E(vib) ... 0.09 +freq. 816.10 E(vib) ... 0.05 +freq. 1290.53 E(vib) ... 0.01 +freq. 1667.52 E(vib) ... 0.00 +freq. 3647.87 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.44562758 Eh +Zero point energy ... 0.01909248 Eh 11.98 kcal/mol +Thermal vibrational correction ... 0.00061792 Eh 0.39 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42308463 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00345046 Eh 2.17 kcal/mol +Non-thermal (ZPE) correction 0.01909248 Eh 11.98 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02254294 Eh 14.15 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42308463 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.42214042 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.734081 0.424590 0.370879 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00090341 Eh 0.57 kcal/mol +Rotational entropy ... 0.00990865 Eh 6.22 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02861438 Eh 17.96 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00990865 Eh 6.22 kcal/mol| +| sn= 2 | S(rot)= 0.00925419 Eh 5.81 kcal/mol| +| sn= 3 | S(rot)= 0.00887136 Eh 5.57 kcal/mol| +| sn= 4 | S(rot)= 0.00859974 Eh 5.40 kcal/mol| +| sn= 5 | S(rot)= 0.00838905 Eh 5.26 kcal/mol| +| sn= 6 | S(rot)= 0.00821690 Eh 5.16 kcal/mol| +| sn= 7 | S(rot)= 0.00807136 Eh 5.06 kcal/mol| +| sn= 8 | S(rot)= 0.00794528 Eh 4.99 kcal/mol| +| sn= 9 | S(rot)= 0.00783407 Eh 4.92 kcal/mol| +| sn=10 | S(rot)= 0.00773459 Eh 4.85 kcal/mol| +| sn=11 | S(rot)= 0.00764460 Eh 4.80 kcal/mol| +| sn=12 | S(rot)= 0.00756245 Eh 4.75 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.42214042 Eh +Total entropy correction ... -0.02861438 Eh -17.96 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.45075480 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00512723 Eh -3.22 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.445627576 Eh +Current gradient norm .... 0.022810088 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.011533968 0.121404834 0.194233674 0.474443773 0.520682073 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999516945 +Lowest eigenvalues of augmented Hessian: + -0.000134657 0.116152945 0.193228956 0.474378993 0.520529828 +Length of the computed step .... 0.031093562 +The final length of the internal step .... 0.031093562 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0126938937 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0066570427 RMS(Int)= 0.0126943912 + Iter 1: RMS(Cart)= 0.0000079050 RMS(Int)= 0.0000155484 + Iter 2: RMS(Cart)= 0.0000000598 RMS(Int)= 0.0000000571 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000008 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0020157180 0.0001000000 NO + MAX gradient 0.0042263135 0.0003000000 NO + RMS step 0.0126938937 0.0020000000 NO + MAX step 0.0301558604 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0160 Max(Angles) 0.33 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4387 0.004226 -0.0160 1.4227 + 2. B(O 2,N 1) 1.1800 0.001108 0.0015 1.1815 + 3. B(H 3,O 0) 0.9755 0.001082 -0.0008 0.9747 + 4. A(N 1,O 0,H 3) 104.85 0.000607 0.22 105.07 + 5. A(O 0,N 1,O 2) 112.79 -0.001937 0.33 113.11 + 6. D(O 2,N 1,O 0,H 3) -32.73 -0.016525 0.00 -32.73 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.700800 -0.368563 0.439684 + N 0.524299 -0.575872 -0.253294 + O 0.874069 0.369336 -0.869872 + H -0.697568 0.575099 0.683481 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.324319 -0.696484 0.830883 + 1 N 7.0000 0 14.007 0.990782 -1.088240 -0.478655 + 2 O 8.0000 0 15.999 1.651751 0.697944 -1.643820 + 3 H 1.0000 0 1.008 -1.318212 1.086779 1.291592 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.422695394291 0.00000000 0.00000000 + O 2 1 0 1.181492876920 113.11285452 0.00000000 + H 1 2 3 0.974651278760 105.07397276 327.27272752 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.688504667201 0.00000000 0.00000000 + O 2 1 0 2.232697966558 113.11285452 0.00000000 + H 1 2 3 1.841823992933 105.07397276 327.27272752 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2243 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2717 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.645605826109 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.514e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7180860312 0.000000000000 0.00048456 0.00001261 0.0026889 0.7000 + 1 -204.7181215594 -0.000035528237 0.00039890 0.00001059 0.0020742 0.7000 + ***Turning on DIIS*** + 2 -204.7181510924 -0.000029532946 0.00102154 0.00002754 0.0015835 0.0000 + 3 -204.7177691691 0.000381923232 0.00038372 0.00001259 0.0004099 0.0000 + 4 -204.7184895152 -0.000720346056 0.00017371 0.00000406 0.0001509 0.0000 + 5 -204.7184568565 0.000032658667 0.00003449 0.00000121 0.0000587 0.0000 + 6 -204.7180196889 0.000437167595 0.00002804 0.00000071 0.0000462 0.0000 + 7 -204.7182515729 -0.000231883914 0.00000704 0.00000027 0.0000119 0.0000 + 8 -204.7182540784 -0.000002505515 0.00000532 0.00000015 0.0000085 0.0000 + 9 -204.7182284247 0.000025653674 0.00000283 0.00000010 0.0000033 0.0000 + 10 -204.7182557592 -0.000027334484 0.00000129 0.00000005 0.0000016 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + +Total Energy : -204.71824644 Eh -5570.66669 eV + Last Energy change ... 9.3185e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.0029e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.206 sec +Reference energy ... -204.718247823 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.375 sec +AO-integral generation ... 0.142 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.380 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.025 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.032 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.031 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.036 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.343 sec +AO-integral generation ... 0.238 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.049 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.158 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.251 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090385820 +EMP2(bb)= -0.090385820 +EMP2(ab)= -0.515259472 + +Initial guess performed in 0.132 sec +E(0) ... -204.718247823 +E(MP2) ... -0.696031111 +Initial E(tot) ... -205.414278935 + ... 0.186948427 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.414278935 -0.696031111 -0.000000000 0.026548415 2.73 0.000002340 + *** Turning on DIIS *** + 1 -205.385724739 -0.667476916 0.028554196 0.010182049 2.70 0.057657406 + 2 -205.405109317 -0.686861494 -0.019384578 0.005920229 2.79 0.060892509 + 3 -205.408827800 -0.690579977 -0.003718483 0.002025921 2.79 0.075239980 + 4 -205.410405888 -0.692158064 -0.001578087 0.001472485 2.83 0.082193022 + 5 -205.410960534 -0.692712711 -0.000554647 0.000858926 2.84 0.087828350 + 6 -205.411068271 -0.692820448 -0.000107737 0.000528596 2.91 0.090551102 + 7 -205.411112822 -0.692864999 -0.000044551 0.000236123 2.95 0.091750213 + 8 -205.411123447 -0.692875623 -0.000010624 0.000117025 2.94 0.092213859 + 9 -205.411119344 -0.692871521 0.000004103 0.000037772 2.92 0.092352611 + 10 -205.411124318 -0.692876495 -0.000004974 0.000023849 2.80 0.092406437 + 11 -205.411121598 -0.692873775 0.000002720 0.000017354 2.85 0.092395827 + 12 -205.411122714 -0.692874891 -0.000001116 0.000011936 2.89 0.092406667 + 13 -205.411122576 -0.692874753 0.000000138 0.000007352 2.87 0.092403672 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.718247823 +E(CORR) ... -0.692874753 +E(TOT) ... -205.411122576 +Singles norm **1/2 ... 0.092403672 ( 0.046201836, 0.046201836) +T1 diagnostic ... 0.021779754 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.059201 + 8a-> 13a -1a-> -1a 0.044292 + 8b-> 13b -1b-> -1b 0.044292 + 10a-> 13a 10b-> 13b 0.042558 + 11a-> 13a 11b-> 13b 0.030111 + 10a-> 13a 8b-> 13b 0.030108 + 8a-> 13a 10b-> 13b 0.030108 + 9a-> 13a 9b-> 13b 0.028592 + 10b-> 13b -1b-> -1b 0.028216 + 10a-> 13a -1a-> -1a 0.028216 + 8a-> 13a 9b-> 13b 0.026607 + 9a-> 13a 8b-> 13b 0.026607 + 5a-> 13a 5b-> 13b 0.026232 + 10a-> 13a 9b-> 13b 0.023240 + 9a-> 13a 10b-> 13b 0.023240 + 8a-> 13a 8b-> 22b 0.022392 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034569858 + alpha-alpha-alpha ... -0.000901310 ( 2.6%) + alpha-alpha-beta ... -0.016383619 ( 47.4%) + alpha-beta -beta ... -0.016383619 ( 47.4%) + beta -beta -beta ... -0.000901310 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034569858 + +Final correlation energy ... -0.727444612 +E(CCSD) ... -205.411122576 +E(CCSD(T)) ... -205.445692435 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.208908941 sqrt= 1.099503952 +W(HF) = 0.827192161 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 55.344 sec + +Fock Matrix Formation ... 0.206 sec ( 0.4%) +Initial Guess ... 0.132 sec ( 0.2%) +DIIS Solver ... 1.872 sec ( 3.4%) +State Vector Update ... 0.083 sec ( 0.1%) +Sigma-vector construction ... 37.845 sec ( 68.4%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.024 sec ( 0.1% of sigma) + (0-ext) ... 0.070 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.025 sec ( 0.1% of sigma) + (2-ext) ... 0.933 sec ( 2.5% of sigma) + (4-ext) ... 20.691 sec ( 54.7% of sigma) + ... 1.519 sec ( 4.0% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.107 sec ( 0.3% of sigma) + Fock-dressing ... 2.108 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.074 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.671 sec ( 25.6% of sigma) + Pair energies ... 0.006 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.789 sec ( 12.3% of ALL) + I/O of integral and amplitudes ... 0.778 sec ( 11.5% of (T)) + External N**7 contributions ... 3.922 sec ( 57.8% of (T)) + Internal N**7 contributions ... 0.312 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.697 sec ( 25.0% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.445692434817 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.006336297 0.001659061 -0.012193719 + 2 N : 0.006210060 0.003366815 0.010508115 + 3 O : -0.004259607 -0.002800592 -0.006703199 + 4 H : 0.004385844 -0.002225284 0.008388804 + +Norm of the cartesian gradient ... 0.022746180 +RMS gradient ... 0.006566256 +MAX gradient ... 0.012193719 + +------- +TIMINGS +------- + +Total numerical gradient time ... 346.557 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.445692435 Eh +Current gradient norm .... 0.022746180 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999998305 +Lowest eigenvalues of augmented Hessian: + -0.000000459 0.121675307 0.195636263 0.474487383 0.519153365 +Length of the computed step .... 0.001841438 +The final length of the internal step .... 0.001841438 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0007517639 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0004008353 RMS(Int)= 0.0007517636 + Iter 1: RMS(Cart)= 0.0000000311 RMS(Int)= 0.0000000494 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000648586 0.0000050000 NO + RMS gradient 0.0001062403 0.0001000000 NO + MAX gradient 0.0002562772 0.0003000000 YES + RMS step 0.0007517639 0.0020000000 YES + MAX step 0.0017863270 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0009 Max(Angles) 0.02 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4227 -0.000256 0.0009 1.4236 + 2. B(O 2,N 1) 1.1815 -0.000003 -0.0001 1.1814 + 3. B(H 3,O 0) 0.9747 -0.000042 0.0000 0.9747 + 4. A(N 1,O 0,H 3) 105.07 -0.000007 -0.02 105.06 + 5. A(O 0,N 1,O 2) 113.11 0.000015 -0.01 113.10 + 6. D(O 2,N 1,O 0,H 3) -32.73 -0.017293 -0.00 -32.73 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.701201 -0.368549 0.439931 + N 0.524698 -0.575915 -0.253556 + O 0.874224 0.369299 -0.869996 + H -0.697720 0.575166 0.683621 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.325078 -0.696457 0.831348 + 1 N 7.0000 0 14.007 0.991535 -1.088322 -0.479152 + 2 O 8.0000 0 15.999 1.652044 0.697874 -1.644053 + 3 H 1.0000 0 1.008 -1.318500 1.086906 1.291857 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.423640677807 0.00000000 0.00000000 + O 2 1 0 1.181353461840 113.10478754 0.00000000 + H 1 2 3 0.974677060647 105.05511524 327.27272752 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.690290994165 0.00000000 0.00000000 + O 2 1 0 2.232434510237 113.10478754 0.00000000 + H 1 2 3 1.841872713639 105.05511524 327.27272752 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2243 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2717 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.629310579351 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.515e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7181824553 0.000000000000 0.00002929 0.00000073 0.0001586 0.7000 + 1 -204.7181825801 -0.000000124777 0.00002414 0.00000061 0.0001228 0.7000 + ***Turning on DIIS*** + 2 -204.7181826839 -0.000000103783 0.00006287 0.00000165 0.0000941 0.0000 + 3 -204.7181967146 -0.000014030763 0.00001982 0.00000072 0.0000229 0.0000 + 4 -204.7181714847 0.000025229982 0.00000923 0.00000024 0.0000071 0.0000 + 5 -204.7181833816 -0.000011896980 0.00000236 0.00000008 0.0000022 0.0000 + 6 -204.7181915886 -0.000008206968 0.00000156 0.00000003 0.0000024 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + +Total Energy : -204.71818188 Eh -5570.66494 eV + Last Energy change ... 9.7068e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.0594e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.205 sec +Reference energy ... -204.718183029 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.370 sec +AO-integral generation ... 0.144 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.375 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.024 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.027 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.032 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.032 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.036 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.030 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.346 sec +AO-integral generation ... 0.239 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.152 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.253 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090391781 +EMP2(bb)= -0.090391781 +EMP2(ab)= -0.515309975 + +Initial guess performed in 0.134 sec +E(0) ... -204.718183029 +E(MP2) ... -0.696093537 +Initial E(tot) ... -205.414276566 + ... 0.187010106 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.414276566 -0.696093537 -0.000000000 0.026531440 2.70 0.000001375 + *** Turning on DIIS *** + 1 -205.385695400 -0.667512371 0.028581166 0.010200401 2.71 0.057685423 + 2 -205.405090480 -0.686907451 -0.019395080 0.005915067 2.79 0.060914108 + 3 -205.408811026 -0.690627997 -0.003720546 0.002022324 2.85 0.075271617 + 4 -205.410390303 -0.692207274 -0.001579277 0.001479764 2.82 0.082229764 + 5 -205.410945968 -0.692762939 -0.000555664 0.000862765 2.87 0.087876691 + 6 -205.411054039 -0.692871010 -0.000108071 0.000530830 2.82 0.090609317 + 7 -205.411098797 -0.692915768 -0.000044758 0.000236793 2.88 0.091815256 + 8 -205.411109504 -0.692926475 -0.000010708 0.000117392 2.88 0.092281553 + 9 -205.411105383 -0.692922354 0.000004121 0.000037655 2.83 0.092420884 + 10 -205.411110384 -0.692927355 -0.000005001 0.000023789 2.79 0.092474997 + 11 -205.411107654 -0.692924625 0.000002730 0.000017307 2.79 0.092464349 + 12 -205.411108771 -0.692925742 -0.000001117 0.000011913 2.80 0.092475241 + 13 -205.411108632 -0.692925603 0.000000138 0.000007359 2.80 0.092472235 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.718183029 +E(CORR) ... -0.692925603 +E(TOT) ... -205.411108632 +Singles norm **1/2 ... 0.092472235 ( 0.046236117, 0.046236117) +T1 diagnostic ... 0.021795915 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.059335 + 8a-> 13a -1a-> -1a 0.044255 + 8b-> 13b -1b-> -1b 0.044255 + 10a-> 13a 10b-> 13b 0.042413 + 10a-> 13a 8b-> 13b 0.030094 + 8a-> 13a 10b-> 13b 0.030094 + 11a-> 13a 11b-> 13b 0.030084 + 9a-> 13a 9b-> 13b 0.028600 + 10b-> 13b -1b-> -1b 0.028388 + 10a-> 13a -1a-> -1a 0.028388 + 8a-> 13a 9b-> 13b 0.026664 + 9a-> 13a 8b-> 13b 0.026664 + 5a-> 13a 5b-> 13b 0.026275 + 10a-> 13a 9b-> 13b 0.023197 + 9a-> 13a 10b-> 13b 0.023197 + 8a-> 13a 8b-> 22b 0.022437 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034584023 + alpha-alpha-alpha ... -0.000901483 ( 2.6%) + alpha-alpha-beta ... -0.016390528 ( 47.4%) + alpha-beta -beta ... -0.016390528 ( 47.4%) + beta -beta -beta ... -0.000901483 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034584023 + +Final correlation energy ... -0.727509626 +E(CCSD) ... -205.411108632 +E(CCSD(T)) ... -205.445692655 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.208996839 sqrt= 1.099543923 +W(HF) = 0.827132022 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 54.313 sec + +Fock Matrix Formation ... 0.205 sec ( 0.4%) +Initial Guess ... 0.134 sec ( 0.2%) +DIIS Solver ... 1.699 sec ( 3.1%) +State Vector Update ... 0.085 sec ( 0.2%) +Sigma-vector construction ... 37.540 sec ( 69.1%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.023 sec ( 0.1% of sigma) + (0-ext) ... 0.068 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.025 sec ( 0.1% of sigma) + (2-ext) ... 0.922 sec ( 2.5% of sigma) + (4-ext) ... 20.867 sec ( 55.6% of sigma) + ... 1.368 sec ( 3.6% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.106 sec ( 0.3% of sigma) + Fock-dressing ... 2.101 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.074 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.341 sec ( 24.9% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.811 sec ( 12.5% of ALL) + I/O of integral and amplitudes ... 0.772 sec ( 11.3% of (T)) + External N**7 contributions ... 4.046 sec ( 59.4% of (T)) + Internal N**7 contributions ... 0.313 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.560 sec ( 22.9% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.445692654895 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.006545763 0.001661946 -0.012036729 + 2 N : 0.006428109 0.003303725 0.010344904 + 3 O : -0.004252325 -0.002786715 -0.006686284 + 4 H : 0.004369979 -0.002178956 0.008378109 + +Norm of the cartesian gradient ... 0.022678974 +RMS gradient ... 0.006546856 +MAX gradient ... 0.012036729 + +------- +TIMINGS +------- + +Total numerical gradient time ... 345.901 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.445692655 Eh +Current gradient norm .... 0.022678974 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999995 +Lowest eigenvalues of augmented Hessian: + -0.000000002 0.126445070 0.199507191 0.474471324 0.518960724 +Length of the computed step .... 0.000103700 +The final length of the internal step .... 0.000103700 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0000423353 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0000249801 RMS(Int)= 0.0000423353 + Iter 1: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000001 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000002201 0.0000050000 YES + RMS gradient 0.0000066450 0.0001000000 YES + MAX gradient 0.0000160718 0.0003000000 YES + RMS step 0.0000423353 0.0020000000 YES + MAX step 0.0001020675 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4236 0.000016 -0.0001 1.4236 + 2. B(O 2,N 1) 1.1814 0.000001 0.0000 1.1814 + 3. B(H 3,O 0) 0.9747 0.000000 0.0000 0.9747 + 4. A(N 1,O 0,H 3) 105.06 0.000002 0.00 105.06 + 5. A(O 0,N 1,O 2) 113.10 0.000001 0.00 113.10 + 6. D(O 2,N 1,O 0,H 3) -32.73 -0.017248 0.00 -32.73 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.701179 -0.368552 0.439916 + N 0.524675 -0.575914 -0.253540 + O 0.874211 0.369303 -0.869985 + H -0.697707 0.575163 0.683610 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.325036 -0.696462 0.831320 + 1 N 7.0000 0 14.007 0.991493 -1.088319 -0.479122 + 2 O 8.0000 0 15.999 1.652019 0.697881 -1.644034 + 3 H 1.0000 0 1.008 -1.318474 1.086901 1.291835 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.423586666027 0.00000000 0.00000000 + O 2 1 0 1.181361012512 113.10498772 0.00000000 + H 1 2 3 0.974677876354 105.05573688 327.27272752 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.690188926693 0.00000000 0.00000000 + O 2 1 0 2.232448778940 113.10498772 0.00000000 + H 1 2 3 1.841874255101 105.05573688 327.27272752 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2243 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2717 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.630278810528 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.6302788105 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.515e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7181866891 0.000000000000 0.00000167 0.00000004 0.0000092 0.7000 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 1 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71818669 Eh -5570.66507 eV + +Components: +Nuclear Repulsion : 69.63027881 Eh 1894.73621 eV +Electronic Energy : -274.34846550 Eh -7465.40128 eV +One Electron Energy: -418.87219470 Eh -11398.09189 eV +Two Electron Energy: 144.52372920 Eh 3932.69061 eV + +Virial components: +Potential Energy : -408.96132821 Eh -11128.40350 eV +Kinetic Energy : 204.24314152 Eh 5557.73843 eV +Virial Ratio : 2.00232588 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -6.6422e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.3742e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.4738e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.1352e-06 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.672935 -562.5392 + 1 1.0000 -20.641564 -561.6855 + 2 1.0000 -15.803202 -430.0270 + 3 1.0000 -1.608804 -43.7778 + 4 1.0000 -1.399904 -38.0933 + 5 1.0000 -0.963800 -26.2263 + 6 1.0000 -0.774834 -21.0843 + 7 1.0000 -0.740169 -20.1410 + 8 1.0000 -0.692954 -18.8562 + 9 1.0000 -0.608756 -16.5651 + 10 1.0000 -0.534036 -14.5319 + 11 1.0000 -0.471411 -12.8277 + 12 0.0000 0.031227 0.8497 + 13 0.0000 0.072922 1.9843 + 14 0.0000 0.094567 2.5733 + 15 0.0000 0.111769 3.0414 + 16 0.0000 0.119008 3.2384 + 17 0.0000 0.148867 4.0509 + 18 0.0000 0.157384 4.2826 + 19 0.0000 0.169902 4.6233 + 20 0.0000 0.182300 4.9606 + 21 0.0000 0.194232 5.2853 + 22 0.0000 0.203949 5.5497 + 23 0.0000 0.233936 6.3657 + 24 0.0000 0.258525 7.0348 + 25 0.0000 0.297262 8.0889 + 26 0.0000 0.310990 8.4625 + 27 0.0000 0.341813 9.3012 + 28 0.0000 0.347890 9.4666 + 29 0.0000 0.388039 10.5591 + 30 0.0000 0.423974 11.5369 + 31 0.0000 0.514819 14.0089 + 32 0.0000 0.525689 14.3047 + 33 0.0000 0.534110 14.5339 + 34 0.0000 0.563219 15.3260 + 35 0.0000 0.614921 16.7328 + 36 0.0000 0.633773 17.2458 + 37 0.0000 0.653992 17.7960 + 38 0.0000 0.689952 18.7746 + 39 0.0000 0.702978 19.1290 + 40 0.0000 0.733423 19.9575 + 41 0.0000 0.748314 20.3627 + 42 0.0000 0.763840 20.7851 + 43 0.0000 0.786765 21.4090 + 44 0.0000 0.806139 21.9361 + 45 0.0000 0.839689 22.8491 + 46 0.0000 0.848196 23.0806 + 47 0.0000 0.878087 23.8940 + 48 0.0000 0.920041 25.0356 + 49 0.0000 0.941362 25.6158 + 50 0.0000 0.964018 26.2323 + 51 0.0000 0.988377 26.8951 + 52 0.0000 1.019482 27.7415 + 53 0.0000 1.040125 28.3032 + 54 0.0000 1.068636 29.0791 + 55 0.0000 1.086631 29.5687 + 56 0.0000 1.173445 31.9311 + 57 0.0000 1.194972 32.5168 + 58 0.0000 1.238553 33.7027 + 59 0.0000 1.278536 34.7907 + 60 0.0000 1.361985 37.0615 + 61 0.0000 1.410360 38.3779 + 62 0.0000 1.438036 39.1310 + 63 0.0000 1.513372 41.1809 + 64 0.0000 1.535512 41.7834 + 65 0.0000 1.551207 42.2105 + 66 0.0000 1.605309 43.6827 + 67 0.0000 1.630901 44.3791 + 68 0.0000 1.655251 45.0417 + 69 0.0000 1.737754 47.2867 + 70 0.0000 1.779215 48.4149 + 71 0.0000 1.812162 49.3114 + 72 0.0000 1.900120 51.7049 + 73 0.0000 1.953275 53.1513 + 74 0.0000 1.982058 53.9346 + 75 0.0000 2.020620 54.9839 + 76 0.0000 2.032605 55.3100 + 77 0.0000 2.086146 56.7669 + 78 0.0000 2.158443 58.7342 + 79 0.0000 2.176280 59.2196 + 80 0.0000 2.259623 61.4875 + 81 0.0000 2.306629 62.7666 + 82 0.0000 2.359432 64.2034 + 83 0.0000 2.393824 65.1393 + 84 0.0000 2.420008 65.8518 + 85 0.0000 2.446037 66.5600 + 86 0.0000 2.465938 67.1016 + 87 0.0000 2.516709 68.4831 + 88 0.0000 2.539848 69.1128 + 89 0.0000 2.556514 69.5663 + 90 0.0000 2.576740 70.1167 + 91 0.0000 2.620955 71.3198 + 92 0.0000 2.657630 72.3178 + 93 0.0000 2.684505 73.0491 + 94 0.0000 2.749557 74.8192 + 95 0.0000 2.803383 76.2839 + 96 0.0000 2.851025 77.5803 + 97 0.0000 2.954290 80.3903 + 98 0.0000 2.979494 81.0761 + 99 0.0000 3.031304 82.4860 + 100 0.0000 3.145137 85.5835 + 101 0.0000 3.168131 86.2092 + 102 0.0000 3.225535 87.7713 + 103 0.0000 3.516585 95.6911 + 104 0.0000 3.701462 100.7219 + 105 0.0000 3.881780 105.6286 + 106 0.0000 4.014820 109.2488 + 107 0.0000 4.149123 112.9034 + 108 0.0000 4.180517 113.7577 + 109 0.0000 4.305512 117.1589 + 110 0.0000 4.373535 119.0099 + 111 0.0000 4.410235 120.0086 + 112 0.0000 4.523632 123.0943 + 113 0.0000 4.567332 124.2834 + 114 0.0000 4.684016 127.4586 + 115 0.0000 4.809870 130.8832 + 116 0.0000 4.847495 131.9070 + 117 0.0000 4.870685 132.5381 + 118 0.0000 4.964826 135.0998 + 119 0.0000 5.003172 136.1432 + 120 0.0000 5.075623 138.1147 + 121 0.0000 5.108932 139.0211 + 122 0.0000 5.189004 141.2000 + 123 0.0000 5.233687 142.4159 + 124 0.0000 5.241073 142.6168 + 125 0.0000 5.283527 143.7721 + 126 0.0000 5.384607 146.5226 + 127 0.0000 5.475383 148.9928 + 128 0.0000 5.540403 150.7620 + 129 0.0000 5.693135 154.9181 + 130 0.0000 5.779739 157.2747 + 131 0.0000 5.943445 161.7294 + 132 0.0000 6.169260 167.8741 + 133 0.0000 6.406190 174.3213 + 134 0.0000 6.501330 176.9102 + 135 0.0000 6.534564 177.8145 + 136 0.0000 6.685756 181.9287 + 137 0.0000 6.723697 182.9611 + 138 0.0000 6.775511 184.3710 + 139 0.0000 6.800380 185.0478 + 140 0.0000 6.912732 188.1050 + 141 0.0000 7.101344 193.2374 + 142 0.0000 7.131664 194.0624 + 143 0.0000 7.170818 195.1279 + 144 0.0000 7.186096 195.5436 + 145 0.0000 7.244430 197.1310 + 146 0.0000 7.268305 197.7806 + 147 0.0000 7.312192 198.9749 + 148 0.0000 7.394627 201.2180 + 149 0.0000 7.458664 202.9606 + 150 0.0000 7.504769 204.2151 + 151 0.0000 7.522144 204.6880 + 152 0.0000 7.574171 206.1037 + 153 0.0000 7.659873 208.4357 + 154 0.0000 7.827722 213.0032 + 155 0.0000 7.880766 214.4466 + 156 0.0000 8.192867 222.9392 + 157 0.0000 8.335638 226.8242 + 158 0.0000 14.087086 383.3291 + 159 0.0000 15.135021 411.8448 + 160 0.0000 15.704169 427.3322 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.672935 -562.5392 + 1 1.0000 -20.641564 -561.6855 + 2 1.0000 -15.803202 -430.0270 + 3 1.0000 -1.608804 -43.7778 + 4 1.0000 -1.399904 -38.0933 + 5 1.0000 -0.963800 -26.2263 + 6 1.0000 -0.774834 -21.0843 + 7 1.0000 -0.740169 -20.1410 + 8 1.0000 -0.692954 -18.8562 + 9 1.0000 -0.608756 -16.5651 + 10 1.0000 -0.534036 -14.5319 + 11 1.0000 -0.471411 -12.8277 + 12 0.0000 0.031227 0.8497 + 13 0.0000 0.072922 1.9843 + 14 0.0000 0.094567 2.5733 + 15 0.0000 0.111769 3.0414 + 16 0.0000 0.119008 3.2384 + 17 0.0000 0.148867 4.0509 + 18 0.0000 0.157384 4.2826 + 19 0.0000 0.169902 4.6233 + 20 0.0000 0.182300 4.9606 + 21 0.0000 0.194232 5.2853 + 22 0.0000 0.203949 5.5497 + 23 0.0000 0.233936 6.3657 + 24 0.0000 0.258525 7.0348 + 25 0.0000 0.297262 8.0889 + 26 0.0000 0.310990 8.4625 + 27 0.0000 0.341813 9.3012 + 28 0.0000 0.347890 9.4666 + 29 0.0000 0.388039 10.5591 + 30 0.0000 0.423974 11.5369 + 31 0.0000 0.514819 14.0089 + 32 0.0000 0.525689 14.3047 + 33 0.0000 0.534110 14.5339 + 34 0.0000 0.563219 15.3260 + 35 0.0000 0.614921 16.7328 + 36 0.0000 0.633773 17.2458 + 37 0.0000 0.653992 17.7960 + 38 0.0000 0.689952 18.7746 + 39 0.0000 0.702978 19.1290 + 40 0.0000 0.733423 19.9575 + 41 0.0000 0.748314 20.3627 + 42 0.0000 0.763840 20.7851 + 43 0.0000 0.786765 21.4090 + 44 0.0000 0.806139 21.9361 + 45 0.0000 0.839689 22.8491 + 46 0.0000 0.848196 23.0806 + 47 0.0000 0.878087 23.8940 + 48 0.0000 0.920041 25.0356 + 49 0.0000 0.941362 25.6158 + 50 0.0000 0.964018 26.2323 + 51 0.0000 0.988377 26.8951 + 52 0.0000 1.019482 27.7415 + 53 0.0000 1.040125 28.3032 + 54 0.0000 1.068636 29.0791 + 55 0.0000 1.086631 29.5687 + 56 0.0000 1.173445 31.9311 + 57 0.0000 1.194972 32.5168 + 58 0.0000 1.238553 33.7027 + 59 0.0000 1.278536 34.7907 + 60 0.0000 1.361985 37.0615 + 61 0.0000 1.410360 38.3779 + 62 0.0000 1.438036 39.1310 + 63 0.0000 1.513372 41.1809 + 64 0.0000 1.535512 41.7834 + 65 0.0000 1.551207 42.2105 + 66 0.0000 1.605309 43.6827 + 67 0.0000 1.630901 44.3791 + 68 0.0000 1.655251 45.0417 + 69 0.0000 1.737754 47.2867 + 70 0.0000 1.779215 48.4149 + 71 0.0000 1.812162 49.3114 + 72 0.0000 1.900120 51.7049 + 73 0.0000 1.953275 53.1513 + 74 0.0000 1.982058 53.9346 + 75 0.0000 2.020620 54.9839 + 76 0.0000 2.032605 55.3100 + 77 0.0000 2.086146 56.7669 + 78 0.0000 2.158443 58.7342 + 79 0.0000 2.176280 59.2196 + 80 0.0000 2.259623 61.4875 + 81 0.0000 2.306629 62.7666 + 82 0.0000 2.359432 64.2034 + 83 0.0000 2.393824 65.1393 + 84 0.0000 2.420008 65.8518 + 85 0.0000 2.446037 66.5600 + 86 0.0000 2.465938 67.1016 + 87 0.0000 2.516709 68.4831 + 88 0.0000 2.539848 69.1128 + 89 0.0000 2.556514 69.5663 + 90 0.0000 2.576740 70.1167 + 91 0.0000 2.620955 71.3198 + 92 0.0000 2.657630 72.3178 + 93 0.0000 2.684505 73.0491 + 94 0.0000 2.749557 74.8192 + 95 0.0000 2.803383 76.2839 + 96 0.0000 2.851025 77.5803 + 97 0.0000 2.954290 80.3903 + 98 0.0000 2.979494 81.0761 + 99 0.0000 3.031304 82.4860 + 100 0.0000 3.145137 85.5835 + 101 0.0000 3.168131 86.2092 + 102 0.0000 3.225535 87.7713 + 103 0.0000 3.516585 95.6911 + 104 0.0000 3.701462 100.7219 + 105 0.0000 3.881780 105.6286 + 106 0.0000 4.014820 109.2488 + 107 0.0000 4.149123 112.9034 + 108 0.0000 4.180517 113.7577 + 109 0.0000 4.305512 117.1589 + 110 0.0000 4.373535 119.0099 + 111 0.0000 4.410235 120.0086 + 112 0.0000 4.523632 123.0943 + 113 0.0000 4.567332 124.2834 + 114 0.0000 4.684016 127.4586 + 115 0.0000 4.809870 130.8832 + 116 0.0000 4.847495 131.9070 + 117 0.0000 4.870685 132.5381 + 118 0.0000 4.964826 135.0998 + 119 0.0000 5.003172 136.1432 + 120 0.0000 5.075623 138.1147 + 121 0.0000 5.108932 139.0211 + 122 0.0000 5.189004 141.2000 + 123 0.0000 5.233687 142.4159 + 124 0.0000 5.241073 142.6168 + 125 0.0000 5.283527 143.7721 + 126 0.0000 5.384607 146.5226 + 127 0.0000 5.475383 148.9928 + 128 0.0000 5.540403 150.7620 + 129 0.0000 5.693135 154.9181 + 130 0.0000 5.779739 157.2747 + 131 0.0000 5.943445 161.7294 + 132 0.0000 6.169260 167.8741 + 133 0.0000 6.406190 174.3213 + 134 0.0000 6.501330 176.9102 + 135 0.0000 6.534564 177.8145 + 136 0.0000 6.685756 181.9287 + 137 0.0000 6.723697 182.9611 + 138 0.0000 6.775511 184.3710 + 139 0.0000 6.800380 185.0478 + 140 0.0000 6.912732 188.1050 + 141 0.0000 7.101344 193.2374 + 142 0.0000 7.131664 194.0624 + 143 0.0000 7.170818 195.1279 + 144 0.0000 7.186096 195.5436 + 145 0.0000 7.244430 197.1310 + 146 0.0000 7.268305 197.7806 + 147 0.0000 7.312192 198.9749 + 148 0.0000 7.394627 201.2180 + 149 0.0000 7.458664 202.9606 + 150 0.0000 7.504769 204.2151 + 151 0.0000 7.522144 204.6880 + 152 0.0000 7.574171 206.1037 + 153 0.0000 7.659873 208.4357 + 154 0.0000 7.827722 213.0032 + 155 0.0000 7.880766 214.4466 + 156 0.0000 8.192867 222.9392 + 157 0.0000 8.335638 226.8242 + 158 0.0000 14.087086 383.3291 + 159 0.0000 15.135021 411.8448 + 160 0.0000 15.704169 427.3322 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.306494 0.000000 + 1 N : 0.345100 0.000000 + 2 O : -0.287629 0.000000 + 3 H : 0.249024 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.816510 s : 3.816510 + pz : 1.693688 p : 4.450336 + px : 1.352958 + py : 1.403690 + dz2 : 0.006903 d : 0.034528 + dxz : 0.007539 + dyz : 0.000421 + dx2y2 : 0.015319 + dxy : 0.004346 + f0 : 0.000520 f : 0.005120 + f+1 : 0.001178 + f-1 : 0.000231 + f+2 : 0.000641 + f-2 : 0.000772 + f+3 : 0.000777 + f-3 : 0.001000 + 1 N s : 3.850684 s : 3.850684 + pz : 0.734947 p : 2.628668 + px : 0.746791 + py : 1.146930 + dz2 : 0.031112 d : 0.142742 + dxz : 0.028821 + dyz : 0.023990 + dx2y2 : 0.037814 + dxy : 0.021005 + f0 : 0.001302 f : 0.032806 + f+1 : 0.004605 + f-1 : 0.005283 + f+2 : 0.003278 + f-2 : 0.005128 + f+3 : 0.006009 + f-3 : 0.007202 + 2 O s : 3.864949 s : 3.864949 + pz : 1.293626 p : 4.354343 + px : 1.678879 + py : 1.381838 + dz2 : 0.016531 d : 0.060852 + dxz : 0.004230 + dyz : 0.014078 + dx2y2 : 0.009220 + dxy : 0.016793 + f0 : 0.000382 f : 0.007485 + f+1 : 0.000146 + f-1 : 0.002064 + f+2 : 0.001366 + f-2 : 0.001036 + f+3 : 0.001243 + f-3 : 0.001249 + 3 H s : 0.643087 s : 0.643087 + pz : 0.039181 p : 0.086548 + px : 0.026892 + py : 0.020476 + dz2 : 0.001347 d : 0.021341 + dxz : -0.000364 + dyz : 0.008448 + dx2y2 : 0.001062 + dxy : 0.010848 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.595988 0.000000 + 1 N : -0.273863 0.000000 + 2 O : 0.244147 0.000000 + 3 H : -0.566271 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.112330 s : 3.112330 + pz : 1.371828 p : 3.912974 + px : 1.237037 + py : 1.304110 + dz2 : 0.039455 d : 0.289795 + dxz : 0.075383 + dyz : 0.031151 + dx2y2 : 0.077340 + dxy : 0.066466 + f0 : 0.008284 f : 0.088913 + f+1 : 0.016092 + f-1 : 0.001406 + f+2 : 0.014559 + f-2 : 0.014709 + f+3 : 0.009861 + f-3 : 0.024001 + 1 N s : 3.009274 s : 3.009274 + pz : 0.778028 p : 2.832570 + px : 0.837055 + py : 1.217487 + dz2 : 0.166797 d : 0.966465 + dxz : 0.210862 + dyz : 0.162153 + dx2y2 : 0.245113 + dxy : 0.181540 + f0 : 0.030323 f : 0.465554 + f+1 : 0.053580 + f-1 : 0.056467 + f+2 : 0.076913 + f-2 : 0.083577 + f+3 : 0.074149 + f-3 : 0.090546 + 2 O s : 3.303632 s : 3.303632 + pz : 1.199194 p : 4.014361 + px : 1.395520 + py : 1.419647 + dz2 : 0.039502 d : 0.321968 + dxz : 0.047716 + dyz : 0.082967 + dx2y2 : 0.102659 + dxy : 0.049123 + f0 : 0.009337 f : 0.115892 + f+1 : 0.004918 + f-1 : 0.018398 + f+2 : 0.025998 + f-2 : 0.020142 + f+3 : 0.011507 + f-3 : 0.025593 + 3 H s : 0.614554 s : 0.614554 + pz : 0.154045 p : 0.550385 + px : 0.135651 + py : 0.260690 + dz2 : 0.046691 d : 0.401332 + dxz : 0.028932 + dyz : 0.114390 + dx2y2 : 0.099682 + dxy : 0.111637 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3065 8.0000 -0.3065 1.8170 1.8170 0.0000 + 1 N 6.6549 7.0000 0.3451 2.5273 2.5273 0.0000 + 2 O 8.2876 8.0000 -0.2876 1.7080 1.7080 0.0000 + 3 H 0.7510 1.0000 0.2490 1.0141 1.0141 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8190 B( 0-O , 3-H ) : 0.9382 B( 1-N , 2-O ) : 1.6403 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.501 sec +Sum of individual times .... 0.300 sec ( 59.9%) + +Fock matrix formation .... 0.215 sec ( 42.9%) +Diagonalization .... 0.023 sec ( 4.5%) +Density matrix formation .... 0.002 sec ( 0.4%) +Population analysis .... 0.039 sec ( 7.8%) +Initial guess .... 0.010 sec ( 1.9%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 1.0%) +DIIS solution .... 0.012 sec ( 2.4%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.205 sec +Reference energy ... -204.718186691 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.390 sec +AO-integral generation ... 0.143 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.394 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.026 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.028 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.032 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.031 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.030 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.349 sec +AO-integral generation ... 0.241 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.053 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.148 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.251 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090391526 +EMP2(bb)= -0.090391526 +EMP2(ab)= -0.515307468 + +Initial guess performed in 0.133 sec +E(0) ... -204.718186691 +E(MP2) ... -0.696090521 +Initial E(tot) ... -205.414277211 + ... 0.187006843 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.414277211 -0.696090521 -0.000000000 0.026531931 2.70 0.000007566 + *** Turning on DIIS *** + 1 -205.385697115 -0.667510424 0.028580096 0.010199329 2.69 0.057682572 + 2 -205.405091625 -0.686904934 -0.019394510 0.005915337 2.78 0.060911386 + 3 -205.408812002 -0.690625311 -0.003720377 0.002022574 2.82 0.075268072 + 4 -205.410391174 -0.692204484 -0.001579173 0.001479579 2.77 0.082225851 + 5 -205.410946773 -0.692760083 -0.000555599 0.000862680 2.87 0.087872235 + 6 -205.411054834 -0.692868143 -0.000108060 0.000530743 2.79 0.090604599 + 7 -205.411099583 -0.692912893 -0.000044749 0.000236760 2.86 0.091810334 + 8 -205.411110288 -0.692923597 -0.000010705 0.000117358 2.88 0.092276571 + 9 -205.411106167 -0.692919476 0.000004121 0.000037664 2.78 0.092415873 + 10 -205.411111167 -0.692924476 -0.000005000 0.000023795 2.77 0.092469979 + 11 -205.411108437 -0.692921746 0.000002730 0.000017311 2.83 0.092459331 + 12 -205.411109554 -0.692922863 -0.000001117 0.000011916 2.78 0.092470222 + 13 -205.411109416 -0.692922725 0.000000138 0.000007359 2.81 0.092467216 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.718186691 +E(CORR) ... -0.692922725 +E(TOT) ... -205.411109416 +Singles norm **1/2 ... 0.092467216 ( 0.046233608, 0.046233608) +T1 diagnostic ... 0.021794732 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.059328 + 8a-> 13a -1a-> -1a 0.044258 + 8b-> 13b -1b-> -1b 0.044258 + 10a-> 13a 10b-> 13b 0.042420 + 8a-> 13a 10b-> 13b 0.030095 + 10a-> 13a 8b-> 13b 0.030095 + 11a-> 13a 11b-> 13b 0.030085 + 9a-> 13a 9b-> 13b 0.028600 + 10a-> 13a -1a-> -1a 0.028386 + 10b-> 13b -1b-> -1b 0.028386 + 9a-> 13a 8b-> 13b 0.026661 + 8a-> 13a 9b-> 13b 0.026661 + 5a-> 13a 5b-> 13b 0.026273 + 9a-> 13a 10b-> 13b 0.023199 + 10a-> 13a 9b-> 13b 0.023199 + 8a-> 22a 8b-> 13b 0.022435 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034583245 + alpha-alpha-alpha ... -0.000901475 ( 2.6%) + alpha-alpha-beta ... -0.016390148 ( 47.4%) + alpha-beta -beta ... -0.016390148 ( 47.4%) + beta -beta -beta ... -0.000901475 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034583245 + +Final correlation energy ... -0.727505969 +E(CCSD) ... -205.411109416 +E(CCSD(T)) ... -205.445692660 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.208991413 sqrt= 1.099541456 +W(HF) = 0.827135734 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.224050 0.000000 + 1 N : 0.155399 -0.000000 + 2 O : -0.166048 0.000000 + 3 H : 0.234699 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.802262 s : 3.802262 + pz : 1.638563 p : 4.348435 + px : 1.330570 + py : 1.379301 + dz2 : 0.013697 d : 0.064576 + dxz : 0.012765 + dyz : 0.007448 + dx2y2 : 0.018821 + dxy : 0.011845 + f0 : 0.001033 f : 0.008778 + f+1 : 0.001744 + f-1 : 0.000875 + f+2 : 0.001013 + f-2 : 0.001299 + f+3 : 0.001276 + f-3 : 0.001538 + 1 N s : 3.902522 s : 3.902522 + pz : 0.824824 p : 2.739253 + px : 0.801550 + py : 1.112879 + dz2 : 0.036074 d : 0.171017 + dxz : 0.036774 + dyz : 0.027116 + dx2y2 : 0.045104 + dxy : 0.025948 + f0 : 0.001636 f : 0.031809 + f+1 : 0.004620 + f-1 : 0.004643 + f+2 : 0.003023 + f-2 : 0.005118 + f+3 : 0.005555 + f-3 : 0.007215 + 2 O s : 3.852276 s : 3.852276 + pz : 1.255561 p : 4.220224 + px : 1.612562 + py : 1.352101 + dz2 : 0.020029 d : 0.083468 + dxz : 0.010934 + dyz : 0.016179 + dx2y2 : 0.015874 + dxy : 0.020451 + f0 : 0.000856 f : 0.010080 + f+1 : 0.000712 + f-1 : 0.002075 + f+2 : 0.001689 + f-2 : 0.001467 + f+3 : 0.001603 + f-3 : 0.001678 + 3 H s : 0.657006 s : 0.657006 + pz : 0.043877 p : 0.088968 + px : 0.030408 + py : 0.014682 + dz2 : 0.001268 d : 0.019327 + dxz : 0.000118 + dyz : 0.007518 + dx2y2 : 0.000427 + dxy : 0.009996 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.610052 0.000000 + 1 N : -0.321999 -0.000000 + 2 O : 0.280852 0.000000 + 3 H : -0.568904 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.120299 s : 3.120299 + pz : 1.335820 p : 3.852006 + px : 1.228001 + py : 1.288185 + dz2 : 0.045998 d : 0.321393 + dxz : 0.082216 + dyz : 0.037756 + dx2y2 : 0.084163 + dxy : 0.071261 + f0 : 0.009151 f : 0.096250 + f+1 : 0.017740 + f-1 : 0.002302 + f+2 : 0.015993 + f-2 : 0.015331 + f+3 : 0.011342 + f-3 : 0.024390 + 1 N s : 3.014814 s : 3.014814 + pz : 0.832093 p : 2.881381 + px : 0.861709 + py : 1.187579 + dz2 : 0.164705 d : 0.971613 + dxz : 0.216412 + dyz : 0.166476 + dx2y2 : 0.247592 + dxy : 0.176428 + f0 : 0.031192 f : 0.454192 + f+1 : 0.048355 + f-1 : 0.055294 + f+2 : 0.076293 + f-2 : 0.081111 + f+3 : 0.074272 + f-3 : 0.087675 + 2 O s : 3.305677 s : 3.305677 + pz : 1.178154 p : 3.934010 + px : 1.355588 + py : 1.400269 + dz2 : 0.050322 d : 0.354779 + dxz : 0.052452 + dyz : 0.089194 + dx2y2 : 0.106594 + dxy : 0.056216 + f0 : 0.010255 f : 0.124682 + f+1 : 0.005925 + f-1 : 0.022629 + f+2 : 0.026479 + f-2 : 0.020696 + f+3 : 0.013516 + f-3 : 0.025183 + 3 H s : 0.618669 s : 0.618669 + pz : 0.157722 p : 0.559403 + px : 0.136416 + py : 0.265265 + dz2 : 0.046011 d : 0.390831 + dxz : 0.028591 + dyz : 0.109423 + dx2y2 : 0.098802 + dxy : 0.108005 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2241 8.0000 -0.2241 2.1905 1.7391 0.4514 + 1 N 6.8446 7.0000 0.1554 2.8103 2.3354 0.4749 + 2 O 8.1660 8.0000 -0.1660 2.1076 1.6093 0.4983 + 3 H 0.7653 1.0000 0.2347 1.0313 0.9571 0.0741 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7710 B( 0-O , 2-O ) : 0.1010 B( 0-O , 3-H ) : 0.8672 +B( 1-N , 2-O ) : 1.4914 + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 54.029 sec + +Fock Matrix Formation ... 0.205 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 1.835 sec ( 3.4%) +State Vector Update ... 0.083 sec ( 0.2%) +Sigma-vector construction ... 37.203 sec ( 68.9%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.023 sec ( 0.1% of sigma) + (0-ext) ... 0.067 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.025 sec ( 0.1% of sigma) + (2-ext) ... 0.922 sec ( 2.5% of sigma) + (4-ext) ... 20.657 sec ( 55.5% of sigma) + ... 1.317 sec ( 3.5% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.107 sec ( 0.3% of sigma) + Fock-dressing ... 2.114 sec ( 5.7% of sigma) + (ik|jl)-dressing ... 0.073 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.297 sec ( 25.0% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.643 sec ( 12.3% of ALL) + I/O of integral and amplitudes ... 0.658 sec ( 9.9% of (T)) + External N**7 contributions ... 3.880 sec ( 58.4% of (T)) + Internal N**7 contributions ... 0.307 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.548 sec ( 23.3% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.445692660186 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.019.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.019.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.378411, -0.300466 -0.391625) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.74022 -0.22143 -0.52546 +Nuclear contribution : -0.84402 0.69119 0.83529 + ----------------------------------------- +Total Dipole Moment : -0.10379 0.46976 0.30983 + ----------------------------------------- +Magnitude (a.u.) : 0.57222 +Magnitude (Debye) : 1.45448 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.767536 0.428145 0.374186 +Rotational constants in MHz : 82968.635706 12835.467493 11217.799302 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.132945 0.462551 0.309535 +x,y,z [Debye]: -0.337920 1.175712 0.786775 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.378411, -0.300466 -0.391625) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.75425 -0.14552 -0.60392 +Nuclear contribution : -0.84402 0.69119 0.83529 + ----------------------------------------- +Total Dipole Moment : -0.08977 0.54567 0.23137 + ----------------------------------------- +Magnitude (a.u.) : 0.59946 +Magnitude (Debye) : 1.52370 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.767536 0.428145 0.374186 +Rotational constants in MHz : 82968.635706 12835.467493 11217.799302 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.053549 0.530237 0.274462 +x,y,z [Debye]: -0.136111 1.347755 0.697628 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 20 * + * * + * Dihedral ( 2, 1, 0, 3) : -24.54545455 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0330322402 RMS(Int)= 0.0008637419 + Iter 1: RMS(Cart)= 0.0001997997 RMS(Int)= 0.0000127415 + Iter 2: RMS(Cart)= 0.0000029473 RMS(Int)= 0.0000001888 + Iter 3: RMS(Cart)= 0.0000000437 RMS(Int)= 0.0000000028 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4249 0.000000 + 2. B(O 2,N 1) 1.1827 0.000000 + 3. B(H 3,O 0) 0.9767 0.000000 + 4. A(N 1,O 0,H 3) 104.8623 0.000000 + 5. A(O 0,N 1,O 2) 112.9386 0.000000 + 6. D(O 2,N 1,O 0,H 3) -24.5455 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.686219 -0.375851 0.468933 + N 0.508997 -0.588437 -0.277123 + O 0.875822 0.381314 -0.846146 + H -0.698599 0.582974 0.654337 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.296765 -0.710256 0.886154 + 1 N 7.0000 0 14.007 0.961864 -1.111984 -0.523687 + 2 O 8.0000 0 15.999 1.655064 0.720578 -1.598985 + 3 H 1.0000 0 1.008 -1.320161 1.101662 1.236518 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.423586666027 0.00000000 0.00000000 + O 2 1 0 1.181361012512 113.10498772 0.00000000 + H 1 2 3 0.974677876354 105.05573688 327.27272752 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.690188926693 0.00000000 0.00000000 + O 2 1 0 2.232448778940 113.10498772 0.00000000 + H 1 2 3 1.841874255101 105.05573688 327.27272752 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2243 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2717 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.603857784848 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.6038577848 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.501e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7155786060 0.000000000000 0.00197240 0.00005310 0.0147926 0.7000 + 1 -204.7163319261 -0.000753320101 0.00176421 0.00004924 0.0123372 0.7000 + ***Turning on DIIS*** + 2 -204.7169877670 -0.000655840935 0.00469461 0.00013588 0.0101088 0.0000 + 3 -204.7202839032 -0.003296136200 0.00213368 0.00006138 0.0044228 0.0000 + 4 -204.7185386894 0.001745213851 0.00099711 0.00003137 0.0018200 0.0000 + 5 -204.7202812410 -0.001742551631 0.00090355 0.00003650 0.0009846 0.0000 + 6 -204.7195846443 0.000696596736 0.00055192 0.00002423 0.0005812 0.0000 + 7 -204.7192947067 0.000289937596 0.00033425 0.00001536 0.0002914 0.0000 + 8 -204.7200020630 -0.000707356359 0.00019440 0.00000880 0.0001867 0.0000 + 9 -204.7195009317 0.000501131345 0.00010407 0.00000327 0.0000759 0.0000 + 10 -204.7195836108 -0.000082679113 0.00003501 0.00000099 0.0000474 0.0000 + 11 -204.7196449341 -0.000061323341 0.00002079 0.00000055 0.0000245 0.0000 + 12 -204.7195997329 0.000045201194 0.00000644 0.00000018 0.0000060 0.0000 + 13 -204.7196128547 -0.000013121724 0.00000168 0.00000006 0.0000026 0.0000 + 14 -204.7196107141 0.000002140549 0.00000089 0.00000003 0.0000013 0.0000 + 15 -204.7196090573 0.000001656814 0.00000055 0.00000002 0.0000011 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 16 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71961111 Eh -5570.70383 eV + +Components: +Nuclear Repulsion : 69.60385778 Eh 1894.01726 eV +Electronic Energy : -274.32346890 Eh -7464.72109 eV +One Electron Energy: -418.81472392 Eh -11396.52803 eV +Two Electron Energy: 144.49125503 Eh 3931.80694 eV + +Virial components: +Potential Energy : -408.94715742 Eh -11128.01789 eV +Kinetic Energy : 204.22754631 Eh 5557.31406 eV +Virial Ratio : 2.00240939 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -2.0533e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.4720e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.3137e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.0566e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.672430 -562.5254 + 1 1.0000 -20.643492 -561.7380 + 2 1.0000 -15.804645 -430.0662 + 3 1.0000 -1.608328 -43.7648 + 4 1.0000 -1.399482 -38.0818 + 5 1.0000 -0.964579 -26.2475 + 6 1.0000 -0.774045 -21.0628 + 7 1.0000 -0.740844 -20.1594 + 8 1.0000 -0.690141 -18.7797 + 9 1.0000 -0.611915 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195.2824 + 145 0.0000 7.239481 196.9963 + 146 0.0000 7.264519 197.6776 + 147 0.0000 7.309452 198.9003 + 148 0.0000 7.396484 201.2686 + 149 0.0000 7.451578 202.7678 + 150 0.0000 7.482507 203.6094 + 151 0.0000 7.507007 204.2761 + 152 0.0000 7.584029 206.3719 + 153 0.0000 7.657039 208.3586 + 154 0.0000 7.854178 213.7231 + 155 0.0000 7.868507 214.1129 + 156 0.0000 8.220240 223.6841 + 157 0.0000 8.319657 226.3894 + 158 0.0000 14.095331 383.5534 + 159 0.0000 15.050522 409.5455 + 160 0.0000 15.660705 426.1494 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.672430 -562.5254 + 1 1.0000 -20.643492 -561.7380 + 2 1.0000 -15.804645 -430.0662 + 3 1.0000 -1.608328 -43.7648 + 4 1.0000 -1.399482 -38.0818 + 5 1.0000 -0.964579 -26.2475 + 6 1.0000 -0.774045 -21.0628 + 7 1.0000 -0.740844 -20.1594 + 8 1.0000 -0.690141 -18.7797 + 9 1.0000 -0.611915 -16.6511 + 10 1.0000 -0.533413 -14.5149 + 11 1.0000 -0.472794 -12.8654 + 12 0.0000 0.031629 0.8607 + 13 0.0000 0.073609 2.0030 + 14 0.0000 0.094605 2.5743 + 15 0.0000 0.112211 3.0534 + 16 0.0000 0.121922 3.3177 + 17 0.0000 0.145971 3.9721 + 18 0.0000 0.157884 4.2962 + 19 0.0000 0.169286 4.6065 + 20 0.0000 0.183518 4.9938 + 21 0.0000 0.194628 5.2961 + 22 0.0000 0.204127 5.5546 + 23 0.0000 0.233206 6.3458 + 24 0.0000 0.255146 6.9429 + 25 0.0000 0.298204 8.1145 + 26 0.0000 0.308847 8.4042 + 27 0.0000 0.341560 9.2943 + 28 0.0000 0.348962 9.4957 + 29 0.0000 0.394892 10.7455 + 30 0.0000 0.427088 11.6217 + 31 0.0000 0.513517 13.9735 + 32 0.0000 0.522344 14.2137 + 33 0.0000 0.534221 14.5369 + 34 0.0000 0.562980 15.3195 + 35 0.0000 0.616914 16.7871 + 36 0.0000 0.634867 17.2756 + 37 0.0000 0.657446 17.8900 + 38 0.0000 0.687619 18.7111 + 39 0.0000 0.700157 19.0522 + 40 0.0000 0.735162 20.0048 + 41 0.0000 0.752027 20.4637 + 42 0.0000 0.761244 20.7145 + 43 0.0000 0.789792 21.4913 + 44 0.0000 0.799986 21.7687 + 45 0.0000 0.842959 22.9381 + 46 0.0000 0.846637 23.0382 + 47 0.0000 0.875263 23.8171 + 48 0.0000 0.920150 25.0386 + 49 0.0000 0.939205 25.5571 + 50 0.0000 0.961086 26.1525 + 51 0.0000 0.996346 27.1120 + 52 0.0000 1.021913 27.8077 + 53 0.0000 1.052837 28.6492 + 54 0.0000 1.075006 29.2524 + 55 0.0000 1.085711 29.5437 + 56 0.0000 1.177462 32.0404 + 57 0.0000 1.194740 32.5105 + 58 0.0000 1.238184 33.6927 + 59 0.0000 1.277297 34.7570 + 60 0.0000 1.359787 37.0017 + 61 0.0000 1.408334 38.3227 + 62 0.0000 1.443860 39.2894 + 63 0.0000 1.504262 40.9331 + 64 0.0000 1.542297 41.9680 + 65 0.0000 1.552007 42.2322 + 66 0.0000 1.594053 43.3764 + 67 0.0000 1.624815 44.2135 + 68 0.0000 1.655892 45.0591 + 69 0.0000 1.742101 47.4050 + 70 0.0000 1.783479 48.5309 + 71 0.0000 1.817445 49.4552 + 72 0.0000 1.899676 51.6928 + 73 0.0000 1.939280 52.7705 + 74 0.0000 1.984821 54.0097 + 75 0.0000 2.011766 54.7429 + 76 0.0000 2.029751 55.2323 + 77 0.0000 2.093872 56.9772 + 78 0.0000 2.158814 58.7443 + 79 0.0000 2.177704 59.2583 + 80 0.0000 2.268008 61.7156 + 81 0.0000 2.306420 62.7609 + 82 0.0000 2.360484 64.2320 + 83 0.0000 2.389135 65.0117 + 84 0.0000 2.429658 66.1144 + 85 0.0000 2.443978 66.5040 + 86 0.0000 2.463571 67.0372 + 87 0.0000 2.516476 68.4768 + 88 0.0000 2.541547 69.1590 + 89 0.0000 2.553537 69.4853 + 90 0.0000 2.577633 70.1410 + 91 0.0000 2.620897 71.3182 + 92 0.0000 2.667478 72.5858 + 93 0.0000 2.675946 72.8162 + 94 0.0000 2.735339 74.4323 + 95 0.0000 2.804054 76.3022 + 96 0.0000 2.863997 77.9333 + 97 0.0000 2.956998 80.4640 + 98 0.0000 2.972921 80.8973 + 99 0.0000 3.037283 82.6487 + 100 0.0000 3.141434 85.4828 + 101 0.0000 3.166963 86.1775 + 102 0.0000 3.219820 87.6158 + 103 0.0000 3.508380 95.4679 + 104 0.0000 3.715115 101.0934 + 105 0.0000 3.868722 105.2733 + 106 0.0000 4.013551 109.2143 + 107 0.0000 4.148321 112.8816 + 108 0.0000 4.177653 113.6797 + 109 0.0000 4.276268 116.3632 + 110 0.0000 4.363788 118.7447 + 111 0.0000 4.418383 120.2303 + 112 0.0000 4.517562 122.9291 + 113 0.0000 4.560895 124.1083 + 114 0.0000 4.684040 127.4592 + 115 0.0000 4.819666 131.1498 + 116 0.0000 4.865839 132.4062 + 117 0.0000 4.880673 132.8099 + 118 0.0000 4.951401 134.7345 + 119 0.0000 5.000376 136.0672 + 120 0.0000 5.072413 138.0274 + 121 0.0000 5.106182 138.9463 + 122 0.0000 5.190368 141.2371 + 123 0.0000 5.228716 142.2806 + 124 0.0000 5.232338 142.3792 + 125 0.0000 5.290583 143.9641 + 126 0.0000 5.380840 146.4201 + 127 0.0000 5.469411 148.8302 + 128 0.0000 5.545032 150.8880 + 129 0.0000 5.682933 154.6405 + 130 0.0000 5.779569 157.2701 + 131 0.0000 5.933077 161.4472 + 132 0.0000 6.168418 167.8512 + 133 0.0000 6.404517 174.2758 + 134 0.0000 6.505458 177.0225 + 135 0.0000 6.541927 178.0149 + 136 0.0000 6.681277 181.8068 + 137 0.0000 6.719629 182.8504 + 138 0.0000 6.771087 184.2506 + 139 0.0000 6.805534 185.1880 + 140 0.0000 6.920587 188.3187 + 141 0.0000 7.099406 193.1847 + 142 0.0000 7.133461 194.1113 + 143 0.0000 7.161139 194.8645 + 144 0.0000 7.176495 195.2824 + 145 0.0000 7.239481 196.9963 + 146 0.0000 7.264519 197.6776 + 147 0.0000 7.309452 198.9003 + 148 0.0000 7.396484 201.2686 + 149 0.0000 7.451578 202.7678 + 150 0.0000 7.482507 203.6094 + 151 0.0000 7.507007 204.2761 + 152 0.0000 7.584029 206.3719 + 153 0.0000 7.657039 208.3586 + 154 0.0000 7.854178 213.7231 + 155 0.0000 7.868507 214.1129 + 156 0.0000 8.220240 223.6841 + 157 0.0000 8.319657 226.3894 + 158 0.0000 14.095331 383.5534 + 159 0.0000 15.050522 409.5455 + 160 0.0000 15.660705 426.1494 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.303539 0.000000 + 1 N : 0.345610 0.000000 + 2 O : -0.291772 0.000000 + 3 H : 0.249701 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.813493 s : 3.813493 + pz : 1.676319 p : 4.449504 + px : 1.381421 + py : 1.391764 + dz2 : 0.007936 d : 0.035326 + dxz : 0.007682 + dyz : 0.000306 + dx2y2 : 0.015863 + dxy : 0.003540 + f0 : 0.000451 f : 0.005216 + f+1 : 0.001237 + f-1 : 0.000272 + f+2 : 0.000703 + f-2 : 0.000918 + f+3 : 0.000675 + f-3 : 0.000959 + 1 N s : 3.856384 s : 3.856384 + pz : 0.724579 p : 2.622579 + px : 0.737499 + py : 1.160502 + dz2 : 0.030293 d : 0.142640 + dxz : 0.028529 + dyz : 0.024980 + dx2y2 : 0.037267 + dxy : 0.021570 + f0 : 0.001333 f : 0.032787 + f+1 : 0.004320 + f-1 : 0.005414 + f+2 : 0.003151 + f-2 : 0.005237 + f+3 : 0.005994 + f-3 : 0.007337 + 2 O s : 3.861866 s : 3.861866 + pz : 1.330315 p : 4.361395 + px : 1.650698 + py : 1.380382 + dz2 : 0.014952 d : 0.060993 + dxz : 0.003707 + dyz : 0.015250 + dx2y2 : 0.009623 + dxy : 0.017461 + f0 : 0.000316 f : 0.007519 + f+1 : 0.000138 + f-1 : 0.002042 + f+2 : 0.001329 + f-2 : 0.001002 + f+3 : 0.001297 + f-3 : 0.001395 + 3 H s : 0.644431 s : 0.644431 + pz : 0.037526 p : 0.084775 + px : 0.027372 + py : 0.019877 + dz2 : 0.000645 d : 0.021093 + dxz : -0.000705 + dyz : 0.009376 + dx2y2 : 0.000733 + dxy : 0.011044 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.595105 0.000000 + 1 N : -0.270427 0.000000 + 2 O : 0.243871 0.000000 + 3 H : -0.568549 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.114352 s : 3.114352 + pz : 1.365371 p : 3.911989 + px : 1.247698 + py : 1.298920 + dz2 : 0.039937 d : 0.289625 + dxz : 0.078320 + dyz : 0.032236 + dx2y2 : 0.074376 + dxy : 0.064756 + f0 : 0.008231 f : 0.088928 + f+1 : 0.015730 + f-1 : 0.002154 + f+2 : 0.014544 + f-2 : 0.016614 + f+3 : 0.008968 + f-3 : 0.022688 + 1 N s : 3.010735 s : 3.010735 + pz : 0.766012 p : 2.830031 + px : 0.825349 + py : 1.238671 + dz2 : 0.168711 d : 0.964309 + dxz : 0.205915 + dyz : 0.159679 + dx2y2 : 0.247699 + dxy : 0.182304 + f0 : 0.030525 f : 0.465352 + f+1 : 0.052384 + f-1 : 0.057777 + f+2 : 0.073597 + f-2 : 0.083539 + f+3 : 0.074530 + f-3 : 0.093000 + 2 O s : 3.301755 s : 3.301755 + pz : 1.209698 p : 4.016867 + px : 1.378514 + py : 1.428654 + dz2 : 0.040901 d : 0.321856 + dxz : 0.045525 + dyz : 0.075859 + dx2y2 : 0.108044 + dxy : 0.051526 + f0 : 0.008984 f : 0.115651 + f+1 : 0.004491 + f-1 : 0.018619 + f+2 : 0.023399 + f-2 : 0.019616 + f+3 : 0.012987 + f-3 : 0.027556 + 3 H s : 0.613892 s : 0.613892 + pz : 0.149390 p : 0.548586 + px : 0.136120 + py : 0.263077 + dz2 : 0.043526 d : 0.406071 + dxz : 0.027946 + dyz : 0.116914 + dx2y2 : 0.102591 + dxy : 0.115094 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3035 8.0000 -0.3035 1.8157 1.8157 -0.0000 + 1 N 6.6544 7.0000 0.3456 2.5233 2.5233 0.0000 + 2 O 8.2918 8.0000 -0.2918 1.6981 1.6981 -0.0000 + 3 H 0.7503 1.0000 0.2497 1.0134 1.0134 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8228 B( 0-O , 3-H ) : 0.9332 B( 1-N , 2-O ) : 1.6293 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.443 sec +Sum of individual times .... 2.220 sec ( 90.9%) + +Fock matrix formation .... 1.796 sec ( 73.5%) +Diagonalization .... 0.190 sec ( 7.8%) +Density matrix formation .... 0.014 sec ( 0.6%) +Population analysis .... 0.038 sec ( 1.6%) +Initial guess .... 0.009 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.2%) +DIIS solution .... 0.173 sec ( 7.1%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.203 sec +Reference energy ... -204.719610018 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.360 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.077 sec +K-integral sorting ... 5.367 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.025 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.034 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.040 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.030 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.039 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.352 sec +AO-integral generation ... 0.247 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.148 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.253 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090579490 +EMP2(bb)= -0.090579490 +EMP2(ab)= -0.515885657 + +Initial guess performed in 0.134 sec +E(0) ... -204.719610018 +E(MP2) ... -0.697044638 +Initial E(tot) ... -205.416654656 + ... 0.187697817 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.416654656 -0.697044638 -0.000000000 0.028011303 2.75 0.000001938 + *** Turning on DIIS *** + 1 -205.387511239 -0.667901221 0.029143417 0.010856980 2.73 0.058403717 + 2 -205.407064711 -0.687454693 -0.019553472 0.006288400 2.80 0.061560795 + 3 -205.410796794 -0.691186776 -0.003732083 0.002223741 2.85 0.076149924 + 4 -205.412397358 -0.692787340 -0.001600564 0.001505761 2.83 0.083245402 + 5 -205.412966330 -0.693356312 -0.000568972 0.000862112 2.91 0.089026300 + 6 -205.413075785 -0.693465767 -0.000109455 0.000534556 2.84 0.091776729 + 7 -205.413121018 -0.693511000 -0.000045233 0.000232586 2.85 0.092974280 + 8 -205.413131961 -0.693521943 -0.000010943 0.000119360 2.90 0.093421910 + 9 -205.413127667 -0.693517649 0.000004294 0.000029135 2.82 0.093553185 + 10 -205.413132740 -0.693522722 -0.000005073 0.000016737 2.79 0.093603059 + 11 -205.413130104 -0.693520086 0.000002636 0.000012247 2.79 0.093592636 + 12 -205.413131067 -0.693521049 -0.000000963 0.000008791 2.78 0.093601787 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.719610018 +E(CORR) ... -0.693521049 +E(TOT) ... -205.413131067 +Singles norm **1/2 ... 0.093601787 ( 0.046800894, 0.046800894) +T1 diagnostic ... 0.022062153 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.063224 + 10a-> 13a 10b-> 13b 0.047198 + 8a-> 13a -1a-> -1a 0.047135 + 8b-> 13b -1b-> -1b 0.047135 + 8a-> 13a 10b-> 13b 0.033038 + 10a-> 13a 8b-> 13b 0.033038 + 11a-> 13a 11b-> 13b 0.029331 + 10a-> 13a -1a-> -1a 0.028835 + 10b-> 13b -1b-> -1b 0.028835 + 5a-> 13a 5b-> 13b 0.026359 + 8a-> 13a 8b-> 22b 0.023893 + 8a-> 22a 8b-> 13b 0.023893 + 9a-> 13a 9b-> 13b 0.022200 + 8a-> 13a 9b-> 13b 0.021771 + 9a-> 13a 8b-> 13b 0.021771 + 11a-> 26a -1a-> -1a 0.021617 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034819516 + alpha-alpha-alpha ... -0.000909366 ( 2.6%) + alpha-alpha-beta ... -0.016500392 ( 47.4%) + alpha-beta -beta ... -0.016500392 ( 47.4%) + beta -beta -beta ... -0.000909366 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034819516 + +Final correlation energy ... -0.728340565 +E(CCSD) ... -205.413131067 +E(CCSD(T)) ... -205.447950583 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209735799 sqrt= 1.099879902 +W(HF) = 0.826626773 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.217496 0.000000 + 1 N : 0.153733 -0.000000 + 2 O : -0.170275 0.000000 + 3 H : 0.234039 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.800133 s : 3.800133 + pz : 1.619843 p : 4.343273 + px : 1.355881 + py : 1.367548 + dz2 : 0.014665 d : 0.065217 + dxz : 0.012684 + dyz : 0.007437 + dx2y2 : 0.019347 + dxy : 0.011085 + f0 : 0.000972 f : 0.008874 + f+1 : 0.001803 + f-1 : 0.000914 + f+2 : 0.001051 + f-2 : 0.001416 + f+3 : 0.001201 + f-3 : 0.001515 + 1 N s : 3.907005 s : 3.907005 + pz : 0.818466 p : 2.737064 + px : 0.798147 + py : 1.120451 + dz2 : 0.035989 d : 0.170366 + dxz : 0.035887 + dyz : 0.027716 + dx2y2 : 0.044717 + dxy : 0.026057 + f0 : 0.001665 f : 0.031832 + f+1 : 0.004335 + f-1 : 0.004870 + f+2 : 0.002872 + f-2 : 0.005232 + f+3 : 0.005508 + f-3 : 0.007351 + 2 O s : 3.849473 s : 3.849473 + pz : 1.288852 p : 4.226887 + px : 1.586434 + py : 1.351601 + dz2 : 0.018972 d : 0.083785 + dxz : 0.010429 + dyz : 0.017171 + dx2y2 : 0.016385 + dxy : 0.020829 + f0 : 0.000806 f : 0.010130 + f+1 : 0.000701 + f-1 : 0.002098 + f+2 : 0.001650 + f-2 : 0.001443 + f+3 : 0.001632 + f-3 : 0.001800 + 3 H s : 0.659713 s : 0.659713 + pz : 0.042336 p : 0.086958 + px : 0.031034 + py : 0.013587 + dz2 : 0.000646 d : 0.019290 + dxz : -0.000140 + dyz : 0.008423 + dx2y2 : 0.000156 + dxy : 0.010205 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.610324 0.000000 + 1 N : -0.319870 -0.000000 + 2 O : 0.280190 -0.000000 + 3 H : -0.570645 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.122647 s : 3.122647 + pz : 1.329245 p : 3.849416 + px : 1.236522 + py : 1.283649 + dz2 : 0.046786 d : 0.321306 + dxz : 0.085117 + dyz : 0.038551 + dx2y2 : 0.081298 + dxy : 0.069554 + f0 : 0.009073 f : 0.096307 + f+1 : 0.017590 + f-1 : 0.003155 + f+2 : 0.015924 + f-2 : 0.017040 + f+3 : 0.010347 + f-3 : 0.023179 + 1 N s : 3.016226 s : 3.016226 + pz : 0.822593 p : 2.880880 + px : 0.854426 + py : 1.203862 + dz2 : 0.166878 d : 0.968904 + dxz : 0.212037 + dyz : 0.162777 + dx2y2 : 0.249567 + dxy : 0.177645 + f0 : 0.031231 f : 0.453859 + f+1 : 0.047118 + f-1 : 0.056325 + f+2 : 0.073460 + f-2 : 0.081142 + f+3 : 0.074642 + f-3 : 0.089940 + 2 O s : 3.303721 s : 3.303721 + pz : 1.186906 p : 3.936316 + px : 1.340118 + py : 1.409292 + dz2 : 0.051291 d : 0.355206 + dxz : 0.050347 + dyz : 0.082781 + dx2y2 : 0.111836 + dxy : 0.058952 + f0 : 0.009749 f : 0.124567 + f+1 : 0.005567 + f-1 : 0.022603 + f+2 : 0.024296 + f-2 : 0.020106 + f+3 : 0.015081 + f-3 : 0.027164 + 3 H s : 0.618435 s : 0.618435 + pz : 0.152504 p : 0.556835 + px : 0.136945 + py : 0.267386 + dz2 : 0.043046 d : 0.395375 + dxz : 0.027822 + dyz : 0.111499 + dx2y2 : 0.101856 + dxy : 0.111153 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2175 8.0000 -0.2175 2.1943 1.7407 0.4536 + 1 N 6.8463 7.0000 0.1537 2.8101 2.3355 0.4746 + 2 O 8.1703 8.0000 -0.1703 2.1016 1.6031 0.4985 + 3 H 0.7660 1.0000 0.2340 1.0315 0.9572 0.0743 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7772 B( 0-O , 2-O ) : 0.1021 B( 0-O , 3-H ) : 0.8613 +B( 1-N , 2-O ) : 1.4817 + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 51.632 sec + +Fock Matrix Formation ... 0.203 sec ( 0.4%) +Initial Guess ... 0.134 sec ( 0.3%) +DIIS Solver ... 1.485 sec ( 2.9%) +State Vector Update ... 0.077 sec ( 0.1%) +Sigma-vector construction ... 35.072 sec ( 67.9%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.023 sec ( 0.1% of sigma) + (0-ext) ... 0.062 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.024 sec ( 0.1% of sigma) + (2-ext) ... 0.856 sec ( 2.4% of sigma) + (4-ext) ... 19.515 sec ( 55.6% of sigma) + ... 1.288 sec ( 3.7% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.007 sec ( 0.0% of sigma) + (1-ext) ... 0.099 sec ( 0.3% of sigma) + Fock-dressing ... 1.987 sec ( 5.7% of sigma) + (ik|jl)-dressing ... 0.068 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 8.701 sec ( 24.8% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.806 sec ( 13.2% of ALL) + I/O of integral and amplitudes ... 0.645 sec ( 9.5% of (T)) + External N**7 contributions ... 3.895 sec ( 57.2% of (T)) + Internal N**7 contributions ... 0.308 sec ( 4.5% of (T)) + N**6 triples energy contributions ... 1.555 sec ( 22.8% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.447950582843 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.008903237 0.001388615 -0.008253630 + 2 N : 0.009179558 -0.000531890 0.006914174 + 3 O : -0.003954622 -0.000504983 -0.005851725 + 4 H : 0.003678301 -0.000351741 0.007191181 + +Norm of the cartesian gradient ... 0.019929243 +RMS gradient ... 0.005753077 +MAX gradient ... 0.009179558 + +------- +TIMINGS +------- + +Total numerical gradient time ... 334.986 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 451.96 cm**-1 + 7: 647.75 cm**-1 + 8: 833.41 cm**-1 + 9: 1309.63 cm**-1 + 10: 1662.75 cm**-1 + 11: 3626.79 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 0.146589 -0.144092 -0.187640 0.056177 -0.025478 0.000085 + 1 0.008810 -0.095295 0.118156 0.074864 0.062031 -0.060861 + 2 -0.006916 0.225984 0.117772 -0.030489 0.012672 -0.011585 + 3 -0.114755 -0.018719 0.342825 0.060029 -0.075378 0.001768 + 4 -0.044289 0.106108 -0.207603 -0.025201 -0.535045 -0.000779 + 5 -0.015322 -0.122069 -0.207385 -0.062214 0.213338 -0.001062 + 6 -0.026192 0.213618 -0.132770 -0.053937 0.126182 -0.000483 + 7 0.018503 0.002081 0.046445 -0.050072 0.407255 -0.000140 + 8 0.077482 -0.096729 0.109396 0.055714 -0.221571 0.000339 + 9 -0.316334 -0.843401 0.321698 -0.869698 -0.550923 -0.018241 + 10 0.181919 0.005045 0.272277 -0.043323 -0.013632 0.979019 + 11 -0.907098 -0.355295 -0.723842 0.464143 0.351141 0.193248 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 451.96 0.020788 105.05 0.014353 (-0.116587 -0.010275 -0.025598) + 7: 647.75 0.008079 40.83 0.003892 (-0.008915 0.023913 -0.056929) + 8: 833.41 0.052317 264.39 0.019590 ( 0.100855 0.003220 -0.096993) + 9: 1309.63 0.001608 8.13 0.000383 (-0.007302 0.018164 0.000005) + 10: 1662.75 0.030489 154.08 0.005722 (-0.054929 -0.019338 0.048280) + 11: 3626.79 0.007547 38.14 0.000649 (-0.009729 0.019174 0.013678) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 451.96 E(vib) ... 0.16 +freq. 647.75 E(vib) ... 0.09 +freq. 833.41 E(vib) ... 0.04 +freq. 1309.63 E(vib) ... 0.01 +freq. 1662.75 E(vib) ... 0.00 +freq. 3626.79 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.44795058 Eh +Zero point energy ... 0.01943800 Eh 12.20 kcal/mol +Thermal vibrational correction ... 0.00048024 Eh 0.30 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42519980 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00331278 Eh 2.08 kcal/mol +Non-thermal (ZPE) correction 0.01943800 Eh 12.20 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02275079 Eh 14.28 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42519980 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.42425559 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.746345 0.429768 0.373608 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00065572 Eh 0.41 kcal/mol +Rotational entropy ... 0.00989735 Eh 6.21 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02835539 Eh 17.79 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00989735 Eh 6.21 kcal/mol| +| sn= 2 | S(rot)= 0.00924289 Eh 5.80 kcal/mol| +| sn= 3 | S(rot)= 0.00886006 Eh 5.56 kcal/mol| +| sn= 4 | S(rot)= 0.00858844 Eh 5.39 kcal/mol| +| sn= 5 | S(rot)= 0.00837775 Eh 5.26 kcal/mol| +| sn= 6 | S(rot)= 0.00820561 Eh 5.15 kcal/mol| +| sn= 7 | S(rot)= 0.00806006 Eh 5.06 kcal/mol| +| sn= 8 | S(rot)= 0.00793398 Eh 4.98 kcal/mol| +| sn= 9 | S(rot)= 0.00782277 Eh 4.91 kcal/mol| +| sn=10 | S(rot)= 0.00772329 Eh 4.85 kcal/mol| +| sn=11 | S(rot)= 0.00763330 Eh 4.79 kcal/mol| +| sn=12 | S(rot)= 0.00755115 Eh 4.74 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.42425559 Eh +Total entropy correction ... -0.02835539 Eh -17.79 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.45261097 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00466039 Eh -2.92 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.447950581 Eh +Current gradient norm .... 0.019929148 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.022452052 0.129528589 0.199834324 0.470569846 0.527074238 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999652987 +Lowest eigenvalues of augmented Hessian: + -0.000106769 0.125859707 0.198881992 0.470536690 0.526992627 +Length of the computed step .... 0.026351243 +The final length of the internal step .... 0.026351243 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0107578499 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0059544067 RMS(Int)= 0.0107581346 + Iter 1: RMS(Cart)= 0.0000044524 RMS(Int)= 0.0000085414 + Iter 2: RMS(Cart)= 0.0000000248 RMS(Int)= 0.0000000267 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000007 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0018743976 0.0001000000 NO + MAX gradient 0.0039810138 0.0003000000 NO + RMS step 0.0107578499 0.0020000000 NO + MAX step 0.0257756609 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0136 Max(Angles) 0.26 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4249 0.003981 -0.0136 1.4113 + 2. B(O 2,N 1) 1.1827 0.001175 0.0012 1.1838 + 3. B(H 3,O 0) 0.9767 0.000973 -0.0007 0.9760 + 4. A(N 1,O 0,H 3) 104.86 0.000722 0.11 104.97 + 5. A(O 0,N 1,O 2) 112.94 -0.001544 0.26 113.19 + 6. D(O 2,N 1,O 0,H 3) -24.55 -0.014301 0.00 -24.55 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.681154 -0.376496 0.465636 + N 0.502892 -0.586557 -0.272983 + O 0.873893 0.381581 -0.844442 + H -0.695630 0.581471 0.651788 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.287194 -0.711474 0.879925 + 1 N 7.0000 0 14.007 0.950328 -1.108431 -0.515862 + 2 O 8.0000 0 15.999 1.651418 0.721084 -1.595764 + 3 H 1.0000 0 1.008 -1.314550 1.098821 1.231701 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.411257218467 0.00000000 0.00000000 + O 2 1 0 1.183849157359 113.19404570 0.00000000 + H 1 2 3 0.975993285931 104.97308403 335.45454535 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.666889647423 0.00000000 0.00000000 + O 2 1 0 2.237150691281 113.19404570 0.00000000 + H 1 2 3 1.844360018956 104.97308403 335.45454535 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2243 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2717 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.855639731738 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.478e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7205971949 0.000000000000 0.00042178 0.00001090 0.0023286 0.7000 + 1 -204.7206232628 -0.000026067826 0.00034750 0.00000917 0.0017866 0.7000 + ***Turning on DIIS*** + 2 -204.7206449304 -0.000021667646 0.00089076 0.00002387 0.0013573 0.0000 + 3 -204.7202332046 0.000411725768 0.00034560 0.00001094 0.0003379 0.0000 + 4 -204.7209341297 -0.000700925100 0.00015953 0.00000362 0.0001423 0.0000 + 5 -204.7209665657 -0.000032435980 0.00003209 0.00000109 0.0000580 0.0000 + 6 -204.7205114662 0.000455099545 0.00002702 0.00000066 0.0000416 0.0000 + 7 -204.7207150331 -0.000203566900 0.00000583 0.00000024 0.0000116 0.0000 + 8 -204.7207255520 -0.000010518975 0.00000423 0.00000013 0.0000066 0.0000 + 9 -204.7206988567 0.000026695369 0.00000182 0.00000007 0.0000025 0.0000 + 10 -204.7207220192 -0.000023162565 0.00000095 0.00000003 0.0000012 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + +Total Energy : -204.72071595 Eh -5570.73389 eV + Last Energy change ... 6.0656e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.8278e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.226 sec +Reference energy ... -204.720716215 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.403 sec +AO-integral generation ... 0.144 sec +Half transformation ... 0.080 sec +K-integral sorting ... 5.400 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.028 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.040 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.039 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.036 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.034 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.024 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.044 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.035 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.394 sec +AO-integral generation ... 0.284 sec +Half transformation ... 0.042 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.164 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.261 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090482476 +EMP2(bb)= -0.090482476 +EMP2(ab)= -0.515070148 + +Initial guess performed in 0.150 sec +E(0) ... -204.720716215 +E(MP2) ... -0.696035100 +Initial E(tot) ... -205.416751315 + ... 0.186694191 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.416751315 -0.696035100 -0.000000000 0.028267348 4.57 0.000001232 + *** Turning on DIIS *** + 1 -205.388038908 -0.667322694 0.028712406 0.010885597 3.33 0.057958087 + 2 -205.407422754 -0.686706539 -0.019383846 0.006358426 3.61 0.061210109 + 3 -205.411121241 -0.690405026 -0.003698487 0.002232495 3.86 0.075637303 + 4 -205.412702526 -0.691986311 -0.001581285 0.001397104 3.99 0.082649154 + 5 -205.413255079 -0.692538864 -0.000552553 0.000805304 3.75 0.088245634 + 6 -205.413359264 -0.692643049 -0.000104185 0.000500551 4.20 0.090845750 + 7 -205.413401366 -0.692685151 -0.000042102 0.000222441 4.10 0.091940169 + 8 -205.413410981 -0.692694766 -0.000009615 0.000113960 4.45 0.092346297 + 9 -205.413406972 -0.692690757 0.000004009 0.000027497 5.27 0.092467224 + 10 -205.413411624 -0.692695409 -0.000004652 0.000017297 3.89 0.092512638 + 11 -205.413409163 -0.692692949 0.000002460 0.000012727 4.23 0.092502658 + 12 -205.413410089 -0.692693875 -0.000000926 0.000009084 3.72 0.092510915 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.720716215 +E(CORR) ... -0.692693875 +E(TOT) ... -205.413410089 +Singles norm **1/2 ... 0.092510915 ( 0.046255457, 0.046255457) +T1 diagnostic ... 0.021805032 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.061211 + 10a-> 13a 10b-> 13b 0.049136 + 8b-> 13b -1b-> -1b 0.047589 + 8a-> 13a -1a-> -1a 0.047589 + 8a-> 13a 10b-> 13b 0.033004 + 10a-> 13a 8b-> 13b 0.033004 + 11a-> 13a 11b-> 13b 0.029751 + 10a-> 13a -1a-> -1a 0.026293 + 10b-> 13b -1b-> -1b 0.026293 + 5a-> 13a 5b-> 13b 0.025713 + 8a-> 13a 8b-> 22b 0.023297 + 8a-> 22a 8b-> 13b 0.023297 + 11b-> 26b -1b-> -1b 0.022423 + 11a-> 26a -1a-> -1a 0.022423 + 10a-> 22a 10b-> 13b 0.022370 + 10a-> 13a 10b-> 22b 0.022370 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034592145 + alpha-alpha-alpha ... -0.000906574 ( 2.6%) + alpha-alpha-beta ... -0.016389499 ( 47.4%) + alpha-beta -beta ... -0.016389499 ( 47.4%) + beta -beta -beta ... -0.000906574 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034592145 + +Final correlation energy ... -0.727286020 +E(CCSD) ... -205.413410089 +E(CCSD(T)) ... -205.448002235 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.208310011 sqrt= 1.099231555 +W(HF) = 0.827602181 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 71.314 sec + +Fock Matrix Formation ... 0.226 sec ( 0.3%) +Initial Guess ... 0.150 sec ( 0.2%) +DIIS Solver ... 2.887 sec ( 4.0%) +State Vector Update ... 0.142 sec ( 0.2%) +Sigma-vector construction ... 49.923 sec ( 70.0%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (0-ext) ... 0.087 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.030 sec ( 0.1% of sigma) + (2-ext) ... 1.098 sec ( 2.2% of sigma) + (4-ext) ... 29.635 sec ( 59.4% of sigma) + ... 2.073 sec ( 4.2% of sigma) + ... 0.003 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.134 sec ( 0.3% of sigma) + Fock-dressing ... 2.555 sec ( 5.1% of sigma) + (ik|jl)-dressing ... 0.095 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 11.317 sec ( 22.7% of sigma) + Pair energies ... 0.008 sec ( 0.0% of sigma) +Total Time for computing (T) ... 9.734 sec ( 13.6% of ALL) + I/O of integral and amplitudes ... 0.961 sec ( 9.9% of (T)) + External N**7 contributions ... 5.161 sec ( 53.0% of (T)) + Internal N**7 contributions ... 0.410 sec ( 4.2% of (T)) + N**6 triples energy contributions ... 2.033 sec ( 20.9% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.448002234643 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.006068945 0.000920878 -0.010364889 + 2 N : 0.005800639 0.002315568 0.009047910 + 3 O : -0.003929882 -0.001889646 -0.005765380 + 4 H : 0.004198188 -0.001346800 0.007082360 + +Norm of the cartesian gradient ... 0.019693598 +RMS gradient ... 0.005685052 +MAX gradient ... 0.010364889 + +------- +TIMINGS +------- + +Total numerical gradient time ... 648.684 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.448002235 Eh +Current gradient norm .... 0.019693598 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999023 +Lowest eigenvalues of augmented Hessian: + -0.000000289 0.130803060 0.201739222 0.470777688 0.525284079 +Length of the computed step .... 0.001398033 +The final length of the internal step .... 0.001398033 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0005707444 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0003233603 RMS(Int)= 0.0005707446 + Iter 1: RMS(Cart)= 0.0000000149 RMS(Int)= 0.0000000221 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000516535 0.0000050000 NO + RMS gradient 0.0000877918 0.0001000000 YES + MAX gradient 0.0002118342 0.0003000000 YES + RMS step 0.0005707444 0.0020000000 YES + MAX step 0.0013659642 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0007 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4113 -0.000212 0.0007 1.4120 + 2. B(O 2,N 1) 1.1838 0.000006 -0.0001 1.1837 + 3. B(H 3,O 0) 0.9760 -0.000034 0.0000 0.9760 + 4. A(N 1,O 0,H 3) 104.97 -0.000014 -0.01 104.96 + 5. A(O 0,N 1,O 2) 113.19 -0.000003 -0.00 113.19 + 6. D(O 2,N 1,O 0,H 3) -24.55 -0.014864 -0.00 -24.55 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.681443 -0.376475 0.465835 + N 0.503194 -0.586582 -0.273203 + O 0.874042 0.381533 -0.844561 + H -0.695791 0.581523 0.651929 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.287741 -0.711435 0.880301 + 1 N 7.0000 0 14.007 0.950898 -1.108478 -0.516280 + 2 O 8.0000 0 15.999 1.651699 0.720994 -1.595989 + 3 H 1.0000 0 1.008 -1.314854 1.098920 1.231967 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.411980055611 0.00000000 0.00000000 + O 2 1 0 1.183733178525 113.18995933 0.00000000 + H 1 2 3 0.976010855552 104.96245521 335.45454535 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.668255611664 0.00000000 0.00000000 + O 2 1 0 2.236931523049 113.18995933 0.00000000 + H 1 2 3 1.844393220727 104.96245521 335.45454535 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2243 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2717 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.842913846984 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.8429138470 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.479e-04 +Time for diagonalization ... 0.005 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.007 sec +Total time needed ... 0.017 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7206680631 0.000000000000 0.00002272 0.00000057 0.0001225 0.7000 + 1 -204.7206681380 -0.000000074921 0.00001875 0.00000048 0.0000944 0.7000 + ***Turning on DIIS*** + 2 -204.7206682004 -0.000000062390 0.00004890 0.00000128 0.0000720 0.0000 + 3 -204.7206804036 -0.000012203199 0.00001568 0.00000056 0.0000172 0.0000 + 4 -204.7206584657 0.000021937916 0.00000767 0.00000019 0.0000056 0.0000 + 5 -204.7206667788 -0.000008313128 0.00000176 0.00000006 0.0000018 0.0000 + 6 -204.7206764343 -0.000009655514 0.00000132 0.00000003 0.0000018 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72066761 Eh -5570.73258 eV + +Components: +Nuclear Repulsion : 69.84291385 Eh 1900.52231 eV +Electronic Energy : -274.56358146 Eh -7471.25488 eV +One Electron Energy: -419.28150080 Eh -11409.22967 eV +Two Electron Energy: 144.71791934 Eh 3937.97479 eV + +Virial components: +Potential Energy : -408.96671799 Eh -11128.55016 eV +Kinetic Energy : 204.24605038 Eh 5557.81758 eV +Virial Ratio : 2.00232375 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 8.8244e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.2084e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.3165e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.4442e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.669747 -562.4524 + 1 1.0000 -20.645830 -561.8016 + 2 1.0000 -15.802972 -430.0207 + 3 1.0000 -1.608490 -43.7692 + 4 1.0000 -1.403688 -38.1963 + 5 1.0000 -0.965338 -26.2682 + 6 1.0000 -0.775688 -21.1075 + 7 1.0000 -0.741708 -20.1829 + 8 1.0000 -0.691586 -18.8190 + 9 1.0000 -0.610953 -16.6249 + 10 1.0000 -0.533742 -14.5239 + 11 1.0000 -0.473088 -12.8734 + 12 0.0000 0.031402 0.8545 + 13 0.0000 0.074850 2.0368 + 14 0.0000 0.094879 2.5818 + 15 0.0000 0.112398 3.0585 + 16 0.0000 0.121711 3.3119 + 17 0.0000 0.145806 3.9676 + 18 0.0000 0.157542 4.2869 + 19 0.0000 0.169565 4.6141 + 20 0.0000 0.183198 4.9851 + 21 0.0000 0.194869 5.3026 + 22 0.0000 0.204586 5.5671 + 23 0.0000 0.233480 6.3533 + 24 0.0000 0.255101 6.9416 + 25 0.0000 0.299602 8.1526 + 26 0.0000 0.311841 8.4856 + 27 0.0000 0.343161 9.3379 + 28 0.0000 0.349890 9.5210 + 29 0.0000 0.394859 10.7447 + 30 0.0000 0.428500 11.6601 + 31 0.0000 0.514144 13.9906 + 32 0.0000 0.522668 14.2225 + 33 0.0000 0.534435 14.5427 + 34 0.0000 0.563349 15.3295 + 35 0.0000 0.617313 16.7979 + 36 0.0000 0.635054 17.2807 + 37 0.0000 0.657645 17.8954 + 38 0.0000 0.687632 18.7114 + 39 0.0000 0.700679 19.0665 + 40 0.0000 0.733973 19.9724 + 41 0.0000 0.752497 20.4765 + 42 0.0000 0.760743 20.7009 + 43 0.0000 0.790399 21.5078 + 44 0.0000 0.799373 21.7520 + 45 0.0000 0.844241 22.9730 + 46 0.0000 0.847309 23.0565 + 47 0.0000 0.875716 23.8294 + 48 0.0000 0.920119 25.0377 + 49 0.0000 0.939114 25.5546 + 50 0.0000 0.960245 26.1296 + 51 0.0000 0.996430 27.1142 + 52 0.0000 1.021723 27.8025 + 53 0.0000 1.053133 28.6572 + 54 0.0000 1.075820 29.2745 + 55 0.0000 1.086263 29.5587 + 56 0.0000 1.179035 32.0832 + 57 0.0000 1.195484 32.5308 + 58 0.0000 1.240127 33.7456 + 59 0.0000 1.277674 34.7673 + 60 0.0000 1.356263 36.9058 + 61 0.0000 1.409455 38.3532 + 62 0.0000 1.443556 39.2811 + 63 0.0000 1.503675 40.9171 + 64 0.0000 1.541944 41.9584 + 65 0.0000 1.554838 42.3093 + 66 0.0000 1.596228 43.4356 + 67 0.0000 1.627169 44.2775 + 68 0.0000 1.656621 45.0789 + 69 0.0000 1.744695 47.4756 + 70 0.0000 1.786131 48.6031 + 71 0.0000 1.819242 49.5041 + 72 0.0000 1.899220 51.6804 + 73 0.0000 1.941915 52.8422 + 74 0.0000 1.986350 54.0513 + 75 0.0000 2.014099 54.8064 + 76 0.0000 2.033282 55.3284 + 77 0.0000 2.097278 57.0698 + 78 0.0000 2.159283 58.7571 + 79 0.0000 2.177581 59.2550 + 80 0.0000 2.270574 61.7855 + 81 0.0000 2.306966 62.7757 + 82 0.0000 2.363023 64.3011 + 83 0.0000 2.388761 65.0015 + 84 0.0000 2.428545 66.0841 + 85 0.0000 2.444687 66.5233 + 86 0.0000 2.464828 67.0714 + 87 0.0000 2.522595 68.6433 + 88 0.0000 2.542912 69.1962 + 89 0.0000 2.553361 69.4805 + 90 0.0000 2.576950 70.1224 + 91 0.0000 2.622938 71.3738 + 92 0.0000 2.668920 72.6250 + 93 0.0000 2.676961 72.8438 + 94 0.0000 2.738240 74.5113 + 95 0.0000 2.805946 76.3537 + 96 0.0000 2.869354 78.0791 + 97 0.0000 2.963373 80.6375 + 98 0.0000 2.982906 81.1690 + 99 0.0000 3.046166 82.8904 + 100 0.0000 3.147602 85.6506 + 101 0.0000 3.162974 86.0689 + 102 0.0000 3.222530 87.6895 + 103 0.0000 3.517257 95.7094 + 104 0.0000 3.716531 101.1320 + 105 0.0000 3.874290 105.4248 + 106 0.0000 4.015602 109.2701 + 107 0.0000 4.148322 112.8816 + 108 0.0000 4.178581 113.7050 + 109 0.0000 4.281533 116.5064 + 110 0.0000 4.365618 118.7945 + 111 0.0000 4.422006 120.3289 + 112 0.0000 4.516463 122.8992 + 113 0.0000 4.562276 124.1458 + 114 0.0000 4.690357 127.6311 + 115 0.0000 4.821464 131.1987 + 116 0.0000 4.871640 132.5641 + 117 0.0000 4.880650 132.8092 + 118 0.0000 4.954661 134.8232 + 119 0.0000 5.004184 136.1708 + 120 0.0000 5.074279 138.0782 + 121 0.0000 5.110723 139.0698 + 122 0.0000 5.193441 141.3207 + 123 0.0000 5.230835 142.3382 + 124 0.0000 5.232629 142.3871 + 125 0.0000 5.291270 143.9828 + 126 0.0000 5.387667 146.6059 + 127 0.0000 5.478851 149.0871 + 128 0.0000 5.545691 150.9059 + 129 0.0000 5.684517 154.6836 + 130 0.0000 5.782335 157.3453 + 131 0.0000 5.933821 161.4675 + 132 0.0000 6.174993 168.0301 + 133 0.0000 6.411549 174.4671 + 134 0.0000 6.507975 177.0910 + 135 0.0000 6.544047 178.0726 + 136 0.0000 6.684284 181.8886 + 137 0.0000 6.718991 182.8330 + 138 0.0000 6.771932 184.2736 + 139 0.0000 6.808861 185.2785 + 140 0.0000 6.928938 188.5460 + 141 0.0000 7.101634 193.2453 + 142 0.0000 7.136039 194.1815 + 143 0.0000 7.163464 194.9278 + 144 0.0000 7.177115 195.2992 + 145 0.0000 7.240098 197.0131 + 146 0.0000 7.275745 197.9831 + 147 0.0000 7.310644 198.9327 + 148 0.0000 7.397431 201.2943 + 149 0.0000 7.453816 202.8286 + 150 0.0000 7.489912 203.8109 + 151 0.0000 7.511387 204.3952 + 152 0.0000 7.597669 206.7431 + 153 0.0000 7.663707 208.5401 + 154 0.0000 7.856921 213.7977 + 155 0.0000 7.889586 214.6865 + 156 0.0000 8.244567 224.3461 + 157 0.0000 8.321966 226.4522 + 158 0.0000 14.136439 384.6721 + 159 0.0000 15.136748 411.8918 + 160 0.0000 15.653291 425.9477 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.669747 -562.4524 + 1 1.0000 -20.645830 -561.8016 + 2 1.0000 -15.802972 -430.0207 + 3 1.0000 -1.608490 -43.7692 + 4 1.0000 -1.403688 -38.1963 + 5 1.0000 -0.965338 -26.2682 + 6 1.0000 -0.775688 -21.1075 + 7 1.0000 -0.741708 -20.1829 + 8 1.0000 -0.691586 -18.8190 + 9 1.0000 -0.610953 -16.6249 + 10 1.0000 -0.533742 -14.5239 + 11 1.0000 -0.473088 -12.8734 + 12 0.0000 0.031402 0.8545 + 13 0.0000 0.074850 2.0368 + 14 0.0000 0.094879 2.5818 + 15 0.0000 0.112398 3.0585 + 16 0.0000 0.121711 3.3119 + 17 0.0000 0.145806 3.9676 + 18 0.0000 0.157542 4.2869 + 19 0.0000 0.169565 4.6141 + 20 0.0000 0.183198 4.9851 + 21 0.0000 0.194869 5.3026 + 22 0.0000 0.204586 5.5671 + 23 0.0000 0.233480 6.3533 + 24 0.0000 0.255101 6.9416 + 25 0.0000 0.299602 8.1526 + 26 0.0000 0.311841 8.4856 + 27 0.0000 0.343161 9.3379 + 28 0.0000 0.349890 9.5210 + 29 0.0000 0.394859 10.7447 + 30 0.0000 0.428500 11.6601 + 31 0.0000 0.514144 13.9906 + 32 0.0000 0.522668 14.2225 + 33 0.0000 0.534435 14.5427 + 34 0.0000 0.563349 15.3295 + 35 0.0000 0.617313 16.7979 + 36 0.0000 0.635054 17.2807 + 37 0.0000 0.657645 17.8954 + 38 0.0000 0.687632 18.7114 + 39 0.0000 0.700679 19.0665 + 40 0.0000 0.733973 19.9724 + 41 0.0000 0.752497 20.4765 + 42 0.0000 0.760743 20.7009 + 43 0.0000 0.790399 21.5078 + 44 0.0000 0.799373 21.7520 + 45 0.0000 0.844241 22.9730 + 46 0.0000 0.847309 23.0565 + 47 0.0000 0.875716 23.8294 + 48 0.0000 0.920119 25.0377 + 49 0.0000 0.939114 25.5546 + 50 0.0000 0.960245 26.1296 + 51 0.0000 0.996430 27.1142 + 52 0.0000 1.021723 27.8025 + 53 0.0000 1.053133 28.6572 + 54 0.0000 1.075820 29.2745 + 55 0.0000 1.086263 29.5587 + 56 0.0000 1.179035 32.0832 + 57 0.0000 1.195484 32.5308 + 58 0.0000 1.240127 33.7456 + 59 0.0000 1.277674 34.7673 + 60 0.0000 1.356263 36.9058 + 61 0.0000 1.409455 38.3532 + 62 0.0000 1.443556 39.2811 + 63 0.0000 1.503675 40.9171 + 64 0.0000 1.541944 41.9584 + 65 0.0000 1.554838 42.3093 + 66 0.0000 1.596228 43.4356 + 67 0.0000 1.627169 44.2775 + 68 0.0000 1.656621 45.0789 + 69 0.0000 1.744695 47.4756 + 70 0.0000 1.786131 48.6031 + 71 0.0000 1.819242 49.5041 + 72 0.0000 1.899220 51.6804 + 73 0.0000 1.941915 52.8422 + 74 0.0000 1.986350 54.0513 + 75 0.0000 2.014099 54.8064 + 76 0.0000 2.033282 55.3284 + 77 0.0000 2.097278 57.0698 + 78 0.0000 2.159283 58.7571 + 79 0.0000 2.177581 59.2550 + 80 0.0000 2.270574 61.7855 + 81 0.0000 2.306966 62.7757 + 82 0.0000 2.363023 64.3011 + 83 0.0000 2.388761 65.0015 + 84 0.0000 2.428545 66.0841 + 85 0.0000 2.444687 66.5233 + 86 0.0000 2.464828 67.0714 + 87 0.0000 2.522595 68.6433 + 88 0.0000 2.542912 69.1962 + 89 0.0000 2.553361 69.4805 + 90 0.0000 2.576950 70.1224 + 91 0.0000 2.622938 71.3738 + 92 0.0000 2.668920 72.6250 + 93 0.0000 2.676961 72.8438 + 94 0.0000 2.738240 74.5113 + 95 0.0000 2.805946 76.3537 + 96 0.0000 2.869354 78.0791 + 97 0.0000 2.963373 80.6375 + 98 0.0000 2.982906 81.1690 + 99 0.0000 3.046166 82.8904 + 100 0.0000 3.147602 85.6506 + 101 0.0000 3.162974 86.0689 + 102 0.0000 3.222530 87.6895 + 103 0.0000 3.517257 95.7094 + 104 0.0000 3.716531 101.1320 + 105 0.0000 3.874290 105.4248 + 106 0.0000 4.015602 109.2701 + 107 0.0000 4.148322 112.8816 + 108 0.0000 4.178581 113.7050 + 109 0.0000 4.281533 116.5064 + 110 0.0000 4.365618 118.7945 + 111 0.0000 4.422006 120.3289 + 112 0.0000 4.516463 122.8992 + 113 0.0000 4.562276 124.1458 + 114 0.0000 4.690357 127.6311 + 115 0.0000 4.821464 131.1987 + 116 0.0000 4.871640 132.5641 + 117 0.0000 4.880650 132.8092 + 118 0.0000 4.954661 134.8232 + 119 0.0000 5.004184 136.1708 + 120 0.0000 5.074279 138.0782 + 121 0.0000 5.110723 139.0698 + 122 0.0000 5.193441 141.3207 + 123 0.0000 5.230835 142.3382 + 124 0.0000 5.232629 142.3871 + 125 0.0000 5.291270 143.9828 + 126 0.0000 5.387667 146.6059 + 127 0.0000 5.478851 149.0871 + 128 0.0000 5.545691 150.9059 + 129 0.0000 5.684517 154.6836 + 130 0.0000 5.782335 157.3453 + 131 0.0000 5.933821 161.4675 + 132 0.0000 6.174993 168.0301 + 133 0.0000 6.411549 174.4671 + 134 0.0000 6.507975 177.0910 + 135 0.0000 6.544047 178.0726 + 136 0.0000 6.684284 181.8886 + 137 0.0000 6.718991 182.8330 + 138 0.0000 6.771932 184.2736 + 139 0.0000 6.808861 185.2785 + 140 0.0000 6.928938 188.5460 + 141 0.0000 7.101634 193.2453 + 142 0.0000 7.136039 194.1815 + 143 0.0000 7.163464 194.9278 + 144 0.0000 7.177115 195.2992 + 145 0.0000 7.240098 197.0131 + 146 0.0000 7.275745 197.9831 + 147 0.0000 7.310644 198.9327 + 148 0.0000 7.397431 201.2943 + 149 0.0000 7.453816 202.8286 + 150 0.0000 7.489912 203.8109 + 151 0.0000 7.511387 204.3952 + 152 0.0000 7.597669 206.7431 + 153 0.0000 7.663707 208.5401 + 154 0.0000 7.856921 213.7977 + 155 0.0000 7.889586 214.6865 + 156 0.0000 8.244567 224.3461 + 157 0.0000 8.321966 226.4522 + 158 0.0000 14.136439 384.6721 + 159 0.0000 15.136748 411.8918 + 160 0.0000 15.653291 425.9477 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.293831 0.000000 + 1 N : 0.340503 0.000000 + 2 O : -0.295815 0.000000 + 3 H : 0.249143 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.809454 s : 3.809454 + pz : 1.672754 p : 4.443271 + px : 1.378283 + py : 1.392234 + dz2 : 0.008214 d : 0.035806 + dxz : 0.007657 + dyz : 0.000337 + dx2y2 : 0.015850 + dxy : 0.003747 + f0 : 0.000447 f : 0.005300 + f+1 : 0.001265 + f-1 : 0.000270 + f+2 : 0.000702 + f-2 : 0.000947 + f+3 : 0.000682 + f-3 : 0.000987 + 1 N s : 3.857119 s : 3.857119 + pz : 0.723908 p : 2.625918 + px : 0.737183 + py : 1.164828 + dz2 : 0.030903 d : 0.143419 + dxz : 0.028405 + dyz : 0.025092 + dx2y2 : 0.037428 + dxy : 0.021591 + f0 : 0.001314 f : 0.033041 + f+1 : 0.004427 + f-1 : 0.005458 + f+2 : 0.003185 + f-2 : 0.005249 + f+3 : 0.006013 + f-3 : 0.007395 + 2 O s : 3.861482 s : 3.861482 + pz : 1.331238 p : 4.366488 + px : 1.652729 + py : 1.382521 + dz2 : 0.014877 d : 0.060378 + dxz : 0.003644 + dyz : 0.015088 + dx2y2 : 0.009507 + dxy : 0.017262 + f0 : 0.000317 f : 0.007467 + f+1 : 0.000141 + f-1 : 0.002023 + f+2 : 0.001334 + f-2 : 0.000987 + f+3 : 0.001280 + f-3 : 0.001386 + 3 H s : 0.644419 s : 0.644419 + pz : 0.037597 p : 0.085144 + px : 0.027430 + py : 0.020117 + dz2 : 0.000667 d : 0.021294 + dxz : -0.000664 + dyz : 0.009436 + dx2y2 : 0.000741 + dxy : 0.011113 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.599142 0.000000 + 1 N : -0.278933 0.000000 + 2 O : 0.244286 0.000000 + 3 H : -0.564495 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.109273 s : 3.109273 + pz : 1.361483 p : 3.905083 + px : 1.247692 + py : 1.295909 + dz2 : 0.040974 d : 0.295047 + dxz : 0.079140 + dyz : 0.033104 + dx2y2 : 0.075079 + dxy : 0.066749 + f0 : 0.008384 f : 0.091455 + f+1 : 0.016285 + f-1 : 0.002163 + f+2 : 0.014806 + f-2 : 0.017230 + f+3 : 0.009183 + f-3 : 0.023405 + 1 N s : 3.004590 s : 3.004590 + pz : 0.765598 p : 2.831441 + px : 0.828859 + py : 1.236984 + dz2 : 0.171617 d : 0.973306 + dxz : 0.207897 + dyz : 0.160474 + dx2y2 : 0.248829 + dxy : 0.184489 + f0 : 0.030738 f : 0.469598 + f+1 : 0.053516 + f-1 : 0.057958 + f+2 : 0.074298 + f-2 : 0.084392 + f+3 : 0.074981 + f-3 : 0.093714 + 2 O s : 3.301160 s : 3.301160 + pz : 1.210277 p : 4.018167 + px : 1.380039 + py : 1.427851 + dz2 : 0.040899 d : 0.320646 + dxz : 0.045610 + dyz : 0.075411 + dx2y2 : 0.107462 + dxy : 0.051265 + f0 : 0.008990 f : 0.115741 + f+1 : 0.004605 + f-1 : 0.018539 + f+2 : 0.023415 + f-2 : 0.019709 + f+3 : 0.012913 + f-3 : 0.027571 + 3 H s : 0.612364 s : 0.612364 + pz : 0.148522 p : 0.546411 + px : 0.135478 + py : 0.262411 + dz2 : 0.043639 d : 0.405720 + dxz : 0.028279 + dyz : 0.116471 + dx2y2 : 0.102472 + dxy : 0.114858 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2938 8.0000 -0.2938 1.8133 1.8133 0.0000 + 1 N 6.6595 7.0000 0.3405 2.5165 2.5165 0.0000 + 2 O 8.2958 8.0000 -0.2958 1.6893 1.6893 0.0000 + 3 H 0.7509 1.0000 0.2491 1.0149 1.0149 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8221 B( 0-O , 3-H ) : 0.9323 B( 1-N , 2-O ) : 1.6211 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 3 sec + +Total time .... 3.821 sec +Sum of individual times .... 3.222 sec ( 84.3%) + +Fock matrix formation .... 2.750 sec ( 72.0%) +Diagonalization .... 0.189 sec ( 4.9%) +Density matrix formation .... 0.016 sec ( 0.4%) +Population analysis .... 0.101 sec ( 2.6%) +Initial guess .... 0.024 sec ( 0.6%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.015 sec ( 0.4%) +DIIS solution .... 0.143 sec ( 3.7%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.615 sec +Reference energy ... -204.720668410 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 11.657 sec +AO-integral generation ... 0.400 sec +Half transformation ... 0.192 sec +K-integral sorting ... 8.775 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.070 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.074 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.111 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.105 s ( 0.001 ms/b) +: 159120 b 0 skpd 0.052 s ( 0.000 ms/b) + 218790 b 0 skpd 0.102 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.094 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.069 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.121 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.068 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.996 sec +AO-integral generation ... 0.775 sec +Half transformation ... 0.096 sec +J-integral sorting ... 0.094 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.332 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.450 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090486606 +EMP2(bb)= -0.090486606 +EMP2(ab)= -0.515107104 + +Initial guess performed in 0.193 sec +E(0) ... -204.720668410 +E(MP2) ... -0.696080317 +Initial E(tot) ... -205.416748727 + ... 0.186739571 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.416748727 -0.696080317 -0.000000000 0.028252149 7.51 0.000000926 + *** Turning on DIIS *** + 1 -205.388017009 -0.667348599 0.028731718 0.010878342 6.98 0.057978984 + 2 -205.407408615 -0.686740205 -0.019391606 0.006354182 7.24 0.061226182 + 3 -205.411108664 -0.690440254 -0.003700049 0.002229695 8.66 0.075661305 + 4 -205.412690854 -0.692022444 -0.001582190 0.001403204 7.41 0.082677310 + 5 -205.413244240 -0.692575830 -0.000553386 0.000808420 6.39 0.088283450 + 6 -205.413348703 -0.692680294 -0.000104463 0.000502329 6.40 0.090891573 + 7 -205.413390968 -0.692722558 -0.000042265 0.000222932 5.75 0.091991275 + 8 -205.413400649 -0.692732239 -0.000009681 0.000114211 6.06 0.092399448 + 9 -205.413396624 -0.692728214 0.000004025 0.000027574 6.81 0.092520823 + 10 -205.413401297 -0.692732887 -0.000004673 0.000017266 6.31 0.092566454 + 11 -205.413398828 -0.692730418 0.000002469 0.000012700 6.26 0.092556451 + 12 -205.413399755 -0.692731346 -0.000000927 0.000009068 7.10 0.092564749 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.720668410 +E(CORR) ... -0.692731346 +E(TOT) ... -205.413399755 +Singles norm **1/2 ... 0.092564749 ( 0.046282375, 0.046282375) +T1 diagnostic ... 0.021817721 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.061317 + 10a-> 13a 10b-> 13b 0.049020 + 8a-> 13a -1a-> -1a 0.047559 + 8b-> 13b -1b-> -1b 0.047559 + 10a-> 13a 8b-> 13b 0.033002 + 8a-> 13a 10b-> 13b 0.033002 + 11a-> 13a 11b-> 13b 0.029735 + 10b-> 13b -1b-> -1b 0.026437 + 10a-> 13a -1a-> -1a 0.026437 + 5a-> 13a 5b-> 13b 0.025746 + 8a-> 13a 8b-> 22b 0.023333 + 8a-> 22a 8b-> 13b 0.023333 + 11b-> 26b -1b-> -1b 0.022458 + 11a-> 26a -1a-> -1a 0.022458 + 10a-> 22a 10b-> 13b 0.022312 + 10a-> 13a 10b-> 22b 0.022312 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034602624 + alpha-alpha-alpha ... -0.000906708 ( 2.6%) + alpha-alpha-beta ... -0.016394604 ( 47.4%) + alpha-beta -beta ... -0.016394604 ( 47.4%) + beta -beta -beta ... -0.000906708 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034602624 + +Final correlation energy ... -0.727333969 +E(CCSD) ... -205.413399755 +E(CCSD(T)) ... -205.448002379 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.208376874 sqrt= 1.099261968 +W(HF) = 0.827556387 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.207800 0.000000 + 1 N : 0.149044 0.000000 + 2 O : -0.174723 -0.000000 + 3 H : 0.233479 -0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.796049 s : 3.796049 + pz : 1.616346 p : 4.337144 + px : 1.352737 + py : 1.368061 + dz2 : 0.014926 d : 0.065662 + dxz : 0.012617 + dyz : 0.007478 + dx2y2 : 0.019332 + dxy : 0.011310 + f0 : 0.000969 f : 0.008945 + f+1 : 0.001821 + f-1 : 0.000912 + f+2 : 0.001055 + f-2 : 0.001439 + f+3 : 0.001211 + f-3 : 0.001537 + 1 N s : 3.908077 s : 3.908077 + pz : 0.818109 p : 2.739689 + px : 0.796813 + py : 1.124767 + dz2 : 0.036457 d : 0.171139 + dxz : 0.035809 + dyz : 0.027856 + dx2y2 : 0.044963 + dxy : 0.026054 + f0 : 0.001647 f : 0.032052 + f+1 : 0.004423 + f-1 : 0.004906 + f+2 : 0.002896 + f-2 : 0.005244 + f+3 : 0.005524 + f-3 : 0.007411 + 2 O s : 3.849045 s : 3.849045 + pz : 1.289261 p : 4.232220 + px : 1.589183 + py : 1.353776 + dz2 : 0.018932 d : 0.083346 + dxz : 0.010365 + dyz : 0.017066 + dx2y2 : 0.016311 + dxy : 0.020673 + f0 : 0.000808 f : 0.010111 + f+1 : 0.000705 + f-1 : 0.002088 + f+2 : 0.001660 + f-2 : 0.001432 + f+3 : 0.001622 + f-3 : 0.001796 + 3 H s : 0.659858 s : 0.659858 + pz : 0.042284 p : 0.087131 + px : 0.031020 + py : 0.013826 + dz2 : 0.000669 d : 0.019533 + dxz : -0.000097 + dyz : 0.008497 + dx2y2 : 0.000178 + dxy : 0.010286 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.614111 0.000000 + 1 N : -0.327636 -0.000000 + 2 O : 0.280510 0.000000 + 3 H : -0.566985 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.117714 s : 3.117714 + pz : 1.325630 p : 3.842635 + px : 1.236234 + py : 1.280770 + dz2 : 0.047881 d : 0.326686 + dxz : 0.085868 + dyz : 0.039427 + dx2y2 : 0.082014 + dxy : 0.071497 + f0 : 0.009214 f : 0.098854 + f+1 : 0.018231 + f-1 : 0.003173 + f+2 : 0.016158 + f-2 : 0.017635 + f+3 : 0.010583 + f-3 : 0.023859 + 1 N s : 3.010140 s : 3.010140 + pz : 0.822289 p : 2.881836 + px : 0.857122 + py : 1.202425 + dz2 : 0.169315 d : 0.977761 + dxz : 0.214202 + dyz : 0.163552 + dx2y2 : 0.250859 + dxy : 0.179832 + f0 : 0.031440 f : 0.457899 + f+1 : 0.048185 + f-1 : 0.056449 + f+2 : 0.074068 + f-2 : 0.082024 + f+3 : 0.075060 + f-3 : 0.090673 + 2 O s : 3.303164 s : 3.303164 + pz : 1.187053 p : 3.937576 + px : 1.342068 + py : 1.408455 + dz2 : 0.051296 d : 0.354120 + dxz : 0.050474 + dyz : 0.082327 + dx2y2 : 0.111304 + dxy : 0.058718 + f0 : 0.009758 f : 0.124630 + f+1 : 0.005689 + f-1 : 0.022527 + f+2 : 0.024305 + f-2 : 0.020189 + f+3 : 0.014992 + f-3 : 0.027170 + 3 H s : 0.617162 s : 0.617162 + pz : 0.151528 p : 0.554603 + px : 0.136362 + py : 0.266713 + dz2 : 0.043165 d : 0.395220 + dxz : 0.028139 + dyz : 0.111164 + dx2y2 : 0.101740 + dxy : 0.111012 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2078 8.0000 -0.2078 2.1887 1.7387 0.4500 + 1 N 6.8510 7.0000 0.1490 2.8025 2.3307 0.4718 + 2 O 8.1747 8.0000 -0.1747 2.0929 1.5949 0.4980 + 3 H 0.7665 1.0000 0.2335 1.0331 0.9591 0.0740 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7777 B( 0-O , 2-O ) : 0.1009 B( 0-O , 3-H ) : 0.8601 +B( 1-N , 2-O ) : 1.4740 + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 123.120 sec + +Fock Matrix Formation ... 0.615 sec ( 0.5%) +Initial Guess ... 0.193 sec ( 0.2%) +DIIS Solver ... 5.055 sec ( 4.1%) +State Vector Update ... 0.218 sec ( 0.2%) +Sigma-vector construction ... 83.606 sec ( 67.9%) + <0|H|D> ... 0.009 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.051 sec ( 0.1% of sigma) + (0-ext) ... 0.164 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.062 sec ( 0.1% of sigma) + (2-ext) ... 2.183 sec ( 2.6% of sigma) + (4-ext) ... 50.034 sec ( 59.8% of sigma) + ... 4.219 sec ( 5.0% of sigma) + ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.022 sec ( 0.0% of sigma) + (1-ext) ... 0.218 sec ( 0.3% of sigma) + Fock-dressing ... 5.724 sec ( 6.8% of sigma) + (ik|jl)-dressing ... 0.183 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 16.766 sec ( 20.1% of sigma) + Pair energies ... 0.020 sec ( 0.0% of sigma) +Total Time for computing (T) ... 18.087 sec ( 14.7% of ALL) + I/O of integral and amplitudes ... 2.094 sec ( 11.6% of (T)) + External N**7 contributions ... 9.811 sec ( 54.2% of (T)) + Internal N**7 contributions ... 0.955 sec ( 5.3% of (T)) + N**6 triples energy contributions ... 2.855 sec ( 15.8% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.448002379090 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.020.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.020.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.378976, -0.303444 -0.370961) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.69273 -0.23845 -0.50699 +Nuclear contribution : -0.84234 0.69870 0.79557 + ----------------------------------------- +Total Dipole Moment : -0.14960 0.46025 0.28859 + ----------------------------------------- +Magnitude (a.u.) : 0.56346 +Magnitude (Debye) : 1.43221 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.774766 0.433010 0.376575 +Rotational constants in MHz : 83185.381910 12981.311123 11289.428207 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.151245 0.489256 0.235041 +x,y,z [Debye]: -0.384434 1.243589 0.597428 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.378976, -0.303444 -0.370961) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.70662 -0.15998 -0.57218 +Nuclear contribution : -0.84234 0.69870 0.79557 + ----------------------------------------- +Total Dipole Moment : -0.13572 0.53872 0.22339 + ----------------------------------------- +Magnitude (a.u.) : 0.59878 +Magnitude (Debye) : 1.52199 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.774766 0.433010 0.376575 +Rotational constants in MHz : 83185.381910 12981.311123 11289.428207 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.078210 0.556299 0.207263 +x,y,z [Debye]: -0.198794 1.413999 0.526820 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 21 * + * * + * Dihedral ( 2, 1, 0, 3) : -16.36363636 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0321699031 RMS(Int)= 0.0007996469 + Iter 1: RMS(Cart)= 0.0001801444 RMS(Int)= 0.0000111411 + Iter 2: RMS(Cart)= 0.0000025099 RMS(Int)= 0.0000001559 + Iter 3: RMS(Cart)= 0.0000000351 RMS(Int)= 0.0000000022 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4134 0.000000 + 2. B(O 2,N 1) 1.1850 0.000000 + 3. B(H 3,O 0) 0.9779 0.000000 + 4. A(N 1,O 0,H 3) 104.7603 0.000000 + 5. A(O 0,N 1,O 2) 113.0164 0.000000 + 6. D(O 2,N 1,O 0,H 3) -16.3636 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.664417 -0.381509 0.494886 + N 0.486107 -0.596465 -0.297456 + O 0.878309 0.390909 -0.822320 + H -0.699998 0.587066 0.624890 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.255566 -0.720948 0.935199 + 1 N 7.0000 0 14.007 0.918609 -1.127156 -0.562110 + 2 O 8.0000 0 15.999 1.659764 0.738710 -1.553960 + 3 H 1.0000 0 1.008 -1.322804 1.109394 1.180871 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.411980055611 0.00000000 0.00000000 + O 2 1 0 1.183733178525 113.18995933 0.00000000 + H 1 2 3 0.976010855552 104.96245521 335.45454535 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.668255611664 0.00000000 0.00000000 + O 2 1 0 2.236931523049 113.18995933 0.00000000 + H 1 2 3 1.844393220727 104.96245521 335.45454535 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2243 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2718 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.810910153149 Eh + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.8109101531 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.469e-04 +Time for diagonalization ... 0.005 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.004 sec +Total time needed ... 0.011 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7177859805 0.000000000000 0.00198195 0.00005420 0.0139350 0.7000 + 1 -204.7185288654 -0.000742884864 0.00176686 0.00005014 0.0116374 0.7000 + ***Turning on DIIS*** + 2 -204.7191765186 -0.000647653275 0.00469172 0.00013796 0.0095487 0.0000 + 3 -204.7223158308 -0.003139312177 0.00214456 0.00006134 0.0042584 0.0000 + 4 -204.7207312583 0.001584572497 0.00099600 0.00003102 0.0017729 0.0000 + 5 -204.7224229879 -0.001691729554 0.00089417 0.00003591 0.0009478 0.0000 + 6 -204.7217117916 0.000711196251 0.00053588 0.00002399 0.0005495 0.0000 + 7 -204.7214709846 0.000240807052 0.00032610 0.00001540 0.0002940 0.0000 + 8 -204.7221481057 -0.000677121088 0.00019332 0.00000865 0.0001876 0.0000 + 9 -204.7216647033 0.000483402334 0.00009510 0.00000303 0.0000662 0.0000 + 10 -204.7217654290 -0.000100725654 0.00003252 0.00000086 0.0000402 0.0000 + 11 -204.7218040575 -0.000038628494 0.00001772 0.00000044 0.0000241 0.0000 + 12 -204.7217605689 0.000043488596 0.00000637 0.00000017 0.0000058 0.0000 + 13 -204.7217733783 -0.000012809452 0.00000171 0.00000006 0.0000025 0.0000 + 14 -204.7217709119 0.000002466438 0.00000085 0.00000003 0.0000012 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 15 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72176947 Eh -5570.76256 eV + +Components: +Nuclear Repulsion : 69.81091015 Eh 1899.65144 eV +Electronic Energy : -274.53267962 Eh -7470.41400 eV +One Electron Energy: -419.21483704 Eh -11407.41566 eV +Two Electron Energy: 144.68215742 Eh 3937.00166 eV + +Virial components: +Potential Energy : -408.95349965 Eh -11128.19047 eV +Kinetic Energy : 204.23173018 Eh 5557.42791 eV +Virial Ratio : 2.00239943 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.4428e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.0744e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.1572e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.5958e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.669460 -562.4446 + 1 1.0000 -20.647317 -561.8421 + 2 1.0000 -15.804199 -430.0541 + 3 1.0000 -1.607994 -43.7557 + 4 1.0000 -1.403095 -38.1802 + 5 1.0000 -0.965922 -26.2841 + 6 1.0000 -0.774915 -21.0865 + 7 1.0000 -0.742170 -20.1955 + 8 1.0000 -0.689108 -18.7516 + 9 1.0000 -0.613602 -16.6970 + 10 1.0000 -0.533227 -14.5098 + 11 1.0000 -0.474251 -12.9050 + 12 0.0000 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3.8764 + 18 0.0000 0.157943 4.2979 + 19 0.0000 0.169186 4.6038 + 20 0.0000 0.184242 5.0135 + 21 0.0000 0.195030 5.3070 + 22 0.0000 0.204848 5.5742 + 23 0.0000 0.232822 6.3354 + 24 0.0000 0.252426 6.8688 + 25 0.0000 0.300646 8.1810 + 26 0.0000 0.309976 8.4349 + 27 0.0000 0.342930 9.3316 + 28 0.0000 0.350547 9.5389 + 29 0.0000 0.399049 10.8587 + 30 0.0000 0.433631 11.7997 + 31 0.0000 0.512828 13.9548 + 32 0.0000 0.519055 14.1242 + 33 0.0000 0.534823 14.5533 + 34 0.0000 0.562807 15.3147 + 35 0.0000 0.617574 16.8050 + 36 0.0000 0.637424 17.3452 + 37 0.0000 0.661887 18.0109 + 38 0.0000 0.685672 18.6581 + 39 0.0000 0.698753 19.0140 + 40 0.0000 0.734927 19.9984 + 41 0.0000 0.754789 20.5389 + 42 0.0000 0.760368 20.6907 + 43 0.0000 0.791918 21.5492 + 44 0.0000 0.793964 21.6048 + 45 0.0000 0.845446 23.0058 + 46 0.0000 0.847497 23.0616 + 47 0.0000 0.872767 23.7492 + 48 0.0000 0.919970 25.0337 + 49 0.0000 0.937411 25.5082 + 50 0.0000 0.957680 26.0598 + 51 0.0000 1.002918 27.2908 + 52 0.0000 1.024607 27.8810 + 53 0.0000 1.063315 28.9343 + 54 0.0000 1.081079 29.4177 + 55 0.0000 1.085387 29.5349 + 56 0.0000 1.178883 32.0790 + 57 0.0000 1.202549 32.7230 + 58 0.0000 1.238900 33.7122 + 59 0.0000 1.272496 34.6264 + 60 0.0000 1.350171 36.7400 + 61 0.0000 1.409234 38.3472 + 62 0.0000 1.453193 39.5434 + 63 0.0000 1.501658 40.8622 + 64 0.0000 1.543944 42.0128 + 65 0.0000 1.555616 42.3305 + 66 0.0000 1.589175 43.2436 + 67 0.0000 1.618772 44.0490 + 68 0.0000 1.656462 45.0746 + 69 0.0000 1.751707 47.6664 + 70 0.0000 1.788031 48.6548 + 71 0.0000 1.820888 49.5489 + 72 0.0000 1.902217 51.7620 + 73 0.0000 1.928534 52.4781 + 74 0.0000 1.987874 54.0928 + 75 0.0000 2.001941 54.4756 + 76 0.0000 2.034626 55.3650 + 77 0.0000 2.107922 57.3595 + 78 0.0000 2.156744 58.6880 + 79 0.0000 2.177966 59.2655 + 80 0.0000 2.280795 62.0636 + 81 0.0000 2.308631 62.8210 + 82 0.0000 2.359071 64.1936 + 83 0.0000 2.385607 64.9157 + 84 0.0000 2.435220 66.2657 + 85 0.0000 2.448044 66.6147 + 86 0.0000 2.465969 67.1024 + 87 0.0000 2.516170 68.4685 + 88 0.0000 2.531397 68.8828 + 89 0.0000 2.556684 69.5709 + 90 0.0000 2.576238 70.1030 + 91 0.0000 2.627349 71.4938 + 92 0.0000 2.667870 72.5964 + 93 0.0000 2.682738 73.0010 + 94 0.0000 2.733552 74.3837 + 95 0.0000 2.802649 76.2640 + 96 0.0000 2.884166 78.4821 + 97 0.0000 2.965550 80.6967 + 98 0.0000 2.972262 80.8794 + 99 0.0000 3.050524 83.0090 + 100 0.0000 3.142933 85.5236 + 101 0.0000 3.160523 86.0022 + 102 0.0000 3.216963 87.5380 + 103 0.0000 3.508698 95.4765 + 104 0.0000 3.733766 101.6009 + 105 0.0000 3.855675 104.9182 + 106 0.0000 4.016737 109.3010 + 107 0.0000 4.149417 112.9114 + 108 0.0000 4.176475 113.6477 + 109 0.0000 4.255601 115.8008 + 110 0.0000 4.358990 118.6141 + 111 0.0000 4.417352 120.2022 + 112 0.0000 4.515995 122.8865 + 113 0.0000 4.563393 124.1762 + 114 0.0000 4.690838 127.6442 + 115 0.0000 4.831314 131.4667 + 116 0.0000 4.876732 132.7026 + 117 0.0000 4.898208 133.2870 + 118 0.0000 4.941466 134.4641 + 119 0.0000 4.999966 136.0560 + 120 0.0000 5.069005 137.9346 + 121 0.0000 5.106043 138.9425 + 122 0.0000 5.194444 141.3480 + 123 0.0000 5.223166 142.1296 + 124 0.0000 5.229946 142.3141 + 125 0.0000 5.297273 144.1461 + 126 0.0000 5.383765 146.4997 + 127 0.0000 5.474633 148.9723 + 128 0.0000 5.550373 151.0333 + 129 0.0000 5.672472 154.3558 + 130 0.0000 5.783997 157.3906 + 131 0.0000 5.925921 161.2525 + 132 0.0000 6.174813 168.0252 + 133 0.0000 6.411421 174.4636 + 134 0.0000 6.512100 177.2032 + 135 0.0000 6.553524 178.3305 + 136 0.0000 6.678238 181.7241 + 137 0.0000 6.711289 182.6235 + 138 0.0000 6.767443 184.1515 + 139 0.0000 6.817475 185.5129 + 140 0.0000 6.935003 188.7110 + 141 0.0000 7.099205 193.1792 + 142 0.0000 7.132828 194.0941 + 143 0.0000 7.153117 194.6462 + 144 0.0000 7.171722 195.1525 + 145 0.0000 7.234062 196.8488 + 146 0.0000 7.274516 197.9496 + 147 0.0000 7.310494 198.9287 + 148 0.0000 7.401432 201.4032 + 149 0.0000 7.444292 202.5695 + 150 0.0000 7.468640 203.2320 + 151 0.0000 7.500053 204.0868 + 152 0.0000 7.599004 206.7794 + 153 0.0000 7.669878 208.7080 + 154 0.0000 7.854553 213.7333 + 155 0.0000 7.904541 215.0935 + 156 0.0000 8.267729 224.9763 + 157 0.0000 8.308697 226.0912 + 158 0.0000 14.143429 384.8623 + 159 0.0000 15.050590 409.5474 + 160 0.0000 15.629692 425.3056 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.291944 0.000000 + 1 N : 0.340076 0.000000 + 2 O : -0.298166 0.000000 + 3 H : 0.250034 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.807351 s : 3.807351 + pz : 1.648838 p : 4.442807 + px : 1.409255 + py : 1.384714 + dz2 : 0.009084 d : 0.036422 + dxz : 0.007708 + dyz : 0.000422 + dx2y2 : 0.016333 + dxy : 0.002876 + f0 : 0.000407 f : 0.005364 + f+1 : 0.001314 + f-1 : 0.000298 + f+2 : 0.000780 + f-2 : 0.001074 + f+3 : 0.000560 + f-3 : 0.000931 + 1 N s : 3.861872 s : 3.861872 + pz : 0.716380 p : 2.621587 + px : 0.730427 + py : 1.174780 + dz2 : 0.030412 d : 0.143445 + dxz : 0.028246 + dyz : 0.025441 + dx2y2 : 0.036775 + dxy : 0.022572 + f0 : 0.001608 f : 0.033020 + f+1 : 0.004044 + f-1 : 0.005493 + f+2 : 0.003101 + f-2 : 0.005371 + f+3 : 0.005881 + f-3 : 0.007523 + 2 O s : 3.859048 s : 3.859048 + pz : 1.370946 p : 4.371258 + px : 1.620522 + py : 1.379790 + dz2 : 0.013411 d : 0.060374 + dxz : 0.003227 + dyz : 0.016143 + dx2y2 : 0.009985 + dxy : 0.017608 + f0 : 0.000301 f : 0.007486 + f+1 : 0.000153 + f-1 : 0.001967 + f+2 : 0.001270 + f-2 : 0.000959 + f+3 : 0.001313 + f-3 : 0.001524 + 3 H s : 0.645516 s : 0.645516 + pz : 0.035566 p : 0.083432 + px : 0.028079 + py : 0.019787 + dz2 : 0.000181 d : 0.021017 + dxz : -0.000882 + dyz : 0.010091 + dx2y2 : 0.000523 + dxy : 0.011106 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.598039 0.000000 + 1 N : -0.275722 0.000000 + 2 O : 0.244234 0.000000 + 3 H : -0.566551 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.111170 s : 3.111170 + pz : 1.353667 p : 3.904666 + px : 1.258635 + py : 1.292364 + dz2 : 0.041653 d : 0.294702 + dxz : 0.081940 + dyz : 0.034868 + dx2y2 : 0.071683 + dxy : 0.064558 + f0 : 0.008331 f : 0.091423 + f+1 : 0.016181 + f-1 : 0.003120 + f+2 : 0.014842 + f-2 : 0.019057 + f+3 : 0.008296 + f-3 : 0.021596 + 1 N s : 3.006013 s : 3.006013 + pz : 0.758955 p : 2.829412 + px : 0.817300 + py : 1.253157 + dz2 : 0.173966 d : 0.971008 + dxz : 0.204086 + dyz : 0.158528 + dx2y2 : 0.249707 + dxy : 0.184721 + f0 : 0.032759 f : 0.469289 + f+1 : 0.052492 + f-1 : 0.059101 + f+2 : 0.070692 + f-2 : 0.084376 + f+3 : 0.074378 + f-3 : 0.095491 + 2 O s : 3.299662 s : 3.299662 + pz : 1.224540 p : 4.020029 + px : 1.361960 + py : 1.433529 + dz2 : 0.042574 d : 0.320531 + dxz : 0.043931 + dyz : 0.068762 + dx2y2 : 0.111520 + dxy : 0.053743 + f0 : 0.008697 f : 0.115545 + f+1 : 0.004408 + f-1 : 0.018995 + f+2 : 0.020689 + f-2 : 0.019214 + f+3 : 0.014461 + f-3 : 0.029082 + 3 H s : 0.611705 s : 0.611705 + pz : 0.144850 p : 0.544898 + px : 0.136127 + py : 0.263921 + dz2 : 0.041469 d : 0.409947 + dxz : 0.028011 + dyz : 0.118364 + dx2y2 : 0.104913 + dxy : 0.117190 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2919 8.0000 -0.2919 1.8111 1.8111 -0.0000 + 1 N 6.6599 7.0000 0.3401 2.5132 2.5132 0.0000 + 2 O 8.2982 8.0000 -0.2982 1.6810 1.6810 -0.0000 + 3 H 0.7500 1.0000 0.2500 1.0136 1.0136 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8248 B( 0-O , 3-H ) : 0.9273 B( 1-N , 2-O ) : 1.6121 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 6 sec + +Total time .... 6.186 sec +Sum of individual times .... 5.689 sec ( 92.0%) + +Fock matrix formation .... 4.953 sec ( 80.1%) +Diagonalization .... 0.340 sec ( 5.5%) +Density matrix formation .... 0.025 sec ( 0.4%) +Population analysis .... 0.089 sec ( 1.4%) +Initial guess .... 0.018 sec ( 0.3%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.011 sec ( 0.2%) +DIIS solution .... 0.264 sec ( 4.3%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.526 sec +Reference energy ... -204.721770255 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 10.354 sec +AO-integral generation ... 0.392 sec +Half transformation ... 0.189 sec +K-integral sorting ... 7.829 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.060 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.065 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.072 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.093 s ( 0.001 ms/b) +: 159120 b 0 skpd 0.049 s ( 0.000 ms/b) + 218790 b 0 skpd 0.090 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.079 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.060 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.103 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.060 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.846 sec +AO-integral generation ... 0.641 sec +Half transformation ... 0.094 sec +J-integral sorting ... 0.085 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.237 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.373 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090642419 +EMP2(bb)= -0.090642419 +EMP2(ab)= -0.515615569 + +Initial guess performed in 0.184 sec +E(0) ... -204.721770255 +E(MP2) ... -0.696900407 +Initial E(tot) ... -205.418670662 + ... 0.187345164 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.418670662 -0.696900407 -0.000000000 0.029563020 5.66 0.000002797 + *** Turning on DIIS *** + 1 -205.389470033 -0.667699778 0.029200630 0.011714022 6.34 0.058547406 + 2 -205.408996464 -0.687226209 -0.019526431 0.006682189 6.16 0.061730527 + 3 -205.412707514 -0.690937259 -0.003711050 0.002378929 6.80 0.076334348 + 4 -205.414306806 -0.692536551 -0.001599292 0.001462917 7.05 0.083445039 + 5 -205.414869459 -0.693099204 -0.000562653 0.000802707 6.29 0.089130427 + 6 -205.414974263 -0.693204008 -0.000104804 0.000502597 6.59 0.091733539 + 7 -205.415016634 -0.693246379 -0.000042371 0.000219650 6.89 0.092819126 + 8 -205.415026412 -0.693256157 -0.000009778 0.000115501 6.82 0.093212174 + 9 -205.415022304 -0.693252049 0.000004108 0.000028818 8.25 0.093327972 + 10 -205.415027014 -0.693256759 -0.000004710 0.000010886 7.25 0.093370868 + 11 -205.415024623 -0.693254368 0.000002391 0.000008046 7.30 0.093361138 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.721770255 +E(CORR) ... -0.693254368 +E(TOT) ... -205.415024623 +Singles norm **1/2 ... 0.093361138 ( 0.046680569, 0.046680569) +T1 diagnostic ... 0.022005431 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.064936 + 10a-> 13a 10b-> 13b 0.052594 + 8b-> 13b -1b-> -1b 0.050096 + 8a-> 13a -1a-> -1a 0.050096 + 8a-> 13a 10b-> 13b 0.035438 + 10a-> 13a 8b-> 13b 0.035438 + 11a-> 13a 11b-> 13b 0.029116 + 10a-> 13a -1a-> -1a 0.026540 + 10b-> 13b -1b-> -1b 0.026540 + 5a-> 13a 5b-> 13b 0.025885 + 8a-> 22a 8b-> 13b 0.024612 + 8a-> 13a 8b-> 22b 0.024612 + 11a-> 26a -1a-> -1a 0.024251 + 11b-> 26b -1b-> -1b 0.024251 + 10a-> 22a 10b-> 13b 0.024003 + 10a-> 13a 10b-> 22b 0.024003 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034796122 + alpha-alpha-alpha ... -0.000912856 ( 2.6%) + alpha-alpha-beta ... -0.016485205 ( 47.4%) + alpha-beta -beta ... -0.016485205 ( 47.4%) + beta -beta -beta ... -0.000912856 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034796122 + +Final correlation energy ... -0.728050490 +E(CCSD) ... -205.415024623 +E(CCSD(T)) ... -205.449820745 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.208979942 sqrt= 1.099536239 +W(HF) = 0.827143583 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.203153 0.000000 + 1 N : 0.147175 -0.000000 + 2 O : -0.177135 0.000000 + 3 H : 0.233114 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.794567 s : 3.794567 + pz : 1.592670 p : 4.333437 + px : 1.380204 + py : 1.360563 + dz2 : 0.015761 d : 0.066139 + dxz : 0.012453 + dyz : 0.007633 + dx2y2 : 0.019821 + dxy : 0.010472 + f0 : 0.000942 f : 0.009011 + f+1 : 0.001855 + f-1 : 0.000940 + f+2 : 0.001118 + f-2 : 0.001539 + f+3 : 0.001117 + f-3 : 0.001500 + 1 N s : 3.911839 s : 3.911839 + pz : 0.812134 p : 2.738258 + px : 0.796107 + py : 1.130017 + dz2 : 0.036585 d : 0.170665 + dxz : 0.035128 + dyz : 0.027950 + dx2y2 : 0.044449 + dxy : 0.026554 + f0 : 0.001889 f : 0.032062 + f+1 : 0.004051 + f-1 : 0.005063 + f+2 : 0.002789 + f-2 : 0.005359 + f+3 : 0.005391 + f-3 : 0.007519 + 2 O s : 3.846762 s : 3.846762 + pz : 1.325499 p : 4.236734 + px : 1.559150 + py : 1.352085 + dz2 : 0.017893 d : 0.083495 + dxz : 0.009961 + dyz : 0.018056 + dx2y2 : 0.016859 + dxy : 0.020726 + f0 : 0.000795 f : 0.010144 + f+1 : 0.000712 + f-1 : 0.002084 + f+2 : 0.001600 + f-2 : 0.001412 + f+3 : 0.001633 + f-3 : 0.001908 + 3 H s : 0.662105 s : 0.662105 + pz : 0.040340 p : 0.085337 + px : 0.031828 + py : 0.013169 + dz2 : 0.000238 d : 0.019444 + dxz : -0.000258 + dyz : 0.009144 + dx2y2 : 0.000013 + dxy : 0.010308 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.613840 0.000000 + 1 N : -0.325443 0.000000 + 2 O : 0.280279 -0.000000 + 3 H : -0.568677 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.119840 s : 3.119840 + pz : 1.318550 p : 3.841077 + px : 1.244826 + py : 1.277702 + dz2 : 0.048870 d : 0.326389 + dxz : 0.088575 + dyz : 0.040887 + dx2y2 : 0.078680 + dxy : 0.069376 + f0 : 0.009201 f : 0.098855 + f+1 : 0.018267 + f-1 : 0.004207 + f+2 : 0.016151 + f-2 : 0.019261 + f+3 : 0.009581 + f-3 : 0.022186 + 1 N s : 3.011520 s : 3.011520 + pz : 0.816397 p : 2.881396 + px : 0.850310 + py : 1.214689 + dz2 : 0.172001 d : 0.975016 + dxz : 0.210921 + dyz : 0.160199 + dx2y2 : 0.251094 + dxy : 0.180800 + f0 : 0.033111 f : 0.457511 + f+1 : 0.047397 + f-1 : 0.057428 + f+2 : 0.070772 + f-2 : 0.082062 + f+3 : 0.074499 + f-3 : 0.092241 + 2 O s : 3.301618 s : 3.301618 + pz : 1.199392 p : 3.939163 + px : 1.325491 + py : 1.414281 + dz2 : 0.052405 d : 0.354408 + dxz : 0.048870 + dyz : 0.076333 + dx2y2 : 0.115341 + dxy : 0.061458 + f0 : 0.009421 f : 0.124532 + f+1 : 0.005563 + f-1 : 0.022537 + f+2 : 0.021992 + f-2 : 0.019650 + f+3 : 0.016559 + f-3 : 0.028811 + 3 H s : 0.616852 s : 0.616852 + pz : 0.147376 p : 0.552529 + px : 0.137112 + py : 0.268042 + dz2 : 0.041113 d : 0.399296 + dxz : 0.028022 + dyz : 0.112821 + dx2y2 : 0.104281 + dxy : 0.113059 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2032 8.0000 -0.2032 2.1903 1.7384 0.4519 + 1 N 6.8528 7.0000 0.1472 2.8024 2.3306 0.4718 + 2 O 8.1771 8.0000 -0.1771 2.0879 1.5897 0.4982 + 3 H 0.7669 1.0000 0.2331 1.0328 0.9587 0.0742 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7822 B( 0-O , 2-O ) : 0.1016 B( 0-O , 3-H ) : 0.8546 +B( 1-N , 2-O ) : 1.4662 + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 112.820 sec + +Fock Matrix Formation ... 0.526 sec ( 0.5%) +Initial Guess ... 0.184 sec ( 0.2%) +DIIS Solver ... 4.777 sec ( 4.2%) +State Vector Update ... 0.231 sec ( 0.2%) +Sigma-vector construction ... 76.400 sec ( 67.7%) + <0|H|D> ... 0.008 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.047 sec ( 0.1% of sigma) + (0-ext) ... 0.152 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.055 sec ( 0.1% of sigma) + (2-ext) ... 1.989 sec ( 2.6% of sigma) + (4-ext) ... 44.395 sec ( 58.1% of sigma) + ... 3.623 sec ( 4.7% of sigma) + ... 0.005 sec ( 0.0% of sigma) + (1-ext) ... 0.020 sec ( 0.0% of sigma) + (1-ext) ... 0.214 sec ( 0.3% of sigma) + Fock-dressing ... 5.012 sec ( 6.6% of sigma) + (ik|jl)-dressing ... 0.201 sec ( 0.3% of sigma) + (ij|ab),(ia|jb)-dressing ... 17.035 sec ( 22.3% of sigma) + Pair energies ... 0.024 sec ( 0.0% of sigma) +Total Time for computing (T) ... 16.958 sec ( 15.0% of ALL) + I/O of integral and amplitudes ... 2.643 sec ( 15.6% of (T)) + External N**7 contributions ... 9.622 sec ( 56.7% of (T)) + Internal N**7 contributions ... 0.963 sec ( 5.7% of (T)) + N**6 triples energy contributions ... 3.530 sec ( 20.8% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.449820745405 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.007248810 0.000593255 -0.005643407 + 2 N : 0.007277625 -0.001380663 0.004810753 + 3 O : -0.002985446 0.000385581 -0.004406881 + 4 H : 0.002956631 0.000401826 0.005239535 + +Norm of the cartesian gradient ... 0.015086307 +RMS gradient ... 0.004355042 +MAX gradient ... 0.007277625 + +------- +TIMINGS +------- + +Total numerical gradient time ... 825.990 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 541.45 cm**-1 + 7: 661.57 cm**-1 + 8: 848.77 cm**-1 + 9: 1323.55 cm**-1 + 10: 1659.26 cm**-1 + 11: 3605.67 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 0.173206 0.084850 -0.194218 0.056388 -0.018731 0.001407 + 1 0.029036 0.074590 0.128617 0.076435 0.065498 -0.061211 + 2 -0.037399 -0.184935 0.141908 -0.036467 0.009878 -0.007865 + 3 -0.115105 0.037414 0.349401 0.061945 -0.081700 0.002081 + 4 -0.061554 -0.085223 -0.217459 -0.017470 -0.517429 -0.000945 + 5 -0.005985 0.101552 -0.242955 -0.062479 0.173590 -0.001363 + 6 -0.055940 -0.169851 -0.132341 -0.057819 0.126417 -0.000455 + 7 0.016071 -0.001134 0.046426 -0.058315 0.388379 -0.000172 + 8 0.100698 0.066966 0.115233 0.058608 -0.187007 0.000310 + 9 -0.261772 0.829233 0.327941 -0.838069 -0.573899 -0.044035 + 10 0.139407 0.018349 0.243490 -0.044845 -0.013841 0.987402 + 11 -0.921519 0.461260 -0.705281 0.516771 0.399221 0.138851 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 541.45 0.017415 88.01 0.010037 (-0.096844 -0.018493 -0.017796) + 7: 661.57 0.009787 49.46 0.004616 ( 0.025799 -0.020166 0.059533) + 8: 848.77 0.053919 272.48 0.019824 ( 0.101243 0.004355 -0.097749) + 9: 1323.55 0.001683 8.50 0.000397 (-0.005489 0.019141 -0.000471) + 10: 1659.26 0.029820 150.70 0.005608 (-0.054482 -0.019140 0.047683) + 11: 3605.67 0.006904 34.89 0.000597 (-0.009653 0.019159 0.011715) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 541.45 E(vib) ... 0.12 +freq. 661.57 E(vib) ... 0.08 +freq. 848.77 E(vib) ... 0.04 +freq. 1323.55 E(vib) ... 0.01 +freq. 1659.26 E(vib) ... 0.00 +freq. 3605.67 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.44982075 Eh +Zero point energy ... 0.01968397 Eh 12.35 kcal/mol +Thermal vibrational correction ... 0.00040247 Eh 0.25 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42690177 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00323501 Eh 2.03 kcal/mol +Non-thermal (ZPE) correction 0.01968397 Eh 12.35 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02291898 Eh 14.38 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42690177 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.42595756 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.755376 0.434260 0.376060 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00053226 Eh 0.33 kcal/mol +Rotational entropy ... 0.00988780 Eh 6.20 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02822238 Eh 17.71 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00988780 Eh 6.20 kcal/mol| +| sn= 2 | S(rot)= 0.00923335 Eh 5.79 kcal/mol| +| sn= 3 | S(rot)= 0.00885052 Eh 5.55 kcal/mol| +| sn= 4 | S(rot)= 0.00857889 Eh 5.38 kcal/mol| +| sn= 5 | S(rot)= 0.00836820 Eh 5.25 kcal/mol| +| sn= 6 | S(rot)= 0.00819606 Eh 5.14 kcal/mol| +| sn= 7 | S(rot)= 0.00805051 Eh 5.05 kcal/mol| +| sn= 8 | S(rot)= 0.00792444 Eh 4.97 kcal/mol| +| sn= 9 | S(rot)= 0.00781323 Eh 4.90 kcal/mol| +| sn=10 | S(rot)= 0.00771375 Eh 4.84 kcal/mol| +| sn=11 | S(rot)= 0.00762376 Eh 4.78 kcal/mol| +| sn=12 | S(rot)= 0.00754160 Eh 4.73 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.42595756 Eh +Total entropy correction ... -0.02822238 Eh -17.71 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.45417994 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00435919 Eh -2.74 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.449820747 Eh +Current gradient norm .... 0.015086309 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.032384633 0.137078900 0.204620947 0.466517425 0.532063318 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999786674 +Lowest eigenvalues of augmented Hessian: + -0.000072766 0.135197266 0.203979307 0.466504168 0.532033459 +Length of the computed step .... 0.020658844 +The final length of the internal step .... 0.020658844 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0084339377 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0047908723 RMS(Int)= 0.0084341055 + Iter 1: RMS(Cart)= 0.0000027952 RMS(Int)= 0.0000049935 + Iter 2: RMS(Cart)= 0.0000000100 RMS(Int)= 0.0000000110 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000005 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0016505041 0.0001000000 NO + MAX gradient 0.0034187996 0.0003000000 NO + RMS step 0.0084339377 0.0020000000 NO + MAX step 0.0202379779 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0107 Max(Angles) 0.20 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4134 0.003419 -0.0107 1.4027 + 2. B(O 2,N 1) 1.1850 0.001285 0.0007 1.1857 + 3. B(H 3,O 0) 0.9779 0.000987 -0.0007 0.9772 + 4. A(N 1,O 0,H 3) 104.76 0.000651 0.06 104.82 + 5. A(O 0,N 1,O 2) 113.02 -0.001268 0.20 113.22 + 6. D(O 2,N 1,O 0,H 3) -16.36 -0.010611 0.00 -16.36 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.660606 -0.382007 0.492177 + N 0.481386 -0.594821 -0.294029 + O 0.876628 0.391094 -0.820848 + H -0.697408 0.585734 0.622700 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.248364 -0.721889 0.930080 + 1 N 7.0000 0 14.007 0.909689 -1.124049 -0.555635 + 2 O 8.0000 0 15.999 1.656587 0.739060 -1.551178 + 3 H 1.0000 0 1.008 -1.317910 1.106878 1.176733 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.402696360871 0.00000000 0.00000000 + O 2 1 0 1.185656845989 113.22110607 0.00000000 + H 1 2 3 0.977197097641 104.81956205 343.63636376 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.650711971094 0.00000000 0.00000000 + O 2 1 0 2.240566727728 113.22110607 0.00000000 + H 1 2 3 1.846634893405 104.81956205 343.63636376 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2243 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2718 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.019341314073 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.451e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.003 sec +Total time needed ... 0.007 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7226033585 0.000000000000 0.00033672 0.00000873 0.0018263 0.7000 + 1 -204.7226196446 -0.000016286088 0.00027749 0.00000734 0.0013922 0.7000 + ***Turning on DIIS*** + 2 -204.7226331621 -0.000013517492 0.00071155 0.00001908 0.0010512 0.0000 + 3 -204.7222183353 0.000414826741 0.00028593 0.00000862 0.0002540 0.0000 + 4 -204.7228518404 -0.000633505109 0.00012959 0.00000288 0.0001216 0.0000 + 5 -204.7229171069 -0.000065266507 0.00002827 0.00000089 0.0000499 0.0000 + 6 -204.7225066508 0.000410456133 0.00002170 0.00000054 0.0000343 0.0000 + 7 -204.7226737923 -0.000167141477 0.00000562 0.00000020 0.0000102 0.0000 + 8 -204.7226872620 -0.000013469697 0.00000333 0.00000011 0.0000056 0.0000 + 9 -204.7226633099 0.000023952028 0.00000170 0.00000006 0.0000021 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 10 CYCLES * + ***************************************************** + +Total Energy : -204.72268155 Eh -5570.78738 eV + Last Energy change ... -1.8236e-05 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.1947e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 2 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.471 sec +Reference energy ... -204.722677624 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 7.762 sec +AO-integral generation ... 0.246 sec +Half transformation ... 0.131 sec +K-integral sorting ... 6.462 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.048 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.039 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.067 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.050 s ( 0.000 ms/b) + 159120 b 0 skpd 0.024 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.063 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.044 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.037 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.062 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.047 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.572 sec +AO-integral generation ... 0.428 sec +Half transformation ... 0.055 sec +J-integral sorting ... 0.070 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.223 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.313 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090562361 +EMP2(bb)= -0.090562361 +EMP2(ab)= -0.514944894 + +Initial guess performed in 0.150 sec +E(0) ... -204.722677624 +E(MP2) ... -0.696069616 +Initial E(tot) ... -205.418747240 + ... 0.186518808 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.418747240 -0.696069616 -0.000000000 0.029758227 4.30 0.000001215 + *** Turning on DIIS *** + 1 -205.389898513 -0.667220889 0.028848727 0.011770519 4.52 0.058179331 + 2 -205.409284795 -0.686607171 -0.019386282 0.006730432 4.95 0.061437596 + 3 -205.412967764 -0.690290140 -0.003682969 0.002404464 4.75 0.075904590 + 4 -205.414550728 -0.691873104 -0.001582964 0.001471732 4.67 0.082943133 + 5 -205.415099416 -0.692421792 -0.000548688 0.000756987 5.52 0.088473843 + 6 -205.415199875 -0.692522251 -0.000100460 0.000475181 5.11 0.090956397 + 7 -205.415239784 -0.692562160 -0.000039909 0.000211514 4.91 0.091962469 + 8 -205.415248515 -0.692570891 -0.000008731 0.000111297 4.80 0.092323306 + 9 -205.415244652 -0.692567028 0.000003864 0.000027740 4.30 0.092431073 + 10 -205.415249024 -0.692571400 -0.000004372 0.000011248 5.06 0.092470467 + 11 -205.415246775 -0.692569151 0.000002249 0.000008358 4.78 0.092461104 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.722677624 +E(CORR) ... -0.692569151 +E(TOT) ... -205.415246775 +Singles norm **1/2 ... 0.092461104 ( 0.046230552, 0.046230552) +T1 diagnostic ... 0.021793291 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.063301 + 10a-> 13a 10b-> 13b 0.054045 + 8a-> 13a -1a-> -1a 0.050381 + 8b-> 13b -1b-> -1b 0.050381 + 10a-> 13a 8b-> 13b 0.035265 + 8a-> 13a 10b-> 13b 0.035265 + 11a-> 13a 11b-> 13b 0.029405 + 5a-> 13a 5b-> 13b 0.025355 + 10a-> 13a 10b-> 22b 0.024836 + 10a-> 22a 10b-> 13b 0.024836 + 10a-> 13a -1a-> -1a 0.024478 + 10b-> 13b -1b-> -1b 0.024478 + 8a-> 22a 8b-> 13b 0.024151 + 8a-> 13a 8b-> 22b 0.024151 + 11a-> 26a -1a-> -1a 0.023240 + 11b-> 26b -1b-> -1b 0.023240 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034609452 + alpha-alpha-alpha ... -0.000910449 ( 2.6%) + alpha-alpha-beta ... -0.016394277 ( 47.4%) + alpha-beta -beta ... -0.016394277 ( 47.4%) + beta -beta -beta ... -0.000910449 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034609452 + +Final correlation energy ... -0.727178603 +E(CCSD) ... -205.415246775 +E(CCSD(T)) ... -205.449856227 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.207803198 sqrt= 1.099001000 +W(HF) = 0.827949455 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 81.229 sec + +Fock Matrix Formation ... 0.471 sec ( 0.6%) +Initial Guess ... 0.150 sec ( 0.2%) +DIIS Solver ... 2.784 sec ( 3.4%) +State Vector Update ... 0.147 sec ( 0.2%) +Sigma-vector construction ... 54.742 sec ( 67.4%) + <0|H|D> ... 0.005 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.028 sec ( 0.1% of sigma) + (0-ext) ... 0.079 sec ( 0.1% of sigma) + (2-ext Fock) ... 0.029 sec ( 0.1% of sigma) + (2-ext) ... 1.039 sec ( 1.9% of sigma) + (4-ext) ... 32.491 sec ( 59.4% of sigma) + ... 2.712 sec ( 5.0% of sigma) + ... 0.004 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.151 sec ( 0.3% of sigma) + Fock-dressing ... 3.108 sec ( 5.7% of sigma) + (ik|jl)-dressing ... 0.086 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 12.146 sec ( 22.2% of sigma) + Pair energies ... 0.017 sec ( 0.0% of sigma) +Total Time for computing (T) ... 12.908 sec ( 15.9% of ALL) + I/O of integral and amplitudes ... 0.935 sec ( 7.2% of (T)) + External N**7 contributions ... 4.939 sec ( 38.3% of (T)) + Internal N**7 contributions ... 0.393 sec ( 3.0% of (T)) + N**6 triples energy contributions ... 1.949 sec ( 15.1% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.449856227062 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.004910220 0.000315755 -0.007450504 + 2 N : 0.004597054 0.001263130 0.006593006 + 3 O : -0.003082243 -0.001001851 -0.004207436 + 4 H : 0.003395409 -0.000577035 0.005064934 + +Norm of the cartesian gradient ... 0.014547780 +RMS gradient ... 0.004199582 +MAX gradient ... 0.007450504 + +------- +TIMINGS +------- + +Total numerical gradient time ... 453.554 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.449856227 Eh +Current gradient norm .... 0.014547780 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999608 +Lowest eigenvalues of augmented Hessian: + -0.000000125 0.139135077 0.206797580 0.466831123 0.530108819 +Length of the computed step .... 0.000885935 +The final length of the internal step .... 0.000885935 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0003616814 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0002158378 RMS(Int)= 0.0003616815 + Iter 1: RMS(Cart)= 0.0000000052 RMS(Int)= 0.0000000076 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000354804 0.0000050000 NO + RMS gradient 0.0000597567 0.0001000000 YES + MAX gradient 0.0001434586 0.0003000000 YES + RMS step 0.0003616814 0.0020000000 YES + MAX step 0.0008685876 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0005 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4027 -0.000143 0.0005 1.4032 + 2. B(O 2,N 1) 1.1857 0.000009 -0.0001 1.1856 + 3. B(H 3,O 0) 0.9772 -0.000023 0.0000 0.9772 + 4. A(N 1,O 0,H 3) 104.82 -0.000013 -0.00 104.81 + 5. A(O 0,N 1,O 2) 113.22 -0.000007 -0.00 113.22 + 6. D(O 2,N 1,O 0,H 3) -16.36 -0.010934 -0.00 -16.36 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.660780 -0.381988 0.492308 + N 0.481578 -0.594833 -0.294179 + O 0.876737 0.391053 -0.820935 + H -0.697533 0.585769 0.622807 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.248694 -0.721853 0.930327 + 1 N 7.0000 0 14.007 0.910050 -1.124072 -0.555918 + 2 O 8.0000 0 15.999 1.656793 0.738983 -1.551343 + 3 H 1.0000 0 1.008 -1.318147 1.106942 1.176935 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.403155997627 0.00000000 0.00000000 + O 2 1 0 1.185577959449 113.21936949 0.00000000 + H 1 2 3 0.977207613635 104.81480288 343.63636376 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.651580558685 0.00000000 0.00000000 + O 2 1 0 2.240417653772 113.21936949 0.00000000 + H 1 2 3 1.846654765752 104.81480288 343.63636376 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2243 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2718 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.011138018363 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 70.0111380184 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.452e-04 +Time for diagonalization ... 0.004 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.003 sec +Total time needed ... 0.008 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7226480242 0.000000000000 0.00001459 0.00000036 0.0000778 0.7000 + 1 -204.7226480553 -0.000000031021 0.00001205 0.00000031 0.0000596 0.7000 + ***Turning on DIIS*** + 2 -204.7226480811 -0.000000025875 0.00003147 0.00000083 0.0000453 0.0000 + 3 -204.7226569725 -0.000008891354 0.00001026 0.00000036 0.0000105 0.0000 + 4 -204.7226412741 0.000015698389 0.00000525 0.00000013 0.0000036 0.0000 + 5 -204.7226458161 -0.000004542003 0.00000110 0.00000004 0.0000014 0.0000 + 6 -204.7226537041 -0.000007887955 0.00000092 0.00000002 0.0000014 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72264771 Eh -5570.78646 eV + +Components: +Nuclear Repulsion : 70.01113802 Eh 1905.09992 eV +Electronic Energy : -274.73378573 Eh -7475.88638 eV +One Electron Energy: -419.60482365 Eh -11418.02773 eV +Two Electron Energy: 144.87103793 Eh 3942.14136 eV + +Virial components: +Potential Energy : -408.97111682 Eh -11128.66986 eV +Kinetic Energy : 204.24846911 Eh 5557.88340 eV +Virial Ratio : 2.00232158 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 5.9952e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.4487e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 9.0388e-09 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.7766e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.667314 -562.3862 + 1 1.0000 -20.649168 -561.8924 + 2 1.0000 -15.802843 -430.0172 + 3 1.0000 -1.608552 -43.7709 + 4 1.0000 -1.406414 -38.2705 + 5 1.0000 -0.966605 -26.3027 + 6 1.0000 -0.776268 -21.1233 + 7 1.0000 -0.743058 -20.2196 + 8 1.0000 -0.690471 -18.7887 + 9 1.0000 -0.612894 -16.6777 + 10 1.0000 -0.533396 -14.5145 + 11 1.0000 -0.474387 -12.9087 + 12 0.0000 0.031576 0.8592 + 13 0.0000 0.076523 2.0823 + 14 0.0000 0.095089 2.5875 + 15 0.0000 0.112812 3.0698 + 16 0.0000 0.124882 3.3982 + 17 0.0000 0.142304 3.8723 + 18 0.0000 0.157692 4.2910 + 19 0.0000 0.169390 4.6093 + 20 0.0000 0.183966 5.0060 + 21 0.0000 0.195215 5.3121 + 22 0.0000 0.205244 5.5850 + 23 0.0000 0.233022 6.3408 + 24 0.0000 0.252413 6.8685 + 25 0.0000 0.300963 8.1896 + 26 0.0000 0.312968 8.5163 + 27 0.0000 0.344131 9.3643 + 28 0.0000 0.351549 9.5661 + 29 0.0000 0.398627 10.8472 + 30 0.0000 0.435393 11.8476 + 31 0.0000 0.513287 13.9672 + 32 0.0000 0.519424 14.1342 + 33 0.0000 0.535030 14.5589 + 34 0.0000 0.563038 15.3210 + 35 0.0000 0.618036 16.8176 + 36 0.0000 0.637601 17.3500 + 37 0.0000 0.661993 18.0138 + 38 0.0000 0.685657 18.6577 + 39 0.0000 0.699200 19.0262 + 40 0.0000 0.734177 19.9780 + 41 0.0000 0.755423 20.5561 + 42 0.0000 0.759509 20.6673 + 43 0.0000 0.791093 21.5267 + 44 0.0000 0.794885 21.6299 + 45 0.0000 0.846175 23.0256 + 46 0.0000 0.848297 23.0833 + 47 0.0000 0.873174 23.7603 + 48 0.0000 0.919860 25.0307 + 49 0.0000 0.937378 25.5074 + 50 0.0000 0.957065 26.0431 + 51 0.0000 1.002927 27.2910 + 52 0.0000 1.024793 27.8860 + 53 0.0000 1.063696 28.9446 + 54 0.0000 1.081718 29.4350 + 55 0.0000 1.085822 29.5467 + 56 0.0000 1.180235 32.1158 + 57 0.0000 1.203328 32.7442 + 58 0.0000 1.240505 33.7559 + 59 0.0000 1.272931 34.6382 + 60 0.0000 1.346997 36.6537 + 61 0.0000 1.410361 38.3779 + 62 0.0000 1.453091 39.5406 + 63 0.0000 1.501409 40.8554 + 64 0.0000 1.543822 42.0095 + 65 0.0000 1.557283 42.3758 + 66 0.0000 1.590716 43.2856 + 67 0.0000 1.620656 44.1003 + 68 0.0000 1.657307 45.0976 + 69 0.0000 1.753777 47.7227 + 70 0.0000 1.790257 48.7154 + 71 0.0000 1.822685 49.5978 + 72 0.0000 1.902041 51.7572 + 73 0.0000 1.930035 52.5189 + 74 0.0000 1.988364 54.1061 + 75 0.0000 2.004684 54.5502 + 76 0.0000 2.037403 55.4405 + 77 0.0000 2.110381 57.4264 + 78 0.0000 2.157387 58.7055 + 79 0.0000 2.177884 59.2632 + 80 0.0000 2.282348 62.1058 + 81 0.0000 2.309448 62.8433 + 82 0.0000 2.360766 64.2397 + 83 0.0000 2.385915 64.9240 + 84 0.0000 2.434754 66.2530 + 85 0.0000 2.447303 66.5945 + 86 0.0000 2.467954 67.1565 + 87 0.0000 2.521197 68.6053 + 88 0.0000 2.532436 68.9111 + 89 0.0000 2.556517 69.5664 + 90 0.0000 2.575880 70.0933 + 91 0.0000 2.629161 71.5431 + 92 0.0000 2.668482 72.6131 + 93 0.0000 2.684549 73.0503 + 94 0.0000 2.735608 74.4397 + 95 0.0000 2.804023 76.3013 + 96 0.0000 2.888630 78.6036 + 97 0.0000 2.968249 80.7702 + 98 0.0000 2.982341 81.1536 + 99 0.0000 3.058012 83.2127 + 100 0.0000 3.147613 85.6509 + 101 0.0000 3.156375 85.8893 + 102 0.0000 3.219952 87.6194 + 103 0.0000 3.516375 95.6854 + 104 0.0000 3.735365 101.6444 + 105 0.0000 3.860111 105.0390 + 106 0.0000 4.019156 109.3668 + 107 0.0000 4.149737 112.9201 + 108 0.0000 4.177325 113.6708 + 109 0.0000 4.260222 115.9265 + 110 0.0000 4.360123 118.6450 + 111 0.0000 4.420134 120.2780 + 112 0.0000 4.515712 122.8788 + 113 0.0000 4.564903 124.2173 + 114 0.0000 4.696374 127.7948 + 115 0.0000 4.833214 131.5184 + 116 0.0000 4.880260 132.7986 + 117 0.0000 4.898955 133.3074 + 118 0.0000 4.944454 134.5454 + 119 0.0000 5.002559 136.1266 + 120 0.0000 5.070492 137.9751 + 121 0.0000 5.110141 139.0540 + 122 0.0000 5.198057 141.4463 + 123 0.0000 5.223256 142.1320 + 124 0.0000 5.231510 142.3566 + 125 0.0000 5.298193 144.1711 + 126 0.0000 5.389957 146.6682 + 127 0.0000 5.482243 149.1794 + 128 0.0000 5.550229 151.0294 + 129 0.0000 5.673818 154.3924 + 130 0.0000 5.785577 157.4336 + 131 0.0000 5.926113 161.2577 + 132 0.0000 6.180893 168.1907 + 133 0.0000 6.417288 174.6233 + 134 0.0000 6.514106 177.2578 + 135 0.0000 6.555379 178.3809 + 136 0.0000 6.681367 181.8092 + 137 0.0000 6.710127 182.5918 + 138 0.0000 6.768254 184.1735 + 139 0.0000 6.821223 185.6149 + 140 0.0000 6.942574 188.9170 + 141 0.0000 7.100143 193.2047 + 142 0.0000 7.135314 194.1618 + 143 0.0000 7.154276 194.6778 + 144 0.0000 7.172781 195.1813 + 145 0.0000 7.234801 196.8689 + 146 0.0000 7.283715 198.2000 + 147 0.0000 7.312451 198.9819 + 148 0.0000 7.402010 201.4189 + 149 0.0000 7.445668 202.6069 + 150 0.0000 7.474679 203.3963 + 151 0.0000 7.503723 204.1867 + 152 0.0000 7.609448 207.0636 + 153 0.0000 7.677421 208.9132 + 154 0.0000 7.859923 213.8794 + 155 0.0000 7.920203 215.5197 + 156 0.0000 8.287246 225.5074 + 157 0.0000 8.310417 226.1379 + 158 0.0000 14.183704 385.9582 + 159 0.0000 15.121803 411.4852 + 160 0.0000 15.632187 425.3734 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.667314 -562.3862 + 1 1.0000 -20.649168 -561.8924 + 2 1.0000 -15.802843 -430.0172 + 3 1.0000 -1.608552 -43.7709 + 4 1.0000 -1.406414 -38.2705 + 5 1.0000 -0.966605 -26.3027 + 6 1.0000 -0.776268 -21.1233 + 7 1.0000 -0.743058 -20.2196 + 8 1.0000 -0.690471 -18.7887 + 9 1.0000 -0.612894 -16.6777 + 10 1.0000 -0.533396 -14.5145 + 11 1.0000 -0.474387 -12.9087 + 12 0.0000 0.031576 0.8592 + 13 0.0000 0.076523 2.0823 + 14 0.0000 0.095089 2.5875 + 15 0.0000 0.112812 3.0698 + 16 0.0000 0.124882 3.3982 + 17 0.0000 0.142304 3.8723 + 18 0.0000 0.157692 4.2910 + 19 0.0000 0.169390 4.6093 + 20 0.0000 0.183966 5.0060 + 21 0.0000 0.195215 5.3121 + 22 0.0000 0.205244 5.5850 + 23 0.0000 0.233022 6.3408 + 24 0.0000 0.252413 6.8685 + 25 0.0000 0.300963 8.1896 + 26 0.0000 0.312968 8.5163 + 27 0.0000 0.344131 9.3643 + 28 0.0000 0.351549 9.5661 + 29 0.0000 0.398627 10.8472 + 30 0.0000 0.435393 11.8476 + 31 0.0000 0.513287 13.9672 + 32 0.0000 0.519424 14.1342 + 33 0.0000 0.535030 14.5589 + 34 0.0000 0.563038 15.3210 + 35 0.0000 0.618036 16.8176 + 36 0.0000 0.637601 17.3500 + 37 0.0000 0.661993 18.0138 + 38 0.0000 0.685657 18.6577 + 39 0.0000 0.699200 19.0262 + 40 0.0000 0.734177 19.9780 + 41 0.0000 0.755423 20.5561 + 42 0.0000 0.759509 20.6673 + 43 0.0000 0.791093 21.5267 + 44 0.0000 0.794885 21.6299 + 45 0.0000 0.846175 23.0256 + 46 0.0000 0.848297 23.0833 + 47 0.0000 0.873174 23.7603 + 48 0.0000 0.919860 25.0307 + 49 0.0000 0.937378 25.5074 + 50 0.0000 0.957065 26.0431 + 51 0.0000 1.002927 27.2910 + 52 0.0000 1.024793 27.8860 + 53 0.0000 1.063696 28.9446 + 54 0.0000 1.081718 29.4350 + 55 0.0000 1.085822 29.5467 + 56 0.0000 1.180235 32.1158 + 57 0.0000 1.203328 32.7442 + 58 0.0000 1.240505 33.7559 + 59 0.0000 1.272931 34.6382 + 60 0.0000 1.346997 36.6537 + 61 0.0000 1.410361 38.3779 + 62 0.0000 1.453091 39.5406 + 63 0.0000 1.501409 40.8554 + 64 0.0000 1.543822 42.0095 + 65 0.0000 1.557283 42.3758 + 66 0.0000 1.590716 43.2856 + 67 0.0000 1.620656 44.1003 + 68 0.0000 1.657307 45.0976 + 69 0.0000 1.753777 47.7227 + 70 0.0000 1.790257 48.7154 + 71 0.0000 1.822685 49.5978 + 72 0.0000 1.902041 51.7572 + 73 0.0000 1.930035 52.5189 + 74 0.0000 1.988364 54.1061 + 75 0.0000 2.004684 54.5502 + 76 0.0000 2.037403 55.4405 + 77 0.0000 2.110381 57.4264 + 78 0.0000 2.157387 58.7055 + 79 0.0000 2.177884 59.2632 + 80 0.0000 2.282348 62.1058 + 81 0.0000 2.309448 62.8433 + 82 0.0000 2.360766 64.2397 + 83 0.0000 2.385915 64.9240 + 84 0.0000 2.434754 66.2530 + 85 0.0000 2.447303 66.5945 + 86 0.0000 2.467954 67.1565 + 87 0.0000 2.521197 68.6053 + 88 0.0000 2.532436 68.9111 + 89 0.0000 2.556517 69.5664 + 90 0.0000 2.575880 70.0933 + 91 0.0000 2.629161 71.5431 + 92 0.0000 2.668482 72.6131 + 93 0.0000 2.684549 73.0503 + 94 0.0000 2.735608 74.4397 + 95 0.0000 2.804023 76.3013 + 96 0.0000 2.888630 78.6036 + 97 0.0000 2.968249 80.7702 + 98 0.0000 2.982341 81.1536 + 99 0.0000 3.058012 83.2127 + 100 0.0000 3.147613 85.6509 + 101 0.0000 3.156375 85.8893 + 102 0.0000 3.219952 87.6194 + 103 0.0000 3.516375 95.6854 + 104 0.0000 3.735365 101.6444 + 105 0.0000 3.860111 105.0390 + 106 0.0000 4.019156 109.3668 + 107 0.0000 4.149737 112.9201 + 108 0.0000 4.177325 113.6708 + 109 0.0000 4.260222 115.9265 + 110 0.0000 4.360123 118.6450 + 111 0.0000 4.420134 120.2780 + 112 0.0000 4.515712 122.8788 + 113 0.0000 4.564903 124.2173 + 114 0.0000 4.696374 127.7948 + 115 0.0000 4.833214 131.5184 + 116 0.0000 4.880260 132.7986 + 117 0.0000 4.898955 133.3074 + 118 0.0000 4.944454 134.5454 + 119 0.0000 5.002559 136.1266 + 120 0.0000 5.070492 137.9751 + 121 0.0000 5.110141 139.0540 + 122 0.0000 5.198057 141.4463 + 123 0.0000 5.223256 142.1320 + 124 0.0000 5.231510 142.3566 + 125 0.0000 5.298193 144.1711 + 126 0.0000 5.389957 146.6682 + 127 0.0000 5.482243 149.1794 + 128 0.0000 5.550229 151.0294 + 129 0.0000 5.673818 154.3924 + 130 0.0000 5.785577 157.4336 + 131 0.0000 5.926113 161.2577 + 132 0.0000 6.180893 168.1907 + 133 0.0000 6.417288 174.6233 + 134 0.0000 6.514106 177.2578 + 135 0.0000 6.555379 178.3809 + 136 0.0000 6.681367 181.8092 + 137 0.0000 6.710127 182.5918 + 138 0.0000 6.768254 184.1735 + 139 0.0000 6.821223 185.6149 + 140 0.0000 6.942574 188.9170 + 141 0.0000 7.100143 193.2047 + 142 0.0000 7.135314 194.1618 + 143 0.0000 7.154276 194.6778 + 144 0.0000 7.172781 195.1813 + 145 0.0000 7.234801 196.8689 + 146 0.0000 7.283715 198.2000 + 147 0.0000 7.312451 198.9819 + 148 0.0000 7.402010 201.4189 + 149 0.0000 7.445668 202.6069 + 150 0.0000 7.474679 203.3963 + 151 0.0000 7.503723 204.1867 + 152 0.0000 7.609448 207.0636 + 153 0.0000 7.677421 208.9132 + 154 0.0000 7.859923 213.8794 + 155 0.0000 7.920203 215.5197 + 156 0.0000 8.287246 225.5074 + 157 0.0000 8.310417 226.1379 + 158 0.0000 14.183704 385.9582 + 159 0.0000 15.121803 411.4852 + 160 0.0000 15.632187 425.3734 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.283919 0.000000 + 1 N : 0.335772 0.000000 + 2 O : -0.301254 0.000000 + 3 H : 0.249400 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.804039 s : 3.804039 + pz : 1.645894 p : 4.437635 + px : 1.406699 + py : 1.385042 + dz2 : 0.009325 d : 0.036818 + dxz : 0.007669 + dyz : 0.000462 + dx2y2 : 0.016333 + dxy : 0.003029 + f0 : 0.000406 f : 0.005427 + f+1 : 0.001334 + f-1 : 0.000296 + f+2 : 0.000778 + f-2 : 0.001100 + f+3 : 0.000564 + f-3 : 0.000950 + 1 N s : 3.862588 s : 3.862588 + pz : 0.715859 p : 2.624319 + px : 0.730154 + py : 1.178307 + dz2 : 0.030943 d : 0.144104 + dxz : 0.028137 + dyz : 0.025509 + dx2y2 : 0.036931 + dxy : 0.022584 + f0 : 0.001601 f : 0.033217 + f+1 : 0.004119 + f-1 : 0.005530 + f+2 : 0.003120 + f-2 : 0.005384 + f+3 : 0.005897 + f-3 : 0.007567 + 2 O s : 3.858575 s : 3.858575 + pz : 1.372044 p : 4.375350 + px : 1.622020 + py : 1.381286 + dz2 : 0.013373 d : 0.059883 + dxz : 0.003175 + dyz : 0.016001 + dx2y2 : 0.009889 + dxy : 0.017445 + f0 : 0.000300 f : 0.007445 + f+1 : 0.000157 + f-1 : 0.001953 + f+2 : 0.001273 + f-2 : 0.000947 + f+3 : 0.001300 + f-3 : 0.001515 + 3 H s : 0.645683 s : 0.645683 + pz : 0.035618 p : 0.083745 + px : 0.028143 + py : 0.019984 + dz2 : 0.000195 d : 0.021172 + dxz : -0.000850 + dyz : 0.010137 + dx2y2 : 0.000537 + dxy : 0.011153 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.601508 0.000000 + 1 N : -0.282490 0.000000 + 2 O : 0.244800 0.000000 + 3 H : -0.563818 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.107060 s : 3.107060 + pz : 1.350726 p : 3.898956 + px : 1.258293 + py : 1.289936 + dz2 : 0.042477 d : 0.299010 + dxz : 0.082572 + dyz : 0.035639 + dx2y2 : 0.072229 + dxy : 0.066093 + f0 : 0.008475 f : 0.093466 + f+1 : 0.016602 + f-1 : 0.003146 + f+2 : 0.015052 + f-2 : 0.019606 + f+3 : 0.008470 + f-3 : 0.022116 + 1 N s : 3.000969 s : 3.000969 + pz : 0.758985 p : 2.830482 + px : 0.819800 + py : 1.251696 + dz2 : 0.176348 d : 0.978348 + dxz : 0.205635 + dyz : 0.159303 + dx2y2 : 0.250628 + dxy : 0.186432 + f0 : 0.032973 f : 0.472691 + f+1 : 0.053347 + f-1 : 0.059288 + f+2 : 0.071207 + f-2 : 0.085145 + f+3 : 0.074740 + f-3 : 0.095990 + 2 O s : 3.298968 s : 3.298968 + pz : 1.225249 p : 4.020936 + px : 1.363006 + py : 1.432680 + dz2 : 0.042584 d : 0.319637 + dxz : 0.044024 + dyz : 0.068440 + dx2y2 : 0.111059 + dxy : 0.053531 + f0 : 0.008699 f : 0.115659 + f+1 : 0.004496 + f-1 : 0.018956 + f+2 : 0.020706 + f-2 : 0.019304 + f+3 : 0.014403 + f-3 : 0.029095 + 3 H s : 0.610557 s : 0.610557 + pz : 0.144238 p : 0.543413 + px : 0.135713 + py : 0.263462 + dz2 : 0.041586 d : 0.409849 + dxz : 0.028321 + dyz : 0.118060 + dx2y2 : 0.104845 + dxy : 0.117038 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2839 8.0000 -0.2839 1.8091 1.8091 -0.0000 + 1 N 6.6642 7.0000 0.3358 2.5077 2.5077 -0.0000 + 2 O 8.3013 8.0000 -0.3013 1.6737 1.6737 0.0000 + 3 H 0.7506 1.0000 0.2494 1.0149 1.0149 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8242 B( 0-O , 3-H ) : 0.9265 B( 1-N , 2-O ) : 1.6052 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.552 sec +Sum of individual times .... 1.285 sec ( 82.8%) + +Fock matrix formation .... 1.036 sec ( 66.8%) +Diagonalization .... 0.103 sec ( 6.6%) +Density matrix formation .... 0.008 sec ( 0.5%) +Population analysis .... 0.051 sec ( 3.3%) +Initial guess .... 0.011 sec ( 0.7%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.006 sec ( 0.4%) +DIIS solution .... 0.075 sec ( 4.8%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.293 sec +Reference energy ... -204.722648169 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 7.370 sec +AO-integral generation ... 0.186 sec +Half transformation ... 0.102 sec +K-integral sorting ... 6.134 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.043 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.057 s ( 0.000 ms/b) +: : 277134 b 0 skpd 0.068 s ( 0.000 ms/b) + 151164 b 0 skpd 0.072 s ( 0.000 ms/b) +: 159120 b 0 skpd 0.031 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.070 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.048 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.034 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.057 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.055 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.694 sec +AO-integral generation ... 0.492 sec +Half transformation ... 0.045 sec +J-integral sorting ... 0.120 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.280 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.356 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090564769 +EMP2(bb)= -0.090564769 +EMP2(ab)= -0.514967550 + +Initial guess performed in 0.170 sec +E(0) ... -204.722648169 +E(MP2) ... -0.696097088 +Initial E(tot) ... -205.418745258 + ... 0.186546774 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.418745258 -0.696097088 -0.000000000 0.029747444 6.75 0.000000561 + *** Turning on DIIS *** + 1 -205.389884925 -0.667236755 0.028860333 0.011766454 5.67 0.058192273 + 2 -205.409275991 -0.686627821 -0.019391066 0.006727617 4.16 0.061447435 + 3 -205.412959932 -0.690311763 -0.003683942 0.002402681 4.66 0.075919469 + 4 -205.414543461 -0.691895292 -0.001583529 0.001471090 4.73 0.082960670 + 5 -205.415092697 -0.692444527 -0.000549235 0.000759034 4.32 0.088497755 + 6 -205.415193339 -0.692545170 -0.000100643 0.000476345 4.40 0.090985484 + 7 -205.415233352 -0.692585182 -0.000040012 0.000211823 4.82 0.091994874 + 8 -205.415242125 -0.692593955 -0.000008773 0.000111448 4.39 0.092356996 + 9 -205.415238251 -0.692590081 0.000003874 0.000027778 4.94 0.092465044 + 10 -205.415242636 -0.692594467 -0.000004385 0.000011227 5.32 0.092504572 + 11 -205.415240382 -0.692592212 0.000002254 0.000008340 4.80 0.092495194 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.722648169 +E(CORR) ... -0.692592212 +E(TOT) ... -205.415240382 +Singles norm **1/2 ... 0.092495194 ( 0.046247597, 0.046247597) +T1 diagnostic ... 0.021801326 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.063370 + 10a-> 13a 10b-> 13b 0.053970 + 8b-> 13b -1b-> -1b 0.050362 + 8a-> 13a -1a-> -1a 0.050362 + 10a-> 13a 8b-> 13b 0.035267 + 8a-> 13a 10b-> 13b 0.035267 + 11a-> 13a 11b-> 13b 0.029396 + 5a-> 13a 5b-> 13b 0.025377 + 10a-> 22a 10b-> 13b 0.024798 + 10a-> 13a 10b-> 22b 0.024798 + 10a-> 13a -1a-> -1a 0.024574 + 10b-> 13b -1b-> -1b 0.024574 + 8a-> 22a 8b-> 13b 0.024174 + 8a-> 13a 8b-> 22b 0.024174 + 11b-> 26b -1b-> -1b 0.023306 + 11a-> 26a -1a-> -1a 0.023306 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034615914 + alpha-alpha-alpha ... -0.000910534 ( 2.6%) + alpha-alpha-beta ... -0.016397423 ( 47.4%) + alpha-beta -beta ... -0.016397423 ( 47.4%) + beta -beta -beta ... -0.000910534 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034615914 + +Final correlation energy ... -0.727208126 +E(CCSD) ... -205.415240382 +E(CCSD(T)) ... -205.449856295 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.207845157 sqrt= 1.099020090 +W(HF) = 0.827920693 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.195246 0.000000 + 1 N : 0.143288 0.000000 + 2 O : -0.180515 -0.000000 + 3 H : 0.232473 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.791266 s : 3.791266 + pz : 1.589840 p : 4.328404 + px : 1.377622 + py : 1.360942 + dz2 : 0.015987 d : 0.066510 + dxz : 0.012379 + dyz : 0.007681 + dx2y2 : 0.019823 + dxy : 0.010640 + f0 : 0.000941 f : 0.009065 + f+1 : 0.001868 + f-1 : 0.000939 + f+2 : 0.001121 + f-2 : 0.001559 + f+3 : 0.001123 + f-3 : 0.001515 + 1 N s : 3.912781 s : 3.912781 + pz : 0.811739 p : 2.740410 + px : 0.795146 + py : 1.133526 + dz2 : 0.037002 d : 0.171292 + dxz : 0.035046 + dyz : 0.028036 + dx2y2 : 0.044657 + dxy : 0.026551 + f0 : 0.001883 f : 0.032230 + f+1 : 0.004111 + f-1 : 0.005094 + f+2 : 0.002801 + f-2 : 0.005370 + f+3 : 0.005405 + f-3 : 0.007565 + 2 O s : 3.846276 s : 3.846276 + pz : 1.326223 p : 4.240955 + px : 1.561087 + py : 1.353645 + dz2 : 0.017883 d : 0.083154 + dxz : 0.009909 + dyz : 0.017962 + dx2y2 : 0.016797 + dxy : 0.020603 + f0 : 0.000796 f : 0.010130 + f+1 : 0.000717 + f-1 : 0.002077 + f+2 : 0.001607 + f-2 : 0.001404 + f+3 : 0.001626 + f-3 : 0.001903 + 3 H s : 0.662392 s : 0.662392 + pz : 0.040298 p : 0.085503 + px : 0.031831 + py : 0.013374 + dz2 : 0.000255 d : 0.019632 + dxz : -0.000224 + dyz : 0.009200 + dx2y2 : 0.000037 + dxy : 0.010364 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.617060 -0.000000 + 1 N : -0.331581 0.000000 + 2 O : 0.280785 -0.000000 + 3 H : -0.566264 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.115836 s : 3.115836 + pz : 1.315845 p : 3.835518 + px : 1.244293 + py : 1.275380 + dz2 : 0.049765 d : 0.330672 + dxz : 0.089138 + dyz : 0.041654 + dx2y2 : 0.079245 + dxy : 0.070871 + f0 : 0.009341 f : 0.100914 + f+1 : 0.018758 + f-1 : 0.004241 + f+2 : 0.016339 + f-2 : 0.019785 + f+3 : 0.009771 + f-3 : 0.022680 + 1 N s : 3.006509 s : 3.006509 + pz : 0.816418 p : 2.882125 + px : 0.852257 + py : 1.213449 + dz2 : 0.174019 d : 0.982196 + dxz : 0.212599 + dyz : 0.160959 + dx2y2 : 0.252107 + dxy : 0.182511 + f0 : 0.033321 f : 0.460751 + f+1 : 0.048207 + f-1 : 0.057573 + f+2 : 0.071217 + f-2 : 0.082846 + f+3 : 0.074833 + f-3 : 0.092755 + 2 O s : 3.300959 s : 3.300959 + pz : 1.199792 p : 3.940019 + px : 1.326798 + py : 1.413429 + dz2 : 0.052418 d : 0.353607 + dxz : 0.048996 + dyz : 0.076009 + dx2y2 : 0.114918 + dxy : 0.061265 + f0 : 0.009423 f : 0.124629 + f+1 : 0.005657 + f-1 : 0.022502 + f+2 : 0.022004 + f-2 : 0.019737 + f+3 : 0.016488 + f-3 : 0.028819 + 3 H s : 0.615906 s : 0.615906 + pz : 0.146698 p : 0.551018 + px : 0.136730 + py : 0.267590 + dz2 : 0.041232 d : 0.399340 + dxz : 0.028311 + dyz : 0.112602 + dx2y2 : 0.104213 + dxy : 0.112983 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.1952 8.0000 -0.1952 2.1855 1.7364 0.4490 + 1 N 6.8567 7.0000 0.1433 2.7960 2.3266 0.4695 + 2 O 8.1805 8.0000 -0.1805 2.0808 1.5831 0.4977 + 3 H 0.7675 1.0000 0.2325 1.0342 0.9603 0.0740 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7823 B( 0-O , 2-O ) : 0.1006 B( 0-O , 3-H ) : 0.8536 +B( 1-N , 2-O ) : 1.4600 + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 79.606 sec + +Fock Matrix Formation ... 0.293 sec ( 0.4%) +Initial Guess ... 0.170 sec ( 0.2%) +DIIS Solver ... 3.093 sec ( 3.9%) +State Vector Update ... 0.147 sec ( 0.2%) +Sigma-vector construction ... 55.724 sec ( 70.0%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.021 sec ( 0.0% of sigma) + (0-ext) ... 0.064 sec ( 0.1% of sigma) + (2-ext Fock) ... 0.024 sec ( 0.0% of sigma) + (2-ext) ... 0.887 sec ( 1.6% of sigma) + (4-ext) ... 33.181 sec ( 59.5% of sigma) + ... 3.189 sec ( 5.7% of sigma) + ... 0.004 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.151 sec ( 0.3% of sigma) + Fock-dressing ... 3.442 sec ( 6.2% of sigma) + (ik|jl)-dressing ... 0.070 sec ( 0.1% of sigma) + (ij|ab),(ia|jb)-dressing ... 11.948 sec ( 21.4% of sigma) + Pair energies ... 0.022 sec ( 0.0% of sigma) +Total Time for computing (T) ... 10.265 sec ( 12.9% of ALL) + I/O of integral and amplitudes ... 1.223 sec ( 11.9% of (T)) + External N**7 contributions ... 4.698 sec ( 45.8% of (T)) + Internal N**7 contributions ... 0.418 sec ( 4.1% of (T)) + N**6 triples energy contributions ... 2.125 sec ( 20.7% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.449856295491 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.021.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.021.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.381757, -0.305342 -0.351733) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.65363 -0.25310 -0.49580 +Nuclear contribution : -0.84518 0.70367 0.75898 + ----------------------------------------- +Total Dipole Moment : -0.19155 0.45058 0.26318 + ----------------------------------------- +Magnitude (a.u.) : 0.55586 +Magnitude (Debye) : 1.41287 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.779286 0.436915 0.378493 +Rotational constants in MHz : 83320.899661 13098.394943 11346.936922 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.165038 0.506707 0.158068 +x,y,z [Debye]: -0.419492 1.287947 0.401778 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.381757, -0.305342 -0.351733) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.67029 -0.17240 -0.54836 +Nuclear contribution : -0.84518 0.70367 0.75898 + ----------------------------------------- +Total Dipole Moment : -0.17489 0.53127 0.21061 + ----------------------------------------- +Magnitude (a.u.) : 0.59766 +Magnitude (Debye) : 1.51913 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.779286 0.436915 0.378493 +Rotational constants in MHz : 83320.899661 13098.394943 11346.936922 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.096169 0.573319 0.138753 +x,y,z [Debye]: -0.244442 1.457260 0.352683 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 22 * + * * + * Dihedral ( 2, 1, 0, 3) : -8.18181818 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0314924384 RMS(Int)= 0.0006972004 + Iter 1: RMS(Cart)= 0.0001537577 RMS(Int)= 0.0000087551 + Iter 2: RMS(Cart)= 0.0000019308 RMS(Int)= 0.0000001104 + Iter 3: RMS(Cart)= 0.0000000243 RMS(Int)= 0.0000000014 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4047 0.000000 + 2. B(O 2,N 1) 1.1868 0.000000 + 3. B(H 3,O 0) 0.9790 0.000000 + 4. A(N 1,O 0,H 3) 104.6061 0.000000 + 5. A(O 0,N 1,O 2) 113.0402 0.000000 + 6. D(O 2,N 1,O 0,H 3) -8.1818 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.641723 -0.384805 0.520985 + N 0.463146 -0.601958 -0.318789 + O 0.883921 0.397673 -0.800605 + H -0.705343 0.589089 0.598408 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.212680 -0.727176 0.984519 + 1 N 7.0000 0 14.007 0.875219 -1.137535 -0.602424 + 2 O 8.0000 0 15.999 1.670369 0.751494 -1.512924 + 3 H 1.0000 0 1.008 -1.332906 1.113217 1.130828 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.403155997627 0.00000000 0.00000000 + O 2 1 0 1.185577959449 113.21936949 0.00000000 + H 1 2 3 0.977207613635 104.81480288 343.63636376 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.651580558685 0.00000000 0.00000000 + O 2 1 0 2.240417653772 113.21936949 0.00000000 + H 1 2 3 1.846654765752 104.81480288 343.63636376 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2243 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2718 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.971832422024 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.9718324220 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.446e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.003 sec +Total time needed ... 0.007 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7192794363 0.000000000000 0.00195191 0.00005526 0.0130478 0.7000 + 1 -204.7200157860 -0.000736349722 0.00173582 0.00005093 0.0109141 0.7000 + ***Turning on DIIS*** + 2 -204.7206584476 -0.000642661577 0.00460188 0.00013969 0.0089705 0.0000 + 3 -204.7237326899 -0.003074242366 0.00212608 0.00006121 0.0040779 0.0000 + 4 -204.7221873729 0.001545317088 0.00098337 0.00003071 0.0017249 0.0000 + 5 -204.7238926805 -0.001705307679 0.00088047 0.00003552 0.0009171 0.0000 + 6 -204.7231292373 0.000763443200 0.00052305 0.00002389 0.0005178 0.0000 + 7 -204.7229383944 0.000190842954 0.00031400 0.00001534 0.0002932 0.0000 + 8 -204.7236127143 -0.000674319947 0.00019289 0.00000851 0.0001847 0.0000 + 9 -204.7231269935 0.000485720820 0.00008479 0.00000285 0.0000638 0.0000 + 10 -204.7232761248 -0.000149131339 0.00003137 0.00000087 0.0000264 0.0000 + 11 -204.7232564169 0.000019707964 0.00001163 0.00000026 0.0000164 0.0000 + 12 -204.7232192056 0.000037211273 0.00000567 0.00000013 0.0000078 0.0000 + 13 -204.7232401902 -0.000020984639 0.00000179 0.00000005 0.0000026 0.0000 + 14 -204.7232358202 0.000004370050 0.00000077 0.00000003 0.0000011 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 15 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72323545 Eh -5570.80245 eV + +Components: +Nuclear Repulsion : 69.97183242 Eh 1904.03036 eV +Electronic Energy : -274.69506787 Eh -7474.83281 eV +One Electron Energy: -419.52619020 Eh -11415.88801 eV +Two Electron Energy: 144.83112233 Eh 3941.05520 eV + +Virial components: +Potential Energy : -408.95894158 Eh -11128.33855 eV +Kinetic Energy : 204.23570613 Eh 5557.53610 eV +Virial Ratio : 2.00238709 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.7363e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.5226e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.9878e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.5909e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.667255 -562.3846 + 1 1.0000 -20.650118 -561.9183 + 2 1.0000 -15.803797 -430.0432 + 3 1.0000 -1.607961 -43.7548 + 4 1.0000 -1.405648 -38.2496 + 5 1.0000 -0.966916 -26.3111 + 6 1.0000 -0.775499 -21.1024 + 7 1.0000 -0.743230 -20.2243 + 8 1.0000 -0.688609 -18.7380 + 9 1.0000 -0.614666 -16.7259 + 10 1.0000 -0.533005 -14.5038 + 11 1.0000 -0.475269 -12.9327 + 12 0.0000 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3.7783 + 18 0.0000 0.157981 4.2989 + 19 0.0000 0.169168 4.6033 + 20 0.0000 0.184711 5.0262 + 21 0.0000 0.195226 5.3124 + 22 0.0000 0.205435 5.5902 + 23 0.0000 0.232533 6.3275 + 24 0.0000 0.250632 6.8200 + 25 0.0000 0.301698 8.2096 + 26 0.0000 0.311642 8.4802 + 27 0.0000 0.343979 9.3601 + 28 0.0000 0.351838 9.5740 + 29 0.0000 0.400521 10.8987 + 30 0.0000 0.440395 11.9838 + 31 0.0000 0.512254 13.9392 + 32 0.0000 0.516319 14.0497 + 33 0.0000 0.535431 14.5698 + 34 0.0000 0.562401 15.3037 + 35 0.0000 0.617455 16.8018 + 36 0.0000 0.639498 17.4016 + 37 0.0000 0.666697 18.1417 + 38 0.0000 0.683895 18.6097 + 39 0.0000 0.697962 18.9925 + 40 0.0000 0.733304 19.9542 + 41 0.0000 0.756406 20.5829 + 42 0.0000 0.762558 20.7503 + 43 0.0000 0.784106 21.3366 + 44 0.0000 0.797685 21.7061 + 45 0.0000 0.845193 22.9989 + 46 0.0000 0.850149 23.1337 + 47 0.0000 0.870615 23.6906 + 48 0.0000 0.918839 25.0029 + 49 0.0000 0.937768 25.5180 + 50 0.0000 0.954915 25.9846 + 51 0.0000 1.006444 27.3867 + 52 0.0000 1.027500 27.9597 + 53 0.0000 1.071464 29.1560 + 54 0.0000 1.081280 29.4231 + 55 0.0000 1.088110 29.6090 + 56 0.0000 1.178651 32.0727 + 57 0.0000 1.213891 33.0317 + 58 0.0000 1.238607 33.7042 + 59 0.0000 1.264426 34.4068 + 60 0.0000 1.342176 36.5225 + 61 0.0000 1.411763 38.4160 + 62 0.0000 1.460942 39.7543 + 63 0.0000 1.503906 40.9234 + 64 0.0000 1.541608 41.9493 + 65 0.0000 1.556093 42.3434 + 66 0.0000 1.591232 43.2996 + 67 0.0000 1.611024 43.8382 + 68 0.0000 1.656600 45.0784 + 69 0.0000 1.762979 47.9731 + 70 0.0000 1.787957 48.6528 + 71 0.0000 1.821138 49.5557 + 72 0.0000 1.905350 51.8472 + 73 0.0000 1.921527 52.2874 + 74 0.0000 1.988955 54.1222 + 75 0.0000 1.997166 54.3456 + 76 0.0000 2.037909 55.4543 + 77 0.0000 2.122128 57.7460 + 78 0.0000 2.150837 58.5273 + 79 0.0000 2.178020 59.2669 + 80 0.0000 2.286426 62.2168 + 81 0.0000 2.318894 63.1003 + 82 0.0000 2.351704 63.9931 + 83 0.0000 2.385291 64.9071 + 84 0.0000 2.435646 66.2773 + 85 0.0000 2.455348 66.8134 + 86 0.0000 2.472048 67.2678 + 87 0.0000 2.510256 68.3075 + 88 0.0000 2.518577 68.5340 + 89 0.0000 2.560086 69.6635 + 90 0.0000 2.575900 70.0938 + 91 0.0000 2.638007 71.7838 + 92 0.0000 2.661060 72.4111 + 93 0.0000 2.690920 73.2237 + 94 0.0000 2.744307 74.6764 + 95 0.0000 2.793183 76.0064 + 96 0.0000 2.904195 79.0272 + 97 0.0000 2.962404 80.6111 + 98 0.0000 2.975001 80.9539 + 99 0.0000 3.060407 83.2779 + 100 0.0000 3.143011 85.5257 + 101 0.0000 3.154318 85.8334 + 102 0.0000 3.215590 87.5006 + 103 0.0000 3.509391 95.4954 + 104 0.0000 3.751129 102.0734 + 105 0.0000 3.841112 104.5220 + 106 0.0000 4.021359 109.4267 + 107 0.0000 4.151753 112.9749 + 108 0.0000 4.173723 113.5728 + 109 0.0000 4.241984 115.4303 + 110 0.0000 4.358425 118.5988 + 111 0.0000 4.409040 119.9761 + 112 0.0000 4.519131 122.9718 + 113 0.0000 4.566932 124.2725 + 114 0.0000 4.696139 127.7884 + 115 0.0000 4.841734 131.7503 + 116 0.0000 4.884321 132.9091 + 117 0.0000 4.899217 133.3145 + 118 0.0000 4.942719 134.4982 + 119 0.0000 4.998620 136.0194 + 120 0.0000 5.065087 137.8280 + 121 0.0000 5.104162 138.8913 + 122 0.0000 5.197609 141.4341 + 123 0.0000 5.218861 142.0124 + 124 0.0000 5.230147 142.3195 + 125 0.0000 5.301671 144.2658 + 126 0.0000 5.385906 146.5580 + 127 0.0000 5.479175 149.0959 + 128 0.0000 5.554333 151.1411 + 129 0.0000 5.662710 154.0902 + 130 0.0000 5.788369 157.5095 + 131 0.0000 5.920973 161.1179 + 132 0.0000 6.181399 168.2044 + 133 0.0000 6.417181 174.6204 + 134 0.0000 6.517376 177.3468 + 135 0.0000 6.564876 178.6394 + 136 0.0000 6.674853 181.6320 + 137 0.0000 6.703318 182.4066 + 138 0.0000 6.764687 184.0765 + 139 0.0000 6.828906 185.8240 + 140 0.0000 6.946040 189.0114 + 141 0.0000 7.099919 193.1986 + 142 0.0000 7.121863 193.7957 + 143 0.0000 7.154821 194.6926 + 144 0.0000 7.166674 195.0151 + 145 0.0000 7.229743 196.7313 + 146 0.0000 7.282549 198.1682 + 147 0.0000 7.313565 199.0122 + 148 0.0000 7.407988 201.5816 + 149 0.0000 7.431144 202.2117 + 150 0.0000 7.462947 203.0771 + 151 0.0000 7.495252 203.9562 + 152 0.0000 7.606445 206.9819 + 153 0.0000 7.684728 209.1121 + 154 0.0000 7.855250 213.7522 + 155 0.0000 7.931678 215.8319 + 156 0.0000 8.299937 225.8528 + 157 0.0000 8.302538 225.9235 + 158 0.0000 14.183021 385.9396 + 159 0.0000 15.047721 409.4693 + 160 0.0000 15.615133 424.9094 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.283696 0.000000 + 1 N : 0.335231 0.000000 + 2 O : -0.302322 0.000000 + 3 H : 0.250787 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.803242 s : 3.803242 + pz : 1.616579 p : 4.437801 + px : 1.439513 + py : 1.381709 + dz2 : 0.009917 d : 0.037189 + dxz : 0.007670 + dyz : 0.000771 + dx2y2 : 0.016654 + dxy : 0.002177 + f0 : 0.000411 f : 0.005463 + f+1 : 0.001365 + f-1 : 0.000313 + f+2 : 0.000864 + f-2 : 0.001196 + f+3 : 0.000432 + f-3 : 0.000882 + 1 N s : 3.865705 s : 3.865705 + pz : 0.710960 p : 2.621683 + px : 0.726030 + py : 1.184693 + dz2 : 0.030749 d : 0.144184 + dxz : 0.028085 + dyz : 0.025203 + dx2y2 : 0.036217 + dxy : 0.023929 + f0 : 0.002148 f : 0.033196 + f+1 : 0.003651 + f-1 : 0.005485 + f+2 : 0.003080 + f-2 : 0.005504 + f+3 : 0.005650 + f-3 : 0.007678 + 2 O s : 3.857112 s : 3.857112 + pz : 1.413422 p : 4.377979 + px : 1.586100 + py : 1.378457 + dz2 : 0.012039 d : 0.059779 + dxz : 0.002890 + dyz : 0.016913 + dx2y2 : 0.010466 + dxy : 0.017471 + f0 : 0.000324 f : 0.007452 + f+1 : 0.000185 + f-1 : 0.001875 + f+2 : 0.001184 + f-2 : 0.000930 + f+3 : 0.001316 + f-3 : 0.001638 + 3 H s : 0.646000 s : 0.646000 + pz : 0.033400 p : 0.082322 + px : 0.029019 + py : 0.019903 + dz2 : -0.000077 d : 0.020891 + dxz : -0.000959 + dyz : 0.010524 + dx2y2 : 0.000462 + dxy : 0.010941 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.600009 0.000000 + 1 N : -0.279729 0.000000 + 2 O : 0.244739 0.000000 + 3 H : -0.565019 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.108834 s : 3.108834 + pz : 1.341883 p : 3.899260 + px : 1.269394 + py : 1.287982 + dz2 : 0.043526 d : 0.298532 + dxz : 0.085020 + dyz : 0.038044 + dx2y2 : 0.068429 + dxy : 0.063514 + f0 : 0.008455 f : 0.093365 + f+1 : 0.016772 + f-1 : 0.004318 + f+2 : 0.015117 + f-2 : 0.021187 + f+3 : 0.007639 + f-3 : 0.019876 + 1 N s : 3.002368 s : 3.002368 + pz : 0.757333 p : 2.829047 + px : 0.808895 + py : 1.262820 + dz2 : 0.179039 d : 0.975995 + dxz : 0.202966 + dyz : 0.157962 + dx2y2 : 0.249726 + dxy : 0.186301 + f0 : 0.036867 f : 0.472319 + f+1 : 0.052376 + f-1 : 0.060159 + f+2 : 0.067410 + f-2 : 0.085305 + f+3 : 0.073264 + f-3 : 0.096938 + 2 O s : 3.298088 s : 3.298088 + pz : 1.242185 p : 4.022162 + px : 1.344058 + py : 1.435918 + dz2 : 0.044285 d : 0.319521 + dxz : 0.042856 + dyz : 0.062540 + dx2y2 : 0.113557 + dxy : 0.056283 + f0 : 0.008492 f : 0.115490 + f+1 : 0.004508 + f-1 : 0.019496 + f+2 : 0.017984 + f-2 : 0.018913 + f+3 : 0.016038 + f-3 : 0.030059 + 3 H s : 0.609869 s : 0.609869 + pz : 0.141537 p : 0.542192 + px : 0.136618 + py : 0.264038 + dz2 : 0.040154 d : 0.412958 + dxz : 0.028569 + dyz : 0.119227 + dx2y2 : 0.106796 + dxy : 0.118212 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2837 8.0000 -0.2837 1.8069 1.8069 0.0000 + 1 N 6.6648 7.0000 0.3352 2.5059 2.5059 -0.0000 + 2 O 8.3023 8.0000 -0.3023 1.6685 1.6685 0.0000 + 3 H 0.7492 1.0000 0.2508 1.0130 1.0130 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8261 B( 0-O , 3-H ) : 0.9223 B( 1-N , 2-O ) : 1.5996 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 3 sec + +Total time .... 3.805 sec +Sum of individual times .... 3.485 sec ( 91.6%) + +Fock matrix formation .... 3.021 sec ( 79.4%) +Diagonalization .... 0.212 sec ( 5.6%) +Density matrix formation .... 0.015 sec ( 0.4%) +Population analysis .... 0.051 sec ( 1.3%) +Initial guess .... 0.014 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.008 sec ( 0.2%) +DIIS solution .... 0.172 sec ( 4.5%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.296 sec +Reference energy ... -204.723235546 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 7.234 sec +AO-integral generation ... 0.174 sec +Half transformation ... 0.095 sec +K-integral sorting ... 5.943 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.049 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.050 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.048 s ( 0.000 ms/b) + 151164 b 0 skpd 0.093 s ( 0.001 ms/b) +: 159120 b 0 skpd 0.030 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.060 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.061 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.063 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.033 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.620 sec +AO-integral generation ... 0.477 sec +Half transformation ... 0.050 sec +J-integral sorting ... 0.072 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.242 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.285 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090682458 +EMP2(bb)= -0.090682458 +EMP2(ab)= -0.515400694 + +Initial guess performed in 0.149 sec +E(0) ... -204.723235546 +E(MP2) ... -0.696765611 +Initial E(tot) ... -205.420001156 + ... 0.187060218 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.420001156 -0.696765611 -0.000000000 0.030696978 4.63 0.000002340 + *** Turning on DIIS *** + 1 -205.390783213 -0.667547667 0.029217944 0.012299087 4.65 0.058598340 + 2 -205.410281534 -0.687045989 -0.019498322 0.006965531 4.73 0.061806091 + 3 -205.413976751 -0.690741206 -0.003695217 0.002505196 4.94 0.076394529 + 4 -205.415573382 -0.692337836 -0.001596631 0.001534131 4.77 0.083498560 + 5 -205.416129110 -0.692893564 -0.000555728 0.000755337 3.44 0.089084670 + 6 -205.416229879 -0.692994333 -0.000100769 0.000476946 3.47 0.091566965 + 7 -205.416269980 -0.693034435 -0.000040102 0.000210453 3.46 0.092568228 + 8 -205.416278833 -0.693043287 -0.000008853 0.000112565 3.44 0.092922307 + 9 -205.416274913 -0.693039368 0.000003920 0.000028652 3.64 0.093027589 + 10 -205.416279337 -0.693043792 -0.000004424 0.000007985 4.55 0.093065861 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.723235546 +E(CORR) ... -0.693043792 +E(TOT) ... -205.416279337 +Singles norm **1/2 ... 0.093065861 ( 0.046532930, 0.046532930) +T1 diagnostic ... 0.021935834 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.066075 + 10a-> 13a 10b-> 13b 0.056234 + 8b-> 13b -1b-> -1b 0.052223 + 8a-> 13a -1a-> -1a 0.052223 + 8a-> 13a 10b-> 13b 0.036966 + 10a-> 13a 8b-> 13b 0.036966 + 11a-> 13a 11b-> 13b 0.028980 + 10a-> 22a 10b-> 13b 0.025787 + 10a-> 13a 10b-> 22b 0.025787 + 5a-> 13a 5b-> 13b 0.025543 + 8a-> 22a 8b-> 13b 0.025066 + 8a-> 13a 8b-> 22b 0.025066 + 11a-> 26a -1a-> -1a 0.024888 + 11b-> 26b -1b-> -1b 0.024888 + 10b-> 13b -1b-> -1b 0.024596 + 10a-> 13a -1a-> -1a 0.024596 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034765816 + alpha-alpha-alpha ... -0.000914866 ( 2.6%) + alpha-alpha-beta ... -0.016468043 ( 47.4%) + alpha-beta -beta ... -0.016468043 ( 47.4%) + beta -beta -beta ... -0.000914866 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034765816 + +Final correlation energy ... -0.727809608 +E(CCSD) ... -205.416279337 +E(CCSD(T)) ... -205.451045154 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.208373497 sqrt= 1.099260432 +W(HF) = 0.827558700 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.193143 0.000000 + 1 N : 0.141858 -0.000000 + 2 O : -0.181528 0.000000 + 3 H : 0.232813 -0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.790763 s : 3.790763 + pz : 1.562206 p : 4.326493 + px : 1.406823 + py : 1.357464 + dz2 : 0.016572 d : 0.066783 + dxz : 0.012192 + dyz : 0.008023 + dx2y2 : 0.020193 + dxy : 0.009803 + f0 : 0.000962 f : 0.009104 + f+1 : 0.001868 + f-1 : 0.000957 + f+2 : 0.001201 + f-2 : 0.001635 + f+3 : 0.001017 + f-3 : 0.001464 + 1 N s : 3.915275 s : 3.915275 + pz : 0.806137 p : 2.739624 + px : 0.796879 + py : 1.136609 + dz2 : 0.037312 d : 0.171011 + dxz : 0.034584 + dyz : 0.027653 + dx2y2 : 0.044024 + dxy : 0.027438 + f0 : 0.002335 f : 0.032231 + f+1 : 0.003666 + f-1 : 0.005185 + f+2 : 0.002747 + f-2 : 0.005479 + f+3 : 0.005189 + f-3 : 0.007631 + 2 O s : 3.844840 s : 3.844840 + pz : 1.364190 p : 4.243381 + px : 1.527475 + py : 1.351717 + dz2 : 0.016876 d : 0.083160 + dxz : 0.009631 + dyz : 0.018919 + dx2y2 : 0.017393 + dxy : 0.020340 + f0 : 0.000816 f : 0.010147 + f+1 : 0.000739 + f-1 : 0.002051 + f+2 : 0.001529 + f-2 : 0.001391 + f+3 : 0.001624 + f-3 : 0.001997 + 3 H s : 0.663583 s : 0.663583 + pz : 0.038121 p : 0.084111 + px : 0.032860 + py : 0.013131 + dz2 : 0.000007 d : 0.019493 + dxz : -0.000301 + dyz : 0.009589 + dx2y2 : 0.000002 + dxy : 0.010196 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.616089 0.000000 + 1 N : -0.329531 -0.000000 + 2 O : 0.280712 0.000000 + 3 H : -0.567270 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.117745 s : 3.117745 + pz : 1.308466 p : 3.835108 + px : 1.252965 + py : 1.273677 + dz2 : 0.051090 d : 0.330222 + dxz : 0.091466 + dyz : 0.043763 + dx2y2 : 0.075461 + dxy : 0.068442 + f0 : 0.009442 f : 0.100837 + f+1 : 0.018968 + f-1 : 0.005441 + f+2 : 0.016380 + f-2 : 0.021188 + f+3 : 0.008821 + f-3 : 0.020596 + 1 N s : 3.007878 s : 3.007878 + pz : 0.813844 p : 2.881762 + px : 0.846127 + py : 1.221791 + dz2 : 0.177157 d : 0.979544 + dxz : 0.210372 + dyz : 0.158116 + dx2y2 : 0.250535 + dxy : 0.183365 + f0 : 0.036679 f : 0.460347 + f+1 : 0.047748 + f-1 : 0.058414 + f+2 : 0.067538 + f-2 : 0.083041 + f+3 : 0.073445 + f-3 : 0.093482 + 2 O s : 3.300056 s : 3.300056 + pz : 1.214731 p : 3.940957 + px : 1.309359 + py : 1.416867 + dz2 : 0.053491 d : 0.353749 + dxz : 0.047892 + dyz : 0.070647 + dx2y2 : 0.117551 + dxy : 0.064168 + f0 : 0.009253 f : 0.124525 + f+1 : 0.005735 + f-1 : 0.022469 + f+2 : 0.019641 + f-2 : 0.019324 + f+3 : 0.018056 + f-3 : 0.030047 + 3 H s : 0.615471 s : 0.615471 + pz : 0.143603 p : 0.549460 + px : 0.137789 + py : 0.268067 + dz2 : 0.039844 d : 0.402339 + dxz : 0.028631 + dyz : 0.113741 + dx2y2 : 0.106201 + dxy : 0.113923 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.1931 8.0000 -0.1931 2.1860 1.7355 0.4506 + 1 N 6.8581 7.0000 0.1419 2.7965 2.3267 0.4699 + 2 O 8.1815 8.0000 -0.1815 2.0778 1.5799 0.4980 + 3 H 0.7672 1.0000 0.2328 1.0333 0.9593 0.0741 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7852 B( 0-O , 2-O ) : 0.1011 B( 0-O , 3-H ) : 0.8492 +B( 1-N , 2-O ) : 1.4551 + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 65.293 sec + +Fock Matrix Formation ... 0.296 sec ( 0.5%) +Initial Guess ... 0.149 sec ( 0.2%) +DIIS Solver ... 2.048 sec ( 3.1%) +State Vector Update ... 0.098 sec ( 0.1%) +Sigma-vector construction ... 43.583 sec ( 66.7%) + <0|H|D> ... 0.003 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.021 sec ( 0.0% of sigma) + (0-ext) ... 0.066 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.025 sec ( 0.1% of sigma) + (2-ext) ... 0.906 sec ( 2.1% of sigma) + (4-ext) ... 25.858 sec ( 59.3% of sigma) + ... 1.942 sec ( 4.5% of sigma) + ... 0.003 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.117 sec ( 0.3% of sigma) + Fock-dressing ... 2.098 sec ( 4.8% of sigma) + (ik|jl)-dressing ... 0.079 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.006 sec ( 23.0% of sigma) + Pair energies ... 0.009 sec ( 0.0% of sigma) +Total Time for computing (T) ... 9.704 sec ( 14.9% of ALL) + I/O of integral and amplitudes ... 0.880 sec ( 9.1% of (T)) + External N**7 contributions ... 4.934 sec ( 50.8% of (T)) + Internal N**7 contributions ... 0.405 sec ( 4.2% of (T)) + N**6 triples energy contributions ... 1.978 sec ( 20.4% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.451045153856 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.004509038 -0.000172310 -0.002500693 + 2 N : 0.004384569 -0.002022646 0.002237138 + 3 O : -0.001561488 0.001158908 -0.002481548 + 4 H : 0.001685957 0.001036047 0.002745102 + +Norm of the cartesian gradient ... 0.008736460 +RMS gradient ... 0.002521999 +MAX gradient ... 0.004509038 + +------- +TIMINGS +------- + +Total numerical gradient time ... 398.666 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 602.29 cm**-1 + 7: 670.99 cm**-1 + 8: 861.03 cm**-1 + 9: 1332.93 cm**-1 + 10: 1656.43 cm**-1 + 11: 3587.33 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 0.223842 0.019087 -0.205227 0.055100 -0.013865 0.003116 + 1 0.066260 0.042125 0.142957 0.077346 0.067769 -0.061301 + 2 -0.101273 -0.134923 0.162359 -0.042685 0.007356 -0.004353 + 3 -0.114423 0.050237 0.365865 0.064779 -0.090565 0.002294 + 4 -0.102414 -0.049340 -0.232874 -0.011014 -0.502551 -0.001103 + 5 0.014586 0.085522 -0.280056 -0.060842 0.140824 -0.001659 + 6 -0.119513 -0.111660 -0.140380 -0.061576 0.129659 -0.000422 + 7 0.015572 -0.001135 0.046794 -0.064858 0.373079 -0.000200 + 8 0.146780 0.022331 0.122486 0.059663 -0.158645 0.000303 + 9 -0.065909 0.771236 0.401474 -0.797366 -0.579414 -0.074629 + 10 0.124285 0.035048 0.224233 -0.045155 -0.013786 0.991467 + 11 -0.924983 0.598652 -0.629448 0.575978 0.444400 0.087333 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 602.29 0.011442 57.82 0.005928 (-0.072538 -0.025582 -0.003490) + 7: 670.99 0.014239 71.96 0.006622 ( 0.044257 -0.012244 0.067185) + 8: 861.03 0.055235 279.14 0.020019 ( 0.103723 0.005295 -0.096086) + 9: 1332.93 0.001762 8.91 0.000413 (-0.003836 0.019946 -0.000104) + 10: 1656.43 0.029308 148.11 0.005521 (-0.054179 -0.018851 0.047231) + 11: 3587.33 0.006444 32.57 0.000561 (-0.009936 0.019137 0.009779) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 602.29 E(vib) ... 0.10 +freq. 670.99 E(vib) ... 0.08 +freq. 861.03 E(vib) ... 0.04 +freq. 1332.93 E(vib) ... 0.01 +freq. 1656.43 E(vib) ... 0.00 +freq. 3587.33 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.45104515 Eh +Zero point energy ... 0.01984512 Eh 12.45 kcal/mol +Thermal vibrational correction ... 0.00035846 Eh 0.22 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42800903 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00319100 Eh 2.00 kcal/mol +Non-thermal (ZPE) correction 0.01984512 Eh 12.45 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02303612 Eh 14.46 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42800903 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.42706482 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.761291 0.437725 0.378068 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00046653 Eh 0.29 kcal/mol +Rotational entropy ... 0.00988053 Eh 6.20 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02814937 Eh 17.66 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00988053 Eh 6.20 kcal/mol| +| sn= 2 | S(rot)= 0.00922607 Eh 5.79 kcal/mol| +| sn= 3 | S(rot)= 0.00884324 Eh 5.55 kcal/mol| +| sn= 4 | S(rot)= 0.00857161 Eh 5.38 kcal/mol| +| sn= 5 | S(rot)= 0.00836093 Eh 5.25 kcal/mol| +| sn= 6 | S(rot)= 0.00818878 Eh 5.14 kcal/mol| +| sn= 7 | S(rot)= 0.00804324 Eh 5.05 kcal/mol| +| sn= 8 | S(rot)= 0.00791716 Eh 4.97 kcal/mol| +| sn= 9 | S(rot)= 0.00780595 Eh 4.90 kcal/mol| +| sn=10 | S(rot)= 0.00770647 Eh 4.84 kcal/mol| +| sn=11 | S(rot)= 0.00761648 Eh 4.78 kcal/mol| +| sn=12 | S(rot)= 0.00753433 Eh 4.73 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.42706482 Eh +Total entropy correction ... -0.02814937 Eh -17.66 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.45521419 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00416904 Eh -2.62 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.451045154 Eh +Current gradient norm .... 0.008736463 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.039764102 0.143469496 0.208746006 0.462967771 0.535654934 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999899712 +Lowest eigenvalues of augmented Hessian: + -0.000039360 0.142978926 0.208526984 0.462966066 0.535653784 +Length of the computed step .... 0.014163521 +The final length of the internal step .... 0.014163521 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0057822334 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0031124728 RMS(Int)= 0.0057821929 + Iter 1: RMS(Cart)= 0.0000024232 RMS(Int)= 0.0000038932 + Iter 2: RMS(Cart)= 0.0000000060 RMS(Int)= 0.0000000069 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000003 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0013607848 0.0001000000 NO + MAX gradient 0.0025001838 0.0003000000 NO + RMS step 0.0057822334 0.0020000000 NO + MAX step 0.0136139308 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0072 Max(Angles) 0.18 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4047 0.002500 -0.0072 1.3975 + 2. B(O 2,N 1) 1.1868 0.001430 0.0000 1.1868 + 3. B(H 3,O 0) 0.9790 0.001138 -0.0010 0.9781 + 4. A(N 1,O 0,H 3) 104.61 0.000360 0.08 104.68 + 5. A(O 0,N 1,O 2) 113.04 -0.001179 0.18 113.22 + 6. D(O 2,N 1,O 0,H 3) -8.18 -0.005695 0.00 -8.18 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.639178 -0.384852 0.519051 + N 0.460066 -0.600452 -0.316474 + O 0.883184 0.397406 -0.799927 + H -0.704070 0.587897 0.597349 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.207872 -0.727265 0.980865 + 1 N 7.0000 0 14.007 0.869398 -1.134690 -0.598049 + 2 O 8.0000 0 15.999 1.668975 0.750989 -1.511642 + 3 H 1.0000 0 1.008 -1.330499 1.110965 1.128826 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.397470255861 0.00000000 0.00000000 + O 2 1 0 1.186792421640 113.22079368 0.00000000 + H 1 2 3 0.978050544936 104.68442620 351.81818159 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.640836063878 0.00000000 0.00000000 + O 2 1 0 2.242712654713 113.22079368 0.00000000 + H 1 2 3 1.848247675061 104.68442620 351.81818159 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2245 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2720 + la=0 lb=0: 557 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.122354197793 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.433e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7239005943 0.000000000000 0.00023092 0.00000625 0.0012104 0.7000 + 1 -204.7239084002 -0.000007805931 0.00019012 0.00000521 0.0009132 0.7000 + ***Turning on DIIS*** + 2 -204.7239148406 -0.000006440389 0.00049401 0.00001376 0.0006817 0.0000 + 3 -204.7235684791 0.000346361441 0.00019160 0.00000537 0.0001511 0.0000 + 4 -204.7240615141 -0.000493034994 0.00006973 0.00000164 0.0000683 0.0000 + 5 -204.7240003385 0.000061175629 0.00002502 0.00000058 0.0000211 0.0000 + 6 -204.7238607770 0.000139561517 0.00000880 0.00000028 0.0000156 0.0000 + 7 -204.7239572332 -0.000096456221 0.00000424 0.00000010 0.0000053 0.0000 + 8 -204.7239318100 0.000025423180 0.00000231 0.00000007 0.0000023 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + +Total Energy : -204.72393499 Eh -5570.82149 eV + Last Energy change ... -3.1780e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.9428e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.204 sec +Reference energy ... -204.723935722 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.407 sec +AO-integral generation ... 0.143 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.401 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.038 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.040 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.023 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.354 sec +AO-integral generation ... 0.248 sec +Half transformation ... 0.042 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.155 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.252 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090615961 +EMP2(bb)= -0.090615961 +EMP2(ab)= -0.514879512 + +Initial guess performed in 0.133 sec +E(0) ... -204.723935722 +E(MP2) ... -0.696111435 +Initial E(tot) ... -205.420047157 + ... 0.186422554 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.420047157 -0.696111435 -0.000000000 0.030791026 2.69 0.000001087 + *** Turning on DIIS *** + 1 -205.391103860 -0.667168137 0.028943298 0.012311227 2.76 0.058317310 + 2 -205.410493930 -0.686558207 -0.019390070 0.006984582 2.95 0.061576631 + 3 -205.414167315 -0.690231593 -0.003673386 0.002520143 2.83 0.076061220 + 4 -205.415751118 -0.691815396 -0.001583803 0.001534676 3.02 0.083109817 + 5 -205.416296550 -0.692360827 -0.000545431 0.000724777 2.94 0.088586307 + 6 -205.416394339 -0.692458617 -0.000097789 0.000458141 3.04 0.090987958 + 7 -205.416432791 -0.692497068 -0.000038452 0.000204566 3.11 0.091937051 + 8 -205.416440939 -0.692505216 -0.000008148 0.000109515 3.08 0.092269585 + 9 -205.416437195 -0.692501473 0.000003743 0.000027953 3.05 0.092369343 + 10 -205.416441381 -0.692505658 -0.000004185 0.000007576 3.08 0.092405161 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.723935722 +E(CORR) ... -0.692505658 +E(TOT) ... -205.416441381 +Singles norm **1/2 ... 0.092405161 ( 0.046202581, 0.046202581) +T1 diagnostic ... 0.021780105 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.064936 + 10a-> 13a 10b-> 13b 0.057081 + 8a-> 13a -1a-> -1a 0.052296 + 8b-> 13b -1b-> -1b 0.052296 + 10a-> 13a 8b-> 13b 0.036739 + 8a-> 13a 10b-> 13b 0.036739 + 11a-> 13a 11b-> 13b 0.029174 + 10a-> 22a 10b-> 13b 0.026335 + 10a-> 13a 10b-> 22b 0.026335 + 5a-> 13a 5b-> 13b 0.025158 + 8a-> 13a 8b-> 22b 0.024781 + 8a-> 22a 8b-> 13b 0.024781 + 11b-> 26b -1b-> -1b 0.023468 + 11a-> 26a -1a-> -1a 0.023468 + 10a-> 13a -1a-> -1a 0.023243 + 10b-> 13b -1b-> -1b 0.023243 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034623195 + alpha-alpha-alpha ... -0.000912907 ( 2.6%) + alpha-alpha-beta ... -0.016398691 ( 47.4%) + alpha-beta -beta ... -0.016398691 ( 47.4%) + beta -beta -beta ... -0.000912907 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034623195 + +Final correlation energy ... -0.727128853 +E(CCSD) ... -205.416441381 +E(CCSD(T)) ... -205.451064576 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.207485987 sqrt= 1.098856672 +W(HF) = 0.828166961 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 48.069 sec + +Fock Matrix Formation ... 0.204 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.3%) +DIIS Solver ... 1.472 sec ( 3.1%) +State Vector Update ... 0.075 sec ( 0.2%) +Sigma-vector construction ... 31.008 sec ( 64.5%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (0-ext) ... 0.056 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (2-ext) ... 0.744 sec ( 2.4% of sigma) + (4-ext) ... 16.883 sec ( 54.4% of sigma) + ... 1.213 sec ( 3.9% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.089 sec ( 0.3% of sigma) + Fock-dressing ... 1.731 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.060 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 8.020 sec ( 25.9% of sigma) + Pair energies ... 0.007 sec ( 0.0% of sigma) +Total Time for computing (T) ... 7.006 sec ( 14.6% of ALL) + I/O of integral and amplitudes ... 0.762 sec ( 10.9% of (T)) + External N**7 contributions ... 3.887 sec ( 55.5% of (T)) + Internal N**7 contributions ... 0.309 sec ( 4.4% of (T)) + N**6 triples energy contributions ... 1.590 sec ( 22.7% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.451064575740 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.002831861 -0.000017830 -0.003822104 + 2 N : 0.002605327 0.000431849 0.003432367 + 3 O : -0.001732455 -0.000323409 -0.002196714 + 4 H : 0.001958989 -0.000090611 0.002586450 + +Norm of the cartesian gradient ... 0.007736324 +RMS gradient ... 0.002233284 +MAX gradient ... 0.003822104 + +------- +TIMINGS +------- + +Total numerical gradient time ... 387.440 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.451064576 Eh +Current gradient norm .... 0.007736324 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999919 +Lowest eigenvalues of augmented Hessian: + -0.000000028 0.145459528 0.210615220 0.463320811 0.533591346 +Length of the computed step .... 0.000403351 +The final length of the internal step .... 0.000403351 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0001646672 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001048126 RMS(Int)= 0.0001646673 + Iter 1: RMS(Cart)= 0.0000000009 RMS(Int)= 0.0000000013 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000194217 0.0000050000 NO + RMS gradient 0.0000290562 0.0001000000 YES + MAX gradient 0.0000689156 0.0003000000 YES + RMS step 0.0001646672 0.0020000000 YES + MAX step 0.0003964008 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0002 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.3975 -0.000069 0.0002 1.3977 + 2. B(O 2,N 1) 1.1868 0.000005 -0.0000 1.1868 + 3. B(H 3,O 0) 0.9781 -0.000013 0.0000 0.9781 + 4. A(N 1,O 0,H 3) 104.68 -0.000010 -0.00 104.68 + 5. A(O 0,N 1,O 2) 113.22 -0.000004 -0.00 113.22 + 6. D(O 2,N 1,O 0,H 3) -8.18 -0.005803 -0.00 -8.18 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.639253 -0.384841 0.519111 + N 0.460154 -0.600457 -0.316546 + O 0.883240 0.397383 -0.799973 + H -0.704140 0.587916 0.597408 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.208013 -0.727244 0.980978 + 1 N 7.0000 0 14.007 0.869565 -1.134700 -0.598186 + 2 O 8.0000 0 15.999 1.669082 0.750944 -1.511729 + 3 H 1.0000 0 1.008 -1.330632 1.110999 1.128938 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.397680022118 0.00000000 0.00000000 + O 2 1 0 1.186754838154 113.22026461 0.00000000 + H 1 2 3 0.978057208066 104.68348439 351.81818159 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.641232464657 0.00000000 0.00000000 + O 2 1 0 2.242641632217 113.22026461 0.00000000 + H 1 2 3 1.848260266553 104.68348439 351.81818159 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2245 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2720 + la=0 lb=0: 557 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.118548822255 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 70.1185488223 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.434e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7239225020 0.000000000000 0.00000668 0.00000017 0.0000351 0.7000 + 1 -204.7239225082 -0.000000006230 0.00000552 0.00000014 0.0000267 0.7000 + ***Turning on DIIS*** + 2 -204.7239225134 -0.000000005207 0.00001444 0.00000038 0.0000202 0.0000 + 3 -204.7239270734 -0.000004560046 0.00000479 0.00000017 0.0000046 0.0000 + 4 -204.7239192187 0.000007854768 0.00000257 0.00000006 0.0000018 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72392079 Eh -5570.82110 eV + +Components: +Nuclear Repulsion : 70.11854882 Eh 1908.02272 eV +Electronic Energy : -274.84246961 Eh -7478.84382 eV +One Electron Energy: -419.81100260 Eh -11423.63815 eV +Two Electron Energy: 144.96853299 Eh 3944.79433 eV + +Virial components: +Potential Energy : -408.97389627 Eh -11128.74549 eV +Kinetic Energy : 204.24997549 Eh 5557.92439 eV +Virial Ratio : 2.00232042 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.5672e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.9544e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.7191e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.1841e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.665803 -562.3451 + 1 1.0000 -20.651290 -561.9502 + 2 1.0000 -15.802792 -430.0158 + 3 1.0000 -1.608735 -43.7759 + 4 1.0000 -1.408027 -38.3144 + 5 1.0000 -0.967436 -26.3253 + 6 1.0000 -0.776597 -21.1323 + 7 1.0000 -0.743979 -20.2447 + 8 1.0000 -0.689732 -18.7686 + 9 1.0000 -0.614229 -16.7140 + 10 1.0000 -0.533137 -14.5074 + 11 1.0000 -0.475217 -12.9313 + 12 0.0000 0.031706 0.8628 + 13 0.0000 0.077669 2.1135 + 14 0.0000 0.095205 2.5906 + 15 0.0000 0.113046 3.0761 + 16 0.0000 0.128226 3.4892 + 17 0.0000 0.138723 3.7749 + 18 0.0000 0.157802 4.2940 + 19 0.0000 0.169308 4.6071 + 20 0.0000 0.184501 5.0205 + 21 0.0000 0.195346 5.3156 + 22 0.0000 0.205751 5.5988 + 23 0.0000 0.232670 6.3313 + 24 0.0000 0.250691 6.8216 + 25 0.0000 0.301626 8.2077 + 26 0.0000 0.313884 8.5412 + 27 0.0000 0.344735 9.3807 + 28 0.0000 0.352636 9.5957 + 29 0.0000 0.400180 10.8894 + 30 0.0000 0.441855 12.0235 + 31 0.0000 0.512633 13.9494 + 32 0.0000 0.516558 14.0562 + 33 0.0000 0.535578 14.5738 + 34 0.0000 0.562592 15.3089 + 35 0.0000 0.617919 16.8144 + 36 0.0000 0.639772 17.4091 + 37 0.0000 0.666849 18.1459 + 38 0.0000 0.683810 18.6074 + 39 0.0000 0.698210 18.9993 + 40 0.0000 0.732987 19.9456 + 41 0.0000 0.756716 20.5913 + 42 0.0000 0.761679 20.7263 + 43 0.0000 0.783719 21.3261 + 44 0.0000 0.798101 21.7174 + 45 0.0000 0.845603 23.0100 + 46 0.0000 0.850766 23.1505 + 47 0.0000 0.871069 23.7030 + 48 0.0000 0.918870 25.0037 + 49 0.0000 0.937707 25.5163 + 50 0.0000 0.954571 25.9752 + 51 0.0000 1.006362 27.3845 + 52 0.0000 1.027749 27.9665 + 53 0.0000 1.071715 29.1628 + 54 0.0000 1.081655 29.4333 + 55 0.0000 1.088317 29.6146 + 56 0.0000 1.179669 32.1004 + 57 0.0000 1.214650 33.0523 + 58 0.0000 1.239590 33.7310 + 59 0.0000 1.264679 34.4137 + 60 0.0000 1.339954 36.4620 + 61 0.0000 1.412575 38.4381 + 62 0.0000 1.461137 39.7596 + 63 0.0000 1.504137 40.9296 + 64 0.0000 1.541634 41.9500 + 65 0.0000 1.557200 42.3736 + 66 0.0000 1.592069 43.3224 + 67 0.0000 1.612523 43.8790 + 68 0.0000 1.657323 45.0981 + 69 0.0000 1.764448 48.0131 + 70 0.0000 1.789711 48.7005 + 71 0.0000 1.822626 49.5962 + 72 0.0000 1.905494 51.8511 + 73 0.0000 1.921944 52.2988 + 74 0.0000 1.988882 54.1202 + 75 0.0000 1.999109 54.3985 + 76 0.0000 2.039995 55.5111 + 77 0.0000 2.123469 57.7825 + 78 0.0000 2.151432 58.5435 + 79 0.0000 2.177974 59.2657 + 80 0.0000 2.286878 62.2291 + 81 0.0000 2.320071 63.1323 + 82 0.0000 2.352534 64.0157 + 83 0.0000 2.386005 64.9265 + 84 0.0000 2.435814 66.2819 + 85 0.0000 2.454052 66.7781 + 86 0.0000 2.473585 67.3097 + 87 0.0000 2.512393 68.3657 + 88 0.0000 2.520969 68.5991 + 89 0.0000 2.560075 69.6632 + 90 0.0000 2.575849 70.0924 + 91 0.0000 2.639345 71.8202 + 92 0.0000 2.661745 72.4298 + 93 0.0000 2.691911 73.2506 + 94 0.0000 2.746162 74.7269 + 95 0.0000 2.794161 76.0330 + 96 0.0000 2.907632 79.1207 + 97 0.0000 2.965216 80.6876 + 98 0.0000 2.980840 81.1128 + 99 0.0000 3.065576 83.4186 + 100 0.0000 3.146249 85.6138 + 101 0.0000 3.151324 85.7519 + 102 0.0000 3.218276 87.5738 + 103 0.0000 3.515468 95.6607 + 104 0.0000 3.753072 102.1263 + 105 0.0000 3.844238 104.6070 + 106 0.0000 4.023420 109.4828 + 107 0.0000 4.152653 112.9994 + 108 0.0000 4.174998 113.6075 + 109 0.0000 4.245833 115.5350 + 110 0.0000 4.359105 118.6173 + 111 0.0000 4.411107 120.0323 + 112 0.0000 4.519418 122.9796 + 113 0.0000 4.568549 124.3165 + 114 0.0000 4.700680 127.9120 + 115 0.0000 4.844092 131.8145 + 116 0.0000 4.886353 132.9644 + 117 0.0000 4.900091 133.3382 + 118 0.0000 4.945045 134.5615 + 119 0.0000 5.000195 136.0622 + 120 0.0000 5.066655 137.8707 + 121 0.0000 5.107199 138.9739 + 122 0.0000 5.201430 141.5381 + 123 0.0000 5.219440 142.0282 + 124 0.0000 5.231436 142.3546 + 125 0.0000 5.302427 144.2864 + 126 0.0000 5.390926 146.6945 + 127 0.0000 5.484647 149.2448 + 128 0.0000 5.554159 151.1364 + 129 0.0000 5.664031 154.1261 + 130 0.0000 5.788994 157.5265 + 131 0.0000 5.921520 161.1328 + 132 0.0000 6.185456 168.3148 + 133 0.0000 6.421580 174.7401 + 134 0.0000 6.518528 177.3782 + 135 0.0000 6.565899 178.6672 + 136 0.0000 6.677179 181.6953 + 137 0.0000 6.702336 182.3798 + 138 0.0000 6.765418 184.0964 + 139 0.0000 6.831599 185.8973 + 140 0.0000 6.951993 189.1734 + 141 0.0000 7.100639 193.2182 + 142 0.0000 7.123736 193.8467 + 143 0.0000 7.156216 194.7305 + 144 0.0000 7.168209 195.0569 + 145 0.0000 7.230478 196.7513 + 146 0.0000 7.289594 198.3599 + 147 0.0000 7.315984 199.0780 + 148 0.0000 7.408627 201.5990 + 149 0.0000 7.432630 202.2522 + 150 0.0000 7.467643 203.2049 + 151 0.0000 7.497848 204.0268 + 152 0.0000 7.613275 207.1677 + 153 0.0000 7.691131 209.2863 + 154 0.0000 7.861020 213.9092 + 155 0.0000 7.942680 216.1313 + 156 0.0000 8.302083 225.9112 + 157 0.0000 8.316136 226.2936 + 158 0.0000 14.217121 386.8675 + 159 0.0000 15.104327 411.0096 + 160 0.0000 15.628779 425.2807 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.665803 -562.3451 + 1 1.0000 -20.651290 -561.9502 + 2 1.0000 -15.802792 -430.0158 + 3 1.0000 -1.608735 -43.7759 + 4 1.0000 -1.408027 -38.3144 + 5 1.0000 -0.967436 -26.3253 + 6 1.0000 -0.776597 -21.1323 + 7 1.0000 -0.743979 -20.2447 + 8 1.0000 -0.689732 -18.7686 + 9 1.0000 -0.614229 -16.7140 + 10 1.0000 -0.533137 -14.5074 + 11 1.0000 -0.475217 -12.9313 + 12 0.0000 0.031706 0.8628 + 13 0.0000 0.077669 2.1135 + 14 0.0000 0.095205 2.5906 + 15 0.0000 0.113046 3.0761 + 16 0.0000 0.128226 3.4892 + 17 0.0000 0.138723 3.7749 + 18 0.0000 0.157802 4.2940 + 19 0.0000 0.169308 4.6071 + 20 0.0000 0.184501 5.0205 + 21 0.0000 0.195346 5.3156 + 22 0.0000 0.205751 5.5988 + 23 0.0000 0.232670 6.3313 + 24 0.0000 0.250691 6.8216 + 25 0.0000 0.301626 8.2077 + 26 0.0000 0.313884 8.5412 + 27 0.0000 0.344735 9.3807 + 28 0.0000 0.352636 9.5957 + 29 0.0000 0.400180 10.8894 + 30 0.0000 0.441855 12.0235 + 31 0.0000 0.512633 13.9494 + 32 0.0000 0.516558 14.0562 + 33 0.0000 0.535578 14.5738 + 34 0.0000 0.562592 15.3089 + 35 0.0000 0.617919 16.8144 + 36 0.0000 0.639772 17.4091 + 37 0.0000 0.666849 18.1459 + 38 0.0000 0.683810 18.6074 + 39 0.0000 0.698210 18.9993 + 40 0.0000 0.732987 19.9456 + 41 0.0000 0.756716 20.5913 + 42 0.0000 0.761679 20.7263 + 43 0.0000 0.783719 21.3261 + 44 0.0000 0.798101 21.7174 + 45 0.0000 0.845603 23.0100 + 46 0.0000 0.850766 23.1505 + 47 0.0000 0.871069 23.7030 + 48 0.0000 0.918870 25.0037 + 49 0.0000 0.937707 25.5163 + 50 0.0000 0.954571 25.9752 + 51 0.0000 1.006362 27.3845 + 52 0.0000 1.027749 27.9665 + 53 0.0000 1.071715 29.1628 + 54 0.0000 1.081655 29.4333 + 55 0.0000 1.088317 29.6146 + 56 0.0000 1.179669 32.1004 + 57 0.0000 1.214650 33.0523 + 58 0.0000 1.239590 33.7310 + 59 0.0000 1.264679 34.4137 + 60 0.0000 1.339954 36.4620 + 61 0.0000 1.412575 38.4381 + 62 0.0000 1.461137 39.7596 + 63 0.0000 1.504137 40.9296 + 64 0.0000 1.541634 41.9500 + 65 0.0000 1.557200 42.3736 + 66 0.0000 1.592069 43.3224 + 67 0.0000 1.612523 43.8790 + 68 0.0000 1.657323 45.0981 + 69 0.0000 1.764448 48.0131 + 70 0.0000 1.789711 48.7005 + 71 0.0000 1.822626 49.5962 + 72 0.0000 1.905494 51.8511 + 73 0.0000 1.921944 52.2988 + 74 0.0000 1.988882 54.1202 + 75 0.0000 1.999109 54.3985 + 76 0.0000 2.039995 55.5111 + 77 0.0000 2.123469 57.7825 + 78 0.0000 2.151432 58.5435 + 79 0.0000 2.177974 59.2657 + 80 0.0000 2.286878 62.2291 + 81 0.0000 2.320071 63.1323 + 82 0.0000 2.352534 64.0157 + 83 0.0000 2.386005 64.9265 + 84 0.0000 2.435814 66.2819 + 85 0.0000 2.454052 66.7781 + 86 0.0000 2.473585 67.3097 + 87 0.0000 2.512393 68.3657 + 88 0.0000 2.520969 68.5991 + 89 0.0000 2.560075 69.6632 + 90 0.0000 2.575849 70.0924 + 91 0.0000 2.639345 71.8202 + 92 0.0000 2.661745 72.4298 + 93 0.0000 2.691911 73.2506 + 94 0.0000 2.746162 74.7269 + 95 0.0000 2.794161 76.0330 + 96 0.0000 2.907632 79.1207 + 97 0.0000 2.965216 80.6876 + 98 0.0000 2.980840 81.1128 + 99 0.0000 3.065576 83.4186 + 100 0.0000 3.146249 85.6138 + 101 0.0000 3.151324 85.7519 + 102 0.0000 3.218276 87.5738 + 103 0.0000 3.515468 95.6607 + 104 0.0000 3.753072 102.1263 + 105 0.0000 3.844238 104.6070 + 106 0.0000 4.023420 109.4828 + 107 0.0000 4.152653 112.9994 + 108 0.0000 4.174998 113.6075 + 109 0.0000 4.245833 115.5350 + 110 0.0000 4.359105 118.6173 + 111 0.0000 4.411107 120.0323 + 112 0.0000 4.519418 122.9796 + 113 0.0000 4.568549 124.3165 + 114 0.0000 4.700680 127.9120 + 115 0.0000 4.844092 131.8145 + 116 0.0000 4.886353 132.9644 + 117 0.0000 4.900091 133.3382 + 118 0.0000 4.945045 134.5615 + 119 0.0000 5.000195 136.0622 + 120 0.0000 5.066655 137.8707 + 121 0.0000 5.107199 138.9739 + 122 0.0000 5.201430 141.5381 + 123 0.0000 5.219440 142.0282 + 124 0.0000 5.231436 142.3546 + 125 0.0000 5.302427 144.2864 + 126 0.0000 5.390926 146.6945 + 127 0.0000 5.484647 149.2448 + 128 0.0000 5.554159 151.1364 + 129 0.0000 5.664031 154.1261 + 130 0.0000 5.788994 157.5265 + 131 0.0000 5.921520 161.1328 + 132 0.0000 6.185456 168.3148 + 133 0.0000 6.421580 174.7401 + 134 0.0000 6.518528 177.3782 + 135 0.0000 6.565899 178.6672 + 136 0.0000 6.677179 181.6953 + 137 0.0000 6.702336 182.3798 + 138 0.0000 6.765418 184.0964 + 139 0.0000 6.831599 185.8973 + 140 0.0000 6.951993 189.1734 + 141 0.0000 7.100639 193.2182 + 142 0.0000 7.123736 193.8467 + 143 0.0000 7.156216 194.7305 + 144 0.0000 7.168209 195.0569 + 145 0.0000 7.230478 196.7513 + 146 0.0000 7.289594 198.3599 + 147 0.0000 7.315984 199.0780 + 148 0.0000 7.408627 201.5990 + 149 0.0000 7.432630 202.2522 + 150 0.0000 7.467643 203.2049 + 151 0.0000 7.497848 204.0268 + 152 0.0000 7.613275 207.1677 + 153 0.0000 7.691131 209.2863 + 154 0.0000 7.861020 213.9092 + 155 0.0000 7.942680 216.1313 + 156 0.0000 8.302083 225.9112 + 157 0.0000 8.316136 226.2936 + 158 0.0000 14.217121 386.8675 + 159 0.0000 15.104327 411.0096 + 160 0.0000 15.628779 425.2807 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.277664 0.000000 + 1 N : 0.332172 0.000000 + 2 O : -0.304180 0.000000 + 3 H : 0.249672 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.800672 s : 3.800672 + pz : 1.614464 p : 4.434026 + px : 1.437771 + py : 1.381792 + dz2 : 0.010080 d : 0.037465 + dxz : 0.007627 + dyz : 0.000826 + dx2y2 : 0.016641 + dxy : 0.002291 + f0 : 0.000412 f : 0.005500 + f+1 : 0.001375 + f-1 : 0.000312 + f+2 : 0.000860 + f-2 : 0.001216 + f+3 : 0.000432 + f-3 : 0.000892 + 1 N s : 3.866284 s : 3.866284 + pz : 0.710594 p : 2.623590 + px : 0.725692 + py : 1.187304 + dz2 : 0.031144 d : 0.144629 + dxz : 0.028013 + dyz : 0.025216 + dx2y2 : 0.036331 + dxy : 0.023924 + f0 : 0.002152 f : 0.033326 + f+1 : 0.003694 + f-1 : 0.005512 + f+2 : 0.003086 + f-2 : 0.005518 + f+3 : 0.005654 + f-3 : 0.007710 + 2 O s : 3.856644 s : 3.856644 + pz : 1.414104 p : 4.380606 + px : 1.586599 + py : 1.379903 + dz2 : 0.012049 d : 0.059503 + dxz : 0.002873 + dyz : 0.016807 + dx2y2 : 0.010411 + dxy : 0.017363 + f0 : 0.000322 f : 0.007428 + f+1 : 0.000189 + f-1 : 0.001868 + f+2 : 0.001185 + f-2 : 0.000925 + f+3 : 0.001308 + f-3 : 0.001631 + 3 H s : 0.646586 s : 0.646586 + pz : 0.033519 p : 0.082691 + px : 0.029166 + py : 0.020006 + dz2 : -0.000065 d : 0.021051 + dxz : -0.000935 + dyz : 0.010573 + dx2y2 : 0.000486 + dxy : 0.010991 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.602961 0.000000 + 1 N : -0.284531 0.000000 + 2 O : 0.245347 0.000000 + 3 H : -0.563777 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.105747 s : 3.105747 + pz : 1.339850 p : 3.895096 + px : 1.268782 + py : 1.286464 + dz2 : 0.044076 d : 0.301444 + dxz : 0.085445 + dyz : 0.038630 + dx2y2 : 0.068778 + dxy : 0.064515 + f0 : 0.008573 f : 0.094753 + f+1 : 0.017040 + f-1 : 0.004354 + f+2 : 0.015258 + f-2 : 0.021593 + f+3 : 0.007757 + f-3 : 0.020178 + 1 N s : 2.998697 s : 2.998697 + pz : 0.757685 p : 2.829831 + px : 0.810339 + py : 1.261807 + dz2 : 0.180769 d : 0.981381 + dxz : 0.204189 + dyz : 0.158573 + dx2y2 : 0.250457 + dxy : 0.187393 + f0 : 0.037055 f : 0.474621 + f+1 : 0.052933 + f-1 : 0.060319 + f+2 : 0.067734 + f-2 : 0.085910 + f+3 : 0.073448 + f-3 : 0.097222 + 2 O s : 3.297436 s : 3.297436 + pz : 1.242640 p : 4.022584 + px : 1.344398 + py : 1.435546 + dz2 : 0.044305 d : 0.319007 + dxz : 0.042962 + dyz : 0.062367 + dx2y2 : 0.113229 + dxy : 0.056144 + f0 : 0.008492 f : 0.115626 + f+1 : 0.004579 + f-1 : 0.019483 + f+2 : 0.018021 + f-2 : 0.018994 + f+3 : 0.016006 + f-3 : 0.030051 + 3 H s : 0.609350 s : 0.609350 + pz : 0.141269 p : 0.541577 + px : 0.136445 + py : 0.263863 + dz2 : 0.040225 d : 0.412850 + dxz : 0.028729 + dyz : 0.119051 + dx2y2 : 0.106748 + dxy : 0.118098 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2777 8.0000 -0.2777 1.8056 1.8056 0.0000 + 1 N 6.6678 7.0000 0.3322 2.5017 2.5017 0.0000 + 2 O 8.3042 8.0000 -0.3042 1.6634 1.6634 -0.0000 + 3 H 0.7503 1.0000 0.2497 1.0146 1.0146 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8253 B( 0-O , 3-H ) : 0.9222 B( 1-N , 2-O ) : 1.5947 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.025 sec +Sum of individual times .... 0.798 sec ( 77.9%) + +Fock matrix formation .... 0.625 sec ( 61.0%) +Diagonalization .... 0.067 sec ( 6.5%) +Density matrix formation .... 0.005 sec ( 0.5%) +Population analysis .... 0.045 sec ( 4.4%) +Initial guess .... 0.009 sec ( 0.9%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.5%) +DIIS solution .... 0.047 sec ( 4.6%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.207 sec +Reference energy ... -204.723922533 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.383 sec +AO-integral generation ... 0.142 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.384 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.022 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.025 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.030 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.346 sec +AO-integral generation ... 0.240 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.150 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.257 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090617011 +EMP2(bb)= -0.090617011 +EMP2(ab)= -0.514889631 + +Initial guess performed in 0.134 sec +E(0) ... -204.723922533 +E(MP2) ... -0.696123652 +Initial E(tot) ... -205.420046185 + ... 0.186435116 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.420046185 -0.696123652 -0.000000000 0.030786170 2.69 0.000001476 + *** Turning on DIIS *** + 1 -205.391097686 -0.667175153 0.028948499 0.012309537 2.69 0.058323103 + 2 -205.410489928 -0.686567395 -0.019392242 0.006983329 2.77 0.061581019 + 3 -205.414163761 -0.690241228 -0.003673833 0.002519351 2.80 0.076067915 + 4 -205.415747826 -0.691825293 -0.001584064 0.001534399 2.77 0.083117732 + 5 -205.416293509 -0.692370976 -0.000545683 0.000725697 2.88 0.088597117 + 6 -205.416391380 -0.692468847 -0.000097871 0.000458671 2.84 0.091001058 + 7 -205.416429877 -0.692507344 -0.000038498 0.000204705 2.88 0.091951609 + 8 -205.416438044 -0.692515511 -0.000008166 0.000109582 2.86 0.092284710 + 9 -205.416434295 -0.692511762 0.000003748 0.000027967 2.80 0.092384593 + 10 -205.416438487 -0.692515954 -0.000004191 0.000007588 2.78 0.092420471 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.723922533 +E(CORR) ... -0.692515954 +E(TOT) ... -205.416438487 +Singles norm **1/2 ... 0.092420471 ( 0.046210235, 0.046210235) +T1 diagnostic ... 0.021783714 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.064969 + 10a-> 13a 10b-> 13b 0.057046 + 8a-> 13a -1a-> -1a 0.052288 + 8b-> 13b -1b-> -1b 0.052288 + 10a-> 13a 8b-> 13b 0.036741 + 8a-> 13a 10b-> 13b 0.036741 + 11a-> 13a 11b-> 13b 0.029170 + 10a-> 13a 10b-> 22b 0.026317 + 10a-> 22a 10b-> 13b 0.026317 + 5a-> 13a 5b-> 13b 0.025167 + 8a-> 13a 8b-> 22b 0.024793 + 8a-> 22a 8b-> 13b 0.024793 + 11a-> 26a -1a-> -1a 0.023509 + 11b-> 26b -1b-> -1b 0.023509 + 10a-> 13a -1a-> -1a 0.023286 + 10b-> 13b -1b-> -1b 0.023286 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034626118 + alpha-alpha-alpha ... -0.000912946 ( 2.6%) + alpha-alpha-beta ... -0.016400112 ( 47.4%) + alpha-beta -beta ... -0.016400112 ( 47.4%) + beta -beta -beta ... -0.000912946 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034626118 + +Final correlation energy ... -0.727142072 +E(CCSD) ... -205.416438487 +E(CCSD(T)) ... -205.451064604 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.207504934 sqrt= 1.098865294 +W(HF) = 0.828153966 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.187374 -0.000000 + 1 N : 0.139182 0.000000 + 2 O : -0.183637 -0.000000 + 3 H : 0.231828 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.788286 s : 3.788286 + pz : 1.560219 p : 4.322905 + px : 1.405057 + py : 1.357629 + dz2 : 0.016725 d : 0.067047 + dxz : 0.012125 + dyz : 0.008084 + dx2y2 : 0.020185 + dxy : 0.009928 + f0 : 0.000963 f : 0.009135 + f+1 : 0.001875 + f-1 : 0.000956 + f+2 : 0.001201 + f-2 : 0.001651 + f+3 : 0.001019 + f-3 : 0.001472 + 1 N s : 3.915977 s : 3.915977 + pz : 0.805712 p : 2.741073 + px : 0.796147 + py : 1.139214 + dz2 : 0.037629 d : 0.171432 + dxz : 0.034530 + dyz : 0.027680 + dx2y2 : 0.044167 + dxy : 0.027426 + f0 : 0.002338 f : 0.032336 + f+1 : 0.003698 + f-1 : 0.005206 + f+2 : 0.002749 + f-2 : 0.005489 + f+3 : 0.005193 + f-3 : 0.007662 + 2 O s : 3.844395 s : 3.844395 + pz : 1.364726 p : 4.246122 + px : 1.528240 + py : 1.353156 + dz2 : 0.016900 d : 0.082980 + dxz : 0.009611 + dyz : 0.018847 + dx2y2 : 0.017366 + dxy : 0.020256 + f0 : 0.000816 f : 0.010140 + f+1 : 0.000743 + f-1 : 0.002048 + f+2 : 0.001532 + f-2 : 0.001387 + f+3 : 0.001620 + f-3 : 0.001994 + 3 H s : 0.664150 s : 0.664150 + pz : 0.038165 p : 0.084360 + px : 0.032955 + py : 0.013240 + dz2 : 0.000022 d : 0.019662 + dxz : -0.000277 + dyz : 0.009639 + dx2y2 : 0.000030 + dxy : 0.010248 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.618823 -0.000000 + 1 N : -0.333843 0.000000 + 2 O : 0.281250 -0.000000 + 3 H : -0.566229 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.114726 s : 3.114726 + pz : 1.306615 p : 3.831100 + px : 1.252258 + py : 1.272226 + dz2 : 0.051700 d : 0.333118 + dxz : 0.091836 + dyz : 0.044341 + dx2y2 : 0.075821 + dxy : 0.069420 + f0 : 0.009562 f : 0.102233 + f+1 : 0.019279 + f-1 : 0.005481 + f+2 : 0.016508 + f-2 : 0.021573 + f+3 : 0.008948 + f-3 : 0.020883 + 1 N s : 3.004228 s : 3.004228 + pz : 0.814069 p : 2.882266 + px : 0.847234 + py : 1.220963 + dz2 : 0.178648 d : 0.984812 + dxz : 0.211673 + dyz : 0.158732 + dx2y2 : 0.251288 + dxy : 0.184472 + f0 : 0.036862 f : 0.462537 + f+1 : 0.048277 + f-1 : 0.058551 + f+2 : 0.067811 + f-2 : 0.083653 + f+3 : 0.073611 + f-3 : 0.093773 + 2 O s : 3.299430 s : 3.299430 + pz : 1.215056 p : 3.941389 + px : 1.309865 + py : 1.416468 + dz2 : 0.053512 d : 0.353283 + dxz : 0.048019 + dyz : 0.070471 + dx2y2 : 0.117244 + dxy : 0.064037 + f0 : 0.009251 f : 0.124649 + f+1 : 0.005811 + f-1 : 0.022460 + f+2 : 0.019669 + f-2 : 0.019407 + f+3 : 0.018011 + f-3 : 0.030039 + 3 H s : 0.615065 s : 0.615065 + pz : 0.143299 p : 0.548838 + px : 0.137629 + py : 0.267909 + dz2 : 0.039919 d : 0.402327 + dxz : 0.028775 + dyz : 0.113620 + dx2y2 : 0.106152 + dxy : 0.113861 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.1874 8.0000 -0.1874 2.1826 1.7342 0.4485 + 1 N 6.8608 7.0000 0.1392 2.7917 2.3237 0.4680 + 2 O 8.1836 8.0000 -0.1836 2.0728 1.5754 0.4974 + 3 H 0.7682 1.0000 0.2318 1.0348 0.9609 0.0739 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7849 B( 0-O , 2-O ) : 0.1004 B( 0-O , 3-H ) : 0.8489 +B( 1-N , 2-O ) : 1.4509 + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 45.662 sec + +Fock Matrix Formation ... 0.207 sec ( 0.5%) +Initial Guess ... 0.134 sec ( 0.3%) +DIIS Solver ... 1.254 sec ( 2.7%) +State Vector Update ... 0.063 sec ( 0.1%) +Sigma-vector construction ... 29.453 sec ( 64.5%) + <0|H|D> ... 0.003 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.019 sec ( 0.1% of sigma) + (0-ext) ... 0.054 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (2-ext) ... 0.734 sec ( 2.5% of sigma) + (4-ext) ... 16.134 sec ( 54.8% of sigma) + ... 1.172 sec ( 4.0% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.085 sec ( 0.3% of sigma) + Fock-dressing ... 1.703 sec ( 5.8% of sigma) + (ik|jl)-dressing ... 0.059 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 7.382 sec ( 25.1% of sigma) + Pair energies ... 0.004 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.689 sec ( 14.6% of ALL) + I/O of integral and amplitudes ... 0.750 sec ( 11.2% of (T)) + External N**7 contributions ... 3.893 sec ( 58.2% of (T)) + Internal N**7 contributions ... 0.310 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.590 sec ( 23.8% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.451064604491 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.022.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.022.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.387454, -0.306185 -0.334638) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.62487 -0.26325 -0.49372 +Nuclear contribution : -0.85401 0.70614 0.72692 + ----------------------------------------- +Total Dipole Moment : -0.22915 0.44289 0.23320 + ----------------------------------------- +Magnitude (a.u.) : 0.55049 +Magnitude (Debye) : 1.39925 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.781532 0.439447 0.379731 +Rotational constants in MHz : 83388.226645 13174.289354 11384.043250 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.173423 0.516388 0.079451 +x,y,z [Debye]: -0.440807 1.312554 0.201948 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.387454, -0.306185 -0.334638) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.64701 -0.18085 -0.53448 +Nuclear contribution : -0.85401 0.70614 0.72692 + ----------------------------------------- +Total Dipole Moment : -0.20701 0.52529 0.19244 + ----------------------------------------- +Magnitude (a.u.) : 0.59650 +Magnitude (Debye) : 1.51618 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.781532 0.439447 0.379731 +Rotational constants in MHz : 83388.226645 13174.289354 11384.043250 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.106784 0.582731 0.069529 +x,y,z [Debye]: -0.271424 1.481185 0.176728 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 23 * + * * + * Dihedral ( 2, 1, 0, 3) : 0.00000000 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0310591889 RMS(Int)= 0.0005615741 + Iter 1: RMS(Cart)= 0.0001221434 RMS(Int)= 0.0000060044 + Iter 2: RMS(Cart)= 0.0000013060 RMS(Int)= 0.0000000644 + Iter 3: RMS(Cart)= 0.0000000140 RMS(Int)= 0.0000000007 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.3993 0.000000 + 2. B(O 2,N 1) 1.1879 0.000000 + 3. B(H 3,O 0) 0.9798 0.000000 + 4. A(N 1,O 0,H 3) 104.4709 0.000000 + 5. A(O 0,N 1,O 2) 113.0377 0.000000 + 6. D(O 2,N 1,O 0,H 3) -0.0000 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.618292 -0.385492 0.546976 + N 0.440525 -0.604720 -0.341151 + O 0.893504 0.401154 -0.781833 + H -0.715736 0.589058 0.576008 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.168402 -0.728474 1.033634 + 1 N 7.0000 0 14.007 0.832472 -1.142755 -0.644682 + 2 O 8.0000 0 15.999 1.688478 0.758071 -1.477450 + 3 H 1.0000 0 1.008 -1.352545 1.113159 1.088497 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.397680022118 0.00000000 0.00000000 + O 2 1 0 1.186754838154 113.22026461 0.00000000 + H 1 2 3 0.978057208066 104.68348439 351.81818159 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.641232464657 0.00000000 0.00000000 + O 2 1 0 2.242641632217 113.22026461 0.00000000 + H 1 2 3 1.848260266553 104.68348439 351.81818159 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2245 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2720 + la=0 lb=0: 557 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.070613503953 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 70.0706135040 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.435e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7199089408 0.000000000000 0.00187507 0.00005590 0.0121259 0.7000 + 1 -204.7206415957 -0.000732654957 0.00166553 0.00005140 0.0101629 0.7000 + ***Turning on DIIS*** + 2 -204.7212815260 -0.000639930284 0.00441166 0.00014070 0.0083706 0.0000 + 3 -204.7243918558 -0.003110329802 0.00207444 0.00006125 0.0038794 0.0000 + 4 -204.7227476671 0.001644188670 0.00096051 0.00003063 0.0016760 0.0000 + 5 -204.7245361252 -0.001788458113 0.00086542 0.00003547 0.0008953 0.0000 + 6 -204.7236902271 0.000845898156 0.00051571 0.00002401 0.0004898 0.0000 + 7 -204.7235348798 0.000155347241 0.00029992 0.00001522 0.0002891 0.0000 + 8 -204.7242491723 -0.000714292417 0.00019393 0.00000842 0.0001744 0.0000 + 9 -204.7237369251 0.000512247130 0.00007795 0.00000270 0.0000550 0.0000 + 10 -204.7238607248 -0.000123799647 0.00002989 0.00000077 0.0000294 0.0000 + 11 -204.7238948852 -0.000034160413 0.00001526 0.00000035 0.0000197 0.0000 + 12 -204.7238392880 0.000055597198 0.00000631 0.00000015 0.0000070 0.0000 + 13 -204.7238561628 -0.000016874786 0.00000195 0.00000005 0.0000022 0.0000 + 14 -204.7238517972 0.000004365544 0.00000083 0.00000003 0.0000011 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 15 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72385173 Eh -5570.81922 eV + +Components: +Nuclear Repulsion : 70.07061350 Eh 1906.71833 eV +Electronic Energy : -274.79446524 Eh -7477.53755 eV +One Electron Energy: -419.71823851 Eh -11421.11391 eV +Two Electron Energy: 144.92377327 Eh 3943.57636 eV + +Virial components: +Potential Energy : -408.96279249 Eh -11128.44334 eV +Kinetic Energy : 204.23894075 Eh 5557.62412 eV +Virial Ratio : 2.00237423 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 6.4818e-08 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.6554e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.0648e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.2844e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.665966 -562.3495 + 1 1.0000 -20.651650 -561.9600 + 2 1.0000 -15.803429 -430.0332 + 3 1.0000 -1.607983 -43.7554 + 4 1.0000 -1.407096 -38.2890 + 5 1.0000 -0.967418 -26.3248 + 6 1.0000 -0.775816 -21.1110 + 7 1.0000 -0.743807 -20.2400 + 8 1.0000 -0.688709 -18.7407 + 9 1.0000 -0.614843 -16.7307 + 10 1.0000 -0.532861 -14.4999 + 11 1.0000 -0.475770 -12.9464 + 12 0.0000 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3.7195 + 18 0.0000 0.157970 4.2986 + 19 0.0000 0.169199 4.6041 + 20 0.0000 0.184830 5.0295 + 21 0.0000 0.195320 5.3149 + 22 0.0000 0.205714 5.5978 + 23 0.0000 0.232449 6.3253 + 24 0.0000 0.249932 6.8010 + 25 0.0000 0.301922 8.2157 + 26 0.0000 0.313073 8.5192 + 27 0.0000 0.344661 9.3787 + 28 0.0000 0.352633 9.5956 + 29 0.0000 0.400574 10.9002 + 30 0.0000 0.443780 12.0759 + 31 0.0000 0.511986 13.9319 + 32 0.0000 0.515359 14.0236 + 33 0.0000 0.535771 14.5791 + 34 0.0000 0.562144 15.2967 + 35 0.0000 0.617327 16.7983 + 36 0.0000 0.640200 17.4207 + 37 0.0000 0.669018 18.2049 + 38 0.0000 0.682977 18.5847 + 39 0.0000 0.697858 18.9897 + 40 0.0000 0.732025 19.9194 + 41 0.0000 0.757557 20.6142 + 42 0.0000 0.764268 20.7968 + 43 0.0000 0.780049 21.2262 + 44 0.0000 0.799611 21.7585 + 45 0.0000 0.845065 22.9954 + 46 0.0000 0.851434 23.1687 + 47 0.0000 0.869610 23.6633 + 48 0.0000 0.917917 24.9778 + 49 0.0000 0.938534 25.5388 + 50 0.0000 0.953583 25.9483 + 51 0.0000 1.007460 27.4144 + 52 0.0000 1.028943 27.9990 + 53 0.0000 1.076947 29.3052 + 54 0.0000 1.078498 29.3474 + 55 0.0000 1.090024 29.6611 + 56 0.0000 1.178681 32.0735 + 57 0.0000 1.221046 33.2264 + 58 0.0000 1.237531 33.6749 + 59 0.0000 1.260167 34.2909 + 60 0.0000 1.338365 36.4188 + 61 0.0000 1.413533 38.4642 + 62 0.0000 1.463460 39.8228 + 63 0.0000 1.505818 40.9754 + 64 0.0000 1.539409 41.8894 + 65 0.0000 1.555760 42.3344 + 66 0.0000 1.595278 43.4097 + 67 0.0000 1.605842 43.6972 + 68 0.0000 1.656829 45.0846 + 69 0.0000 1.770874 48.1879 + 70 0.0000 1.784807 48.5671 + 71 0.0000 1.821311 49.5604 + 72 0.0000 1.906221 51.8709 + 73 0.0000 1.919936 52.2441 + 74 0.0000 1.989480 54.1365 + 75 0.0000 1.997136 54.3448 + 76 0.0000 2.039390 55.4946 + 77 0.0000 2.131008 57.9877 + 78 0.0000 2.145648 58.3861 + 79 0.0000 2.178138 59.2702 + 80 0.0000 2.286780 62.2265 + 81 0.0000 2.329506 63.3891 + 82 0.0000 2.344053 63.7849 + 83 0.0000 2.385854 64.9224 + 84 0.0000 2.435554 66.2748 + 85 0.0000 2.459022 66.9134 + 86 0.0000 2.475492 67.3616 + 87 0.0000 2.505434 68.1763 + 88 0.0000 2.514664 68.4275 + 89 0.0000 2.561229 69.6946 + 90 0.0000 2.575916 70.0942 + 91 0.0000 2.649793 72.1045 + 92 0.0000 2.651474 72.1503 + 93 0.0000 2.694797 73.3292 + 94 0.0000 2.754628 74.9572 + 95 0.0000 2.783905 75.7539 + 96 0.0000 2.915078 79.3233 + 97 0.0000 2.957243 80.4707 + 98 0.0000 2.979076 81.0648 + 99 0.0000 3.066059 83.4317 + 100 0.0000 3.143517 85.5395 + 101 0.0000 3.150579 85.7316 + 102 0.0000 3.215609 87.5012 + 103 0.0000 3.510934 95.5374 + 104 0.0000 3.758683 102.2790 + 105 0.0000 3.834756 104.3490 + 106 0.0000 4.024319 109.5073 + 107 0.0000 4.152963 113.0079 + 108 0.0000 4.170804 113.4933 + 109 0.0000 4.237999 115.3218 + 110 0.0000 4.359270 118.6218 + 111 0.0000 4.404353 119.8485 + 112 0.0000 4.521608 123.0392 + 113 0.0000 4.567968 124.3007 + 114 0.0000 4.698774 127.8601 + 115 0.0000 4.846545 131.8812 + 116 0.0000 4.890573 133.0793 + 117 0.0000 4.891580 133.1067 + 118 0.0000 4.947162 134.6191 + 119 0.0000 4.998187 136.0076 + 120 0.0000 5.063039 137.7723 + 121 0.0000 5.103665 138.8778 + 122 0.0000 5.199054 141.4734 + 123 0.0000 5.216644 141.9521 + 124 0.0000 5.230479 142.3286 + 125 0.0000 5.303409 144.3131 + 126 0.0000 5.387560 146.6030 + 127 0.0000 5.482404 149.1838 + 128 0.0000 5.555726 151.1790 + 129 0.0000 5.658184 153.9670 + 130 0.0000 5.790455 157.5663 + 131 0.0000 5.918635 161.0542 + 132 0.0000 6.186370 168.3397 + 133 0.0000 6.420323 174.7059 + 134 0.0000 6.520121 177.4215 + 135 0.0000 6.570952 178.8047 + 136 0.0000 6.673604 181.5980 + 137 0.0000 6.699880 182.3130 + 138 0.0000 6.763728 184.0504 + 139 0.0000 6.835143 185.9937 + 140 0.0000 6.951731 189.1662 + 141 0.0000 7.101297 193.2361 + 142 0.0000 7.114344 193.5911 + 143 0.0000 7.158691 194.7979 + 144 0.0000 7.161857 194.8840 + 145 0.0000 7.228209 196.6896 + 146 0.0000 7.286673 198.2805 + 147 0.0000 7.315115 199.0544 + 148 0.0000 7.414567 201.7606 + 149 0.0000 7.420407 201.9195 + 150 0.0000 7.462336 203.0605 + 151 0.0000 7.493990 203.9218 + 152 0.0000 7.610346 207.0880 + 153 0.0000 7.692784 209.3313 + 154 0.0000 7.857287 213.8076 + 155 0.0000 7.943608 216.1566 + 156 0.0000 8.297889 225.7970 + 157 0.0000 8.317004 226.3172 + 158 0.0000 14.204716 386.5300 + 159 0.0000 15.053123 409.6163 + 160 0.0000 15.604003 424.6065 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.279511 0.000000 + 1 N : 0.332370 0.000000 + 2 O : -0.304626 0.000000 + 3 H : 0.251766 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.801438 s : 3.801438 + pz : 1.581194 p : 4.435002 + px : 1.471397 + py : 1.382412 + dz2 : 0.010343 d : 0.037554 + dxz : 0.007626 + dyz : 0.001360 + dx2y2 : 0.016686 + dxy : 0.001540 + f0 : 0.000466 f : 0.005516 + f+1 : 0.001385 + f-1 : 0.000327 + f+2 : 0.000942 + f-2 : 0.001273 + f+3 : 0.000307 + f-3 : 0.000816 + 1 N s : 3.867219 s : 3.867219 + pz : 0.708372 p : 2.622443 + px : 0.723913 + py : 1.190158 + dz2 : 0.031173 d : 0.144664 + dxz : 0.028049 + dyz : 0.024381 + dx2y2 : 0.035605 + dxy : 0.025456 + f0 : 0.002906 f : 0.033305 + f+1 : 0.003183 + f-1 : 0.005415 + f+2 : 0.003091 + f-2 : 0.005622 + f+3 : 0.005300 + f-3 : 0.007789 + 2 O s : 3.856357 s : 3.856357 + pz : 1.455903 p : 4.381481 + px : 1.547580 + py : 1.377999 + dz2 : 0.010837 d : 0.059361 + dxz : 0.002738 + dyz : 0.017549 + dx2y2 : 0.011113 + dxy : 0.017125 + f0 : 0.000378 f : 0.007426 + f+1 : 0.000228 + f-1 : 0.001773 + f+2 : 0.001076 + f-2 : 0.000922 + f+3 : 0.001313 + f-3 : 0.001737 + 3 H s : 0.645683 s : 0.645683 + pz : 0.031342 p : 0.081767 + px : 0.030280 + py : 0.020144 + dz2 : -0.000151 d : 0.020784 + dxz : -0.000949 + dyz : 0.010712 + dx2y2 : 0.000582 + dxy : 0.010590 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.600912 0.000000 + 1 N : -0.282414 0.000000 + 2 O : 0.245037 0.000000 + 3 H : -0.563534 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.107416 s : 3.107416 + pz : 1.330263 p : 3.896211 + px : 1.279904 + py : 1.286044 + dz2 : 0.045702 d : 0.300892 + dxz : 0.087338 + dyz : 0.041568 + dx2y2 : 0.064604 + dxy : 0.061681 + f0 : 0.008621 f : 0.094570 + f+1 : 0.017452 + f-1 : 0.005745 + f+2 : 0.015326 + f-2 : 0.022762 + f+3 : 0.007044 + f-3 : 0.017620 + 1 N s : 3.000087 s : 3.000087 + pz : 0.760461 p : 2.829034 + px : 0.800723 + py : 1.267850 + dz2 : 0.183776 d : 0.979068 + dxz : 0.202636 + dyz : 0.157820 + dx2y2 : 0.247738 + dxy : 0.187097 + f0 : 0.042637 f : 0.474225 + f+1 : 0.051998 + f-1 : 0.060901 + f+2 : 0.063801 + f-2 : 0.086344 + f+3 : 0.071339 + f-3 : 0.097205 + 2 O s : 3.297381 s : 3.297381 + pz : 1.261273 p : 4.023231 + px : 1.324848 + py : 1.437110 + dz2 : 0.045852 d : 0.318889 + dxz : 0.042306 + dyz : 0.057375 + dx2y2 : 0.113970 + dxy : 0.059386 + f0 : 0.008397 f : 0.115462 + f+1 : 0.004780 + f-1 : 0.019963 + f+2 : 0.015406 + f-2 : 0.018767 + f+3 : 0.017749 + f-3 : 0.030402 + 3 H s : 0.608613 s : 0.608613 + pz : 0.139442 p : 0.540596 + px : 0.137695 + py : 0.263460 + dz2 : 0.039248 d : 0.414325 + dxz : 0.029339 + dyz : 0.119391 + dx2y2 : 0.108214 + dxy : 0.118132 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2795 8.0000 -0.2795 1.8044 1.8044 -0.0000 + 1 N 6.6676 7.0000 0.3324 2.5023 2.5023 -0.0000 + 2 O 8.3046 8.0000 -0.3046 1.6622 1.6622 -0.0000 + 3 H 0.7482 1.0000 0.2518 1.0122 1.0122 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8268 B( 0-O , 3-H ) : 0.9195 B( 1-N , 2-O ) : 1.5935 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.330 sec +Sum of individual times .... 2.097 sec ( 90.0%) + +Fock matrix formation .... 1.689 sec ( 72.5%) +Diagonalization .... 0.177 sec ( 7.6%) +Density matrix formation .... 0.013 sec ( 0.6%) +Population analysis .... 0.045 sec ( 1.9%) +Initial guess .... 0.010 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.006 sec ( 0.3%) +DIIS solution .... 0.162 sec ( 7.0%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.203 sec +Reference energy ... -204.723851604 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.386 sec +AO-integral generation ... 0.142 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.386 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.022 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.025 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.038 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.023 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.039 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.347 sec +AO-integral generation ... 0.241 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.153 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.256 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090692920 +EMP2(bb)= -0.090692920 +EMP2(ab)= -0.515246209 + +Initial guess performed in 0.134 sec +E(0) ... -204.723851604 +E(MP2) ... -0.696632050 +Initial E(tot) ... -205.420483653 + ... 0.186854809 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.420483653 -0.696632050 -0.000000000 0.031191274 2.72 0.000002322 + *** Turning on DIIS *** + 1 -205.391298047 -0.667446444 0.029185606 0.012520624 2.71 0.058562583 + 2 -205.410768234 -0.686916630 -0.019470186 0.007088501 2.79 0.061794919 + 3 -205.414454249 -0.690602645 -0.003686015 0.002564835 2.83 0.076354324 + 4 -205.416047722 -0.692196119 -0.001593473 0.001564018 2.79 0.083443013 + 5 -205.416598119 -0.692746515 -0.000550397 0.000727635 2.90 0.088958258 + 6 -205.416696426 -0.692844823 -0.000098307 0.000461742 2.86 0.091369578 + 7 -205.416735197 -0.692883593 -0.000038771 0.000205820 2.92 0.092324169 + 8 -205.416743500 -0.692891897 -0.000008304 0.000110888 2.89 0.092658069 + 9 -205.416739710 -0.692888107 0.000003790 0.000028512 2.80 0.092758318 + 10 -205.416743966 -0.692892363 -0.000004256 0.000008052 2.76 0.092794349 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.723851604 +E(CORR) ... -0.692892363 +E(TOT) ... -205.416743966 +Singles norm **1/2 ... 0.092794349 ( 0.046397174, 0.046397174) +T1 diagnostic ... 0.021871838 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.066139 + 10a-> 13a 10b-> 13b 0.057894 + 8b-> 13b -1b-> -1b 0.053131 + 8a-> 13a -1a-> -1a 0.053131 + 8a-> 13a 10b-> 13b 0.037459 + 10a-> 13a 8b-> 13b 0.037459 + 11a-> 13a 11b-> 13b 0.028964 + 10a-> 22a 10b-> 13b 0.026597 + 10a-> 13a 10b-> 22b 0.026597 + 5a-> 13a 5b-> 13b 0.025336 + 8a-> 22a 8b-> 13b 0.025097 + 8a-> 13a 8b-> 22b 0.025097 + 11a-> 26a -1a-> -1a 0.024321 + 11b-> 26b -1b-> -1b 0.024321 + 10a-> 13a -1a-> -1a 0.023367 + 10b-> 13b -1b-> -1b 0.023367 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034729192 + alpha-alpha-alpha ... -0.000915278 ( 2.6%) + alpha-alpha-beta ... -0.016449318 ( 47.4%) + alpha-beta -beta ... -0.016449318 ( 47.4%) + beta -beta -beta ... -0.000915278 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034729192 + +Final correlation energy ... -0.727621555 +E(CCSD) ... -205.416743966 +E(CCSD(T)) ... -205.451473158 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.207977948 sqrt= 1.099080501 +W(HF) = 0.827829682 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.188226 0.000000 + 1 N : 0.138912 0.000000 + 2 O : -0.183885 0.000000 + 3 H : 0.233199 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.788993 s : 3.788993 + pz : 1.529810 p : 4.322986 + px : 1.435227 + py : 1.357949 + dz2 : 0.016994 d : 0.067095 + dxz : 0.011981 + dyz : 0.008615 + dx2y2 : 0.020340 + dxy : 0.009165 + f0 : 0.001035 f : 0.009152 + f+1 : 0.001838 + f-1 : 0.000972 + f+2 : 0.001286 + f-2 : 0.001694 + f+3 : 0.000917 + f-3 : 0.001410 + 1 N s : 3.916698 s : 3.916698 + pz : 0.800764 p : 2.740739 + px : 0.799693 + py : 1.140282 + dz2 : 0.038050 d : 0.171315 + dxz : 0.034291 + dyz : 0.026961 + dx2y2 : 0.043432 + dxy : 0.028580 + f0 : 0.002967 f : 0.032336 + f+1 : 0.003213 + f-1 : 0.005246 + f+2 : 0.002753 + f-2 : 0.005581 + f+3 : 0.004905 + f-3 : 0.007671 + 2 O s : 3.844055 s : 3.844055 + pz : 1.403287 p : 4.246803 + px : 1.491713 + py : 1.351802 + dz2 : 0.015919 d : 0.082885 + dxz : 0.009477 + dyz : 0.019729 + dx2y2 : 0.018017 + dxy : 0.019743 + f0 : 0.000865 f : 0.010143 + f+1 : 0.000775 + f-1 : 0.002001 + f+2 : 0.001440 + f-2 : 0.001385 + f+3 : 0.001612 + f-3 : 0.002066 + 3 H s : 0.663788 s : 0.663788 + pz : 0.035961 p : 0.083534 + px : 0.034190 + py : 0.013382 + dz2 : -0.000069 d : 0.019478 + dxz : -0.000281 + dyz : 0.009787 + dx2y2 : 0.000143 + dxy : 0.009899 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.617043 0.000000 + 1 N : -0.332139 -0.000000 + 2 O : 0.281033 0.000000 + 3 H : -0.565937 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.116428 s : 3.116428 + pz : 1.299072 p : 3.831885 + px : 1.261007 + py : 1.271807 + dz2 : 0.053523 d : 0.332581 + dxz : 0.093615 + dyz : 0.047009 + dx2y2 : 0.071616 + dxy : 0.066818 + f0 : 0.009809 f : 0.102062 + f+1 : 0.019627 + f-1 : 0.006840 + f+2 : 0.016567 + f-2 : 0.022620 + f+3 : 0.008120 + f-3 : 0.018479 + 1 N s : 3.005594 s : 3.005594 + pz : 0.814418 p : 2.882006 + px : 0.842109 + py : 1.225479 + dz2 : 0.182224 d : 0.982383 + dxz : 0.210426 + dyz : 0.156471 + dx2y2 : 0.247889 + dxy : 0.185374 + f0 : 0.041757 f : 0.462157 + f+1 : 0.048087 + f-1 : 0.059228 + f+2 : 0.063824 + f-2 : 0.084099 + f+3 : 0.071614 + f-3 : 0.093548 + 2 O s : 3.299365 s : 3.299365 + pz : 1.231720 p : 3.941810 + px : 1.291896 + py : 1.418194 + dz2 : 0.054434 d : 0.353277 + dxz : 0.047419 + dyz : 0.065836 + dx2y2 : 0.118305 + dxy : 0.067283 + f0 : 0.009237 f : 0.124516 + f+1 : 0.006068 + f-1 : 0.022322 + f+2 : 0.017319 + f-2 : 0.019182 + f+3 : 0.019590 + f-3 : 0.030798 + 3 H s : 0.614461 s : 0.614461 + pz : 0.141164 p : 0.547740 + px : 0.139092 + py : 0.267484 + dz2 : 0.038934 d : 0.403737 + dxz : 0.029367 + dyz : 0.114116 + dx2y2 : 0.107575 + dxy : 0.113744 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.1882 8.0000 -0.1882 2.1831 1.7335 0.4496 + 1 N 6.8611 7.0000 0.1389 2.7934 2.3246 0.4688 + 2 O 8.1839 8.0000 -0.1839 2.0728 1.5748 0.4979 + 3 H 0.7668 1.0000 0.2332 1.0331 0.9592 0.0740 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7866 B( 0-O , 2-O ) : 0.1006 B( 0-O , 3-H ) : 0.8463 +B( 1-N , 2-O ) : 1.4497 + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 45.979 sec + +Fock Matrix Formation ... 0.203 sec ( 0.4%) +Initial Guess ... 0.134 sec ( 0.3%) +DIIS Solver ... 1.334 sec ( 2.9%) +State Vector Update ... 0.063 sec ( 0.1%) +Sigma-vector construction ... 29.580 sec ( 64.3%) + <0|H|D> ... 0.003 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.019 sec ( 0.1% of sigma) + (0-ext) ... 0.053 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (2-ext) ... 0.726 sec ( 2.5% of sigma) + (4-ext) ... 16.285 sec ( 55.1% of sigma) + ... 1.152 sec ( 3.9% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.085 sec ( 0.3% of sigma) + Fock-dressing ... 1.708 sec ( 5.8% of sigma) + (ik|jl)-dressing ... 0.058 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 7.390 sec ( 25.0% of sigma) + Pair energies ... 0.004 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.776 sec ( 14.7% of ALL) + I/O of integral and amplitudes ... 0.619 sec ( 9.1% of (T)) + External N**7 contributions ... 3.884 sec ( 57.3% of (T)) + Internal N**7 contributions ... 0.307 sec ( 4.5% of (T)) + N**6 triples energy contributions ... 1.560 sec ( 23.0% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.451473158348 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.000886219 -0.000791347 0.000798455 + 2 N : 0.000722166 -0.002315803 -0.000486029 + 3 O : 0.000259045 0.001681570 -0.000313676 + 4 H : -0.000094992 0.001425580 0.000001250 + +Norm of the cartesian gradient ... 0.003633774 +RMS gradient ... 0.001048980 +MAX gradient ... 0.002315803 + +------- +TIMINGS +------- + +Total numerical gradient time ... 312.544 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 628.84 cm**-1 + 7: 677.98 cm**-1 + 8: 870.44 cm**-1 + 9: 1338.82 cm**-1 + 10: 1653.96 cm**-1 + 11: 3575.09 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 -0.272590 -0.059293 -0.216463 0.051807 -0.011326 0.005271 + 1 -0.117233 -0.003654 0.151316 0.077390 0.068887 -0.061172 + 2 0.238234 -0.069274 0.176360 -0.048337 0.005809 -0.001158 + 3 0.088389 0.061755 0.376671 0.068405 -0.102997 0.002366 + 4 0.166793 0.003745 -0.242639 -0.007057 -0.493446 -0.001222 + 5 -0.084359 0.071862 -0.307556 -0.057753 0.114837 -0.001887 + 6 0.234647 -0.035178 -0.147153 -0.064579 0.137314 -0.000400 + 7 -0.017548 -0.002227 0.047108 -0.068507 0.363951 -0.000209 + 8 -0.198535 -0.041072 0.122911 0.058680 -0.136856 0.000319 + 9 -0.626015 0.641322 0.537172 -0.747835 -0.568444 -0.110193 + 10 -0.178477 0.041300 0.222279 -0.042926 -0.013170 0.991217 + 11 0.542138 0.752829 -0.476295 0.638372 0.484212 0.039541 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 628.84 0.006031 30.48 0.002993 ( 0.034847 0.028364 -0.031207) + 7: 677.98 0.018583 93.91 0.008553 ( 0.060201 0.003815 0.070105) + 8: 870.44 0.056035 283.18 0.020089 ( 0.107585 0.006208 -0.092067) + 9: 1338.82 0.001827 9.23 0.000426 (-0.002335 0.020484 0.000944) + 10: 1653.96 0.028961 146.36 0.005464 (-0.053996 -0.018580 0.046942) + 11: 3575.09 0.006242 31.55 0.000545 (-0.010695 0.019118 0.008062) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 628.84 E(vib) ... 0.09 +freq. 677.98 E(vib) ... 0.08 +freq. 870.44 E(vib) ... 0.04 +freq. 1338.82 E(vib) ... 0.01 +freq. 1653.96 E(vib) ... 0.00 +freq. 3575.09 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.45147316 Eh +Zero point energy ... 0.01992288 Eh 12.50 kcal/mol +Thermal vibrational correction ... 0.00033910 Eh 0.21 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42837863 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00317164 Eh 1.99 kcal/mol +Non-thermal (ZPE) correction 0.01992288 Eh 12.50 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02309453 Eh 14.49 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42837863 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.42743442 Eh + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: Cs, Symmetry Number: 1 +Rotational constants in cm-1: 2.764626 0.439768 0.379414 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00043860 Eh 0.28 kcal/mol +Rotational entropy ... 0.00987608 Eh 6.20 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02811699 Eh 17.64 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00987608 Eh 6.20 kcal/mol| +| sn= 2 | S(rot)= 0.00922162 Eh 5.79 kcal/mol| +| sn= 3 | S(rot)= 0.00883879 Eh 5.55 kcal/mol| +| sn= 4 | S(rot)= 0.00856717 Eh 5.38 kcal/mol| +| sn= 5 | S(rot)= 0.00835648 Eh 5.24 kcal/mol| +| sn= 6 | S(rot)= 0.00818434 Eh 5.14 kcal/mol| +| sn= 7 | S(rot)= 0.00803879 Eh 5.04 kcal/mol| +| sn= 8 | S(rot)= 0.00791271 Eh 4.97 kcal/mol| +| sn= 9 | S(rot)= 0.00780150 Eh 4.90 kcal/mol| +| sn=10 | S(rot)= 0.00770202 Eh 4.83 kcal/mol| +| sn=11 | S(rot)= 0.00761203 Eh 4.78 kcal/mol| +| sn=12 | S(rot)= 0.00752988 Eh 4.73 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.42743442 Eh +Total entropy correction ... -0.02811699 Eh -17.64 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.45555142 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00407826 Eh -2.56 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.451473158 Eh +Current gradient norm .... 0.003633773 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.042881373 0.148058873 0.212542761 0.460522902 0.537664187 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999964546 +Lowest eigenvalues of augmented Hessian: + -0.000019470 0.148066000 0.212542840 0.460525083 0.537672072 +Length of the computed step .... 0.008420934 +The final length of the internal step .... 0.008420934 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0034378319 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0019222412 RMS(Int)= 0.0034369364 + Iter 1: RMS(Cart)= 0.0000040887 RMS(Int)= 0.0000054791 + Iter 2: RMS(Cart)= 0.0000000085 RMS(Int)= 0.0000000121 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000002 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0011624584 0.0001000000 NO + MAX gradient 0.0016395404 0.0003000000 NO + RMS step 0.0034378319 0.0020000000 NO + MAX step 0.0066047806 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0035 Max(Angles) 0.18 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.3993 0.001349 -0.0035 1.3958 + 2. B(O 2,N 1) 1.1879 0.001640 -0.0008 1.1872 + 3. B(H 3,O 0) 0.9798 0.001427 -0.0015 0.9784 + 4. A(N 1,O 0,H 3) 104.47 -0.000115 0.16 104.63 + 5. A(O 0,N 1,O 2) 113.04 -0.001245 0.18 113.22 + 6. D(O 2,N 1,O 0,H 3) -0.00 0.000000 0.00 -0.00 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.616970 -0.384843 0.545817 + N 0.439227 -0.603248 -0.340129 + O 0.894203 0.400138 -0.782371 + H -0.716459 0.587954 0.576683 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.165905 -0.727248 1.031444 + 1 N 7.0000 0 14.007 0.830020 -1.139974 -0.642751 + 2 O 8.0000 0 15.999 1.689798 0.756151 -1.478466 + 3 H 1.0000 0 1.008 -1.353911 1.111071 1.089773 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.395762940812 0.00000000 0.00000000 + O 2 1 0 1.187166230279 113.21650620 0.00000000 + H 1 2 3 0.978358024005 104.62924527 0.00000000 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.637609706011 0.00000000 0.00000000 + O 2 1 0 2.243419050666 113.21650620 0.00000000 + H 1 2 3 1.848828726294 104.62924527 0.00000000 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2245 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2720 + la=0 lb=0: 557 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.156962020230 Eh + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.427e-04 +Time for diagonalization ... 0.005 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.003 sec +Total time needed ... 0.008 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7243534800 0.000000000000 0.00011987 0.00000432 0.0005748 0.7000 + 1 -204.7243566624 -0.000003182437 0.00009595 0.00000354 0.0004505 0.7000 + ***Turning on DIIS*** + 2 -204.7243592465 -0.000002584065 0.00024724 0.00000913 0.0003582 0.0000 + 3 -204.7240521751 0.000307071392 0.00010321 0.00000290 0.0001073 0.0000 + 4 -204.7243661089 -0.000313933845 0.00002119 0.00000070 0.0000443 0.0000 + 5 -204.7244959445 -0.000129835558 0.00001169 0.00000024 0.0000152 0.0000 + 6 -204.7243261377 0.000169806766 0.00000317 0.00000013 0.0000066 0.0000 + 7 -204.7243673338 -0.000041196018 0.00000199 0.00000007 0.0000040 0.0000 + 8 -204.7243720703 -0.000004736584 0.00000105 0.00000003 0.0000012 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + +Total Energy : -204.72436352 Eh -5570.83315 eV + Last Energy change ... 8.5479e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.5083e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 3 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.481 sec +Reference energy ... -204.724367270 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 9.455 sec +AO-integral generation ... 0.327 sec +Half transformation ... 0.166 sec +K-integral sorting ... 7.193 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.051 s ( 0.000 ms/b) + 377910 b 0 skpd 0.060 s ( 0.000 ms/b) +: : 277134 b 0 skpd 0.075 s ( 0.000 ms/b) + 151164 b 0 skpd 0.070 s ( 0.000 ms/b) +: 159120 b 0 skpd 0.036 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.066 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.073 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.053 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.090 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.053 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.730 sec +AO-integral generation ... 0.567 sec +Half transformation ... 0.064 sec +J-integral sorting ... 0.077 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.293 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.366 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090634998 +EMP2(bb)= -0.090634998 +EMP2(ab)= -0.514861226 + +Initial guess performed in 0.166 sec +E(0) ... -204.724367270 +E(MP2) ... -0.696131222 +Initial E(tot) ... -205.420498492 + ... 0.186394121 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.420498492 -0.696131222 -0.000000000 0.031161344 4.66 0.000001030 + *** Turning on DIIS *** + 1 -205.391520728 -0.667153458 0.028977763 0.012493443 5.05 0.058365112 + 2 -205.410912799 -0.686545530 -0.019392071 0.007075073 5.95 0.061624091 + 3 -205.414583025 -0.690215756 -0.003670226 0.002560938 5.60 0.076113892 + 4 -205.416167112 -0.691799843 -0.001584087 0.001556868 5.89 0.083165033 + 5 -205.416711346 -0.692344076 -0.000544233 0.000713815 5.93 0.088621634 + 6 -205.416808196 -0.692440926 -0.000096850 0.000452317 5.98 0.090995277 + 7 -205.416846151 -0.692478882 -0.000037955 0.000202219 4.79 0.091925183 + 8 -205.416854101 -0.692486831 -0.000007950 0.000108904 4.80 0.092248274 + 9 -205.416850402 -0.692483133 0.000003699 0.000028041 5.94 0.092345372 + 10 -205.416854523 -0.692487254 -0.000004121 0.000007851 5.35 0.092380019 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.724367270 +E(CORR) ... -0.692487254 +E(TOT) ... -205.416854523 +Singles norm **1/2 ... 0.092380019 ( 0.046190009, 0.046190009) +T1 diagnostic ... 0.021774179 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.065570 + 10a-> 13a 10b-> 13b 0.058100 + 8a-> 13a -1a-> -1a 0.052974 + 8b-> 13b -1b-> -1b 0.052974 + 10a-> 13a 8b-> 13b 0.037256 + 8a-> 13a 10b-> 13b 0.037256 + 11a-> 13a 11b-> 13b 0.029091 + 10a-> 13a 10b-> 22b 0.026831 + 10a-> 22a 10b-> 13b 0.026831 + 5a-> 13a 5b-> 13b 0.025098 + 8a-> 13a 8b-> 22b 0.025021 + 8a-> 22a 8b-> 13b 0.025021 + 11a-> 26a -1a-> -1a 0.023500 + 11b-> 26b -1b-> -1b 0.023500 + 10a-> 13a -1a-> -1a 0.022828 + 10b-> 13b -1b-> -1b 0.022828 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034628396 + alpha-alpha-alpha ... -0.000913736 ( 2.6%) + alpha-alpha-beta ... -0.016400462 ( 47.4%) + alpha-beta -beta ... -0.016400462 ( 47.4%) + beta -beta -beta ... -0.000913736 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034628396 + +Final correlation energy ... -0.727115650 +E(CCSD) ... -205.416854523 +E(CCSD(T)) ... -205.451482919 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.207378155 sqrt= 1.098807606 +W(HF) = 0.828240925 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 85.947 sec + +Fock Matrix Formation ... 0.481 sec ( 0.6%) +Initial Guess ... 0.166 sec ( 0.2%) +DIIS Solver ... 3.328 sec ( 3.9%) +State Vector Update ... 0.220 sec ( 0.3%) +Sigma-vector construction ... 56.401 sec ( 65.6%) + <0|H|D> ... 0.008 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.041 sec ( 0.1% of sigma) + (0-ext) ... 0.136 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.037 sec ( 0.1% of sigma) + (2-ext) ... 1.260 sec ( 2.2% of sigma) + (4-ext) ... 33.220 sec ( 58.9% of sigma) + ... 2.636 sec ( 4.7% of sigma) + ... 0.004 sec ( 0.0% of sigma) + (1-ext) ... 0.011 sec ( 0.0% of sigma) + (1-ext) ... 0.153 sec ( 0.3% of sigma) + Fock-dressing ... 3.621 sec ( 6.4% of sigma) + (ik|jl)-dressing ... 0.100 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 12.300 sec ( 21.8% of sigma) + Pair energies ... 0.016 sec ( 0.0% of sigma) +Total Time for computing (T) ... 13.151 sec ( 15.3% of ALL) + I/O of integral and amplitudes ... 1.011 sec ( 7.7% of (T)) + External N**7 contributions ... 5.317 sec ( 40.4% of (T)) + Internal N**7 contributions ... 0.433 sec ( 3.3% of (T)) + N**6 triples energy contributions ... 2.140 sec ( 16.3% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.451482919316 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.000008268 0.000005214 -0.000006456 + 2 N : -0.000009529 0.000005321 0.000007911 + 3 O : -0.000003877 -0.000002363 0.000002865 + 4 H : 0.000005139 -0.000008172 -0.000004320 + +Norm of the cartesian gradient ... 0.000021439 +RMS gradient ... 0.000006189 +MAX gradient ... 0.000009529 + +------- +TIMINGS +------- + +Total numerical gradient time ... 498.689 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.451482919 Eh +Current gradient norm .... 0.000021439 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999996 +Lowest eigenvalues of augmented Hessian: + -0.000000002 0.148422342 0.212871301 0.461453430 0.536546082 +Length of the computed step .... 0.000094793 +The final length of the internal step .... 0.000094793 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0000386989 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0000420948 RMS(Int)= 0.0000386990 + Iter 1: RMS(Cart)= 0.0000000003 RMS(Int)= 0.0000000007 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000097618 0.0000050000 NO + RMS gradient 0.0000097255 0.0001000000 YES + MAX gradient 0.0000174829 0.0003000000 YES + RMS step 0.0000386989 0.0020000000 YES + MAX step 0.0000822483 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0000 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.3958 -0.000017 0.0000 1.3958 + 2. B(O 2,N 1) 1.1872 -0.000004 -0.0000 1.1872 + 3. B(H 3,O 0) 0.9784 -0.000009 0.0000 0.9784 + 4. A(N 1,O 0,H 3) 104.63 -0.000010 0.00 104.63 + 5. A(O 0,N 1,O 2) 113.22 -0.000007 0.00 113.22 + 6. D(O 2,N 1,O 0,H 3) 0.00 0.000000 -0.00 -0.00 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.616981 -0.384838 0.545825 + N 0.439250 -0.603249 -0.340148 + O 0.894233 0.400124 -0.782396 + H -0.716501 0.587963 0.576719 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.165925 -0.727239 1.031460 + 1 N 7.0000 0 14.007 0.830062 -1.139975 -0.642787 + 2 O 8.0000 0 15.999 1.689856 0.756125 -1.478514 + 3 H 1.0000 0 1.008 -1.353991 1.111089 1.089840 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.395806464753 0.00000000 0.00000000 + O 2 1 0 1.187160635644 113.21728847 0.00000000 + H 1 2 3 0.978366128175 104.63159938 0.00000000 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.637691954341 0.00000000 0.00000000 + O 2 1 0 2.243408478339 113.21728847 0.00000000 + H 1 2 3 1.848844040956 104.63159938 0.00000000 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2245 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2720 + la=0 lb=0: 557 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.155906522624 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 70.1559065226 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.427e-04 +Time for diagonalization ... 0.004 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.003 sec +Total time needed ... 0.008 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7243640375 0.000000000000 0.00000136 0.00000004 0.0000081 0.7000 + 1 -204.7243640375 0.000000000007 0.00000114 0.00000004 0.0000060 0.7000 + ***Turning on DIIS*** + 2 -204.7243640374 0.000000000083 0.00000301 0.00000010 0.0000044 0.0000 + 3 -204.7243665247 -0.000002487334 0.00000125 0.00000005 0.0000015 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 4 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72436350 Eh -5570.83315 eV + +Components: +Nuclear Repulsion : 70.15590652 Eh 1909.03927 eV +Electronic Energy : -274.88027002 Eh -7479.87242 eV +One Electron Energy: -419.88267252 Eh -11425.58838 eV +Two Electron Energy: 145.00240250 Eh 3945.71597 eV + +Virial components: +Potential Energy : -408.97487751 Eh -11128.77219 eV +Kinetic Energy : 204.25051401 Eh 5557.93905 eV +Virial Ratio : 2.00231994 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.0246e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.8501e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.6156e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.1806e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.665291 -562.3312 + 1 1.0000 -20.652017 -561.9700 + 2 1.0000 -15.802775 -430.0154 + 3 1.0000 -1.608825 -43.7784 + 4 1.0000 -1.408561 -38.3289 + 5 1.0000 -0.967726 -26.3332 + 6 1.0000 -0.776705 -21.1352 + 7 1.0000 -0.744306 -20.2536 + 8 1.0000 -0.689475 -18.7616 + 9 1.0000 -0.614702 -16.7269 + 10 1.0000 -0.533041 -14.5048 + 11 1.0000 -0.475504 -12.9391 + 12 0.0000 0.031754 0.8641 + 13 0.0000 0.078081 2.1247 + 14 0.0000 0.095241 2.5916 + 15 0.0000 0.113121 3.0782 + 16 0.0000 0.130249 3.5443 + 17 0.0000 0.136613 3.7174 + 18 0.0000 0.157842 4.2951 + 19 0.0000 0.169284 4.6065 + 20 0.0000 0.184696 5.0258 + 21 0.0000 0.195373 5.3164 + 22 0.0000 0.205943 5.6040 + 23 0.0000 0.232537 6.3276 + 24 0.0000 0.250097 6.8055 + 25 0.0000 0.301824 8.2130 + 26 0.0000 0.314233 8.5507 + 27 0.0000 0.344946 9.3865 + 28 0.0000 0.353017 9.6061 + 29 0.0000 0.400574 10.9002 + 30 0.0000 0.444529 12.0963 + 31 0.0000 0.512395 13.9430 + 32 0.0000 0.515344 14.0232 + 33 0.0000 0.535799 14.5798 + 34 0.0000 0.562388 15.3034 + 35 0.0000 0.617791 16.8109 + 36 0.0000 0.640546 17.4301 + 37 0.0000 0.669465 18.2171 + 38 0.0000 0.682707 18.5774 + 39 0.0000 0.697818 18.9886 + 40 0.0000 0.732051 19.9201 + 41 0.0000 0.757376 20.6092 + 42 0.0000 0.763537 20.7769 + 43 0.0000 0.779945 21.2234 + 44 0.0000 0.799444 21.7540 + 45 0.0000 0.845339 23.0028 + 46 0.0000 0.851692 23.1757 + 47 0.0000 0.870228 23.6801 + 48 0.0000 0.918271 24.9874 + 49 0.0000 0.938368 25.5343 + 50 0.0000 0.953498 25.9460 + 51 0.0000 1.007342 27.4112 + 52 0.0000 1.028948 27.9991 + 53 0.0000 1.076886 29.3035 + 54 0.0000 1.078525 29.3482 + 55 0.0000 1.089942 29.6588 + 56 0.0000 1.179361 32.0921 + 57 0.0000 1.221642 33.2426 + 58 0.0000 1.237724 33.6802 + 59 0.0000 1.260011 34.2866 + 60 0.0000 1.337476 36.3946 + 61 0.0000 1.413759 38.4704 + 62 0.0000 1.464195 39.8428 + 63 0.0000 1.506389 40.9909 + 64 0.0000 1.539729 41.8981 + 65 0.0000 1.556541 42.3556 + 66 0.0000 1.595757 43.4228 + 67 0.0000 1.606993 43.7285 + 68 0.0000 1.657238 45.0957 + 69 0.0000 1.771298 48.1995 + 70 0.0000 1.786668 48.6177 + 71 0.0000 1.822023 49.5798 + 72 0.0000 1.906622 51.8818 + 73 0.0000 1.919668 52.2368 + 74 0.0000 1.988827 54.1187 + 75 0.0000 1.997425 54.3527 + 76 0.0000 2.040879 55.5351 + 77 0.0000 2.131509 58.0013 + 78 0.0000 2.145733 58.3884 + 79 0.0000 2.178031 59.2672 + 80 0.0000 2.286935 62.2307 + 81 0.0000 2.330541 63.4172 + 82 0.0000 2.344308 63.7919 + 83 0.0000 2.386414 64.9376 + 84 0.0000 2.435723 66.2794 + 85 0.0000 2.458040 66.8867 + 86 0.0000 2.476341 67.3847 + 87 0.0000 2.506398 68.2026 + 88 0.0000 2.516679 68.4823 + 89 0.0000 2.561525 69.7026 + 90 0.0000 2.575940 70.0949 + 91 0.0000 2.650479 72.1232 + 92 0.0000 2.651915 72.1623 + 93 0.0000 2.694417 73.3188 + 94 0.0000 2.756962 75.0207 + 95 0.0000 2.784554 75.7716 + 96 0.0000 2.917919 79.4006 + 97 0.0000 2.959622 80.5354 + 98 0.0000 2.981056 81.1187 + 99 0.0000 3.068164 83.4890 + 100 0.0000 3.145448 85.5920 + 101 0.0000 3.149532 85.7031 + 102 0.0000 3.217708 87.5583 + 103 0.0000 3.515159 95.6523 + 104 0.0000 3.761306 102.3503 + 105 0.0000 3.836376 104.3931 + 106 0.0000 4.025352 109.5354 + 107 0.0000 4.154511 113.0500 + 108 0.0000 4.173237 113.5596 + 109 0.0000 4.240864 115.3998 + 110 0.0000 4.359941 118.6400 + 111 0.0000 4.406017 119.8938 + 112 0.0000 4.521632 123.0399 + 113 0.0000 4.569871 124.3525 + 114 0.0000 4.702255 127.9549 + 115 0.0000 4.849408 131.9591 + 116 0.0000 4.890958 133.0897 + 117 0.0000 4.893542 133.1600 + 118 0.0000 4.948327 134.6508 + 119 0.0000 4.999090 136.0322 + 120 0.0000 5.065082 137.8279 + 121 0.0000 5.105476 138.9271 + 122 0.0000 5.202627 141.5707 + 123 0.0000 5.218448 142.0012 + 124 0.0000 5.231617 142.3595 + 125 0.0000 5.303767 144.3228 + 126 0.0000 5.391129 146.7001 + 127 0.0000 5.485523 149.2687 + 128 0.0000 5.555910 151.1840 + 129 0.0000 5.659927 154.0144 + 130 0.0000 5.790505 157.5677 + 131 0.0000 5.920075 161.0934 + 132 0.0000 6.187205 168.3624 + 133 0.0000 6.423176 174.7835 + 134 0.0000 6.520159 177.4226 + 135 0.0000 6.570508 178.7926 + 136 0.0000 6.674763 181.6295 + 137 0.0000 6.699455 182.3014 + 138 0.0000 6.764345 184.0672 + 139 0.0000 6.835615 186.0066 + 140 0.0000 6.955449 189.2674 + 141 0.0000 7.103012 193.2828 + 142 0.0000 7.115808 193.6310 + 143 0.0000 7.161359 194.8705 + 144 0.0000 7.163129 194.9186 + 145 0.0000 7.228811 196.7059 + 146 0.0000 7.291783 198.4195 + 147 0.0000 7.317796 199.1273 + 148 0.0000 7.415614 201.7891 + 149 0.0000 7.422361 201.9727 + 150 0.0000 7.466079 203.1623 + 151 0.0000 7.495566 203.9647 + 152 0.0000 7.614161 207.1918 + 153 0.0000 7.696464 209.4314 + 154 0.0000 7.861724 213.9284 + 155 0.0000 7.950560 216.3457 + 156 0.0000 8.299300 225.8354 + 157 0.0000 8.326174 226.5667 + 158 0.0000 14.229212 387.1966 + 159 0.0000 15.097127 410.8137 + 160 0.0000 15.629487 425.3000 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.665291 -562.3312 + 1 1.0000 -20.652017 -561.9700 + 2 1.0000 -15.802775 -430.0154 + 3 1.0000 -1.608825 -43.7784 + 4 1.0000 -1.408561 -38.3289 + 5 1.0000 -0.967726 -26.3332 + 6 1.0000 -0.776705 -21.1352 + 7 1.0000 -0.744306 -20.2536 + 8 1.0000 -0.689475 -18.7616 + 9 1.0000 -0.614702 -16.7269 + 10 1.0000 -0.533041 -14.5048 + 11 1.0000 -0.475504 -12.9391 + 12 0.0000 0.031754 0.8641 + 13 0.0000 0.078081 2.1247 + 14 0.0000 0.095241 2.5916 + 15 0.0000 0.113121 3.0782 + 16 0.0000 0.130249 3.5443 + 17 0.0000 0.136613 3.7174 + 18 0.0000 0.157842 4.2951 + 19 0.0000 0.169284 4.6065 + 20 0.0000 0.184696 5.0258 + 21 0.0000 0.195373 5.3164 + 22 0.0000 0.205943 5.6040 + 23 0.0000 0.232537 6.3276 + 24 0.0000 0.250097 6.8055 + 25 0.0000 0.301824 8.2130 + 26 0.0000 0.314233 8.5507 + 27 0.0000 0.344946 9.3865 + 28 0.0000 0.353017 9.6061 + 29 0.0000 0.400574 10.9002 + 30 0.0000 0.444529 12.0963 + 31 0.0000 0.512395 13.9430 + 32 0.0000 0.515344 14.0232 + 33 0.0000 0.535799 14.5798 + 34 0.0000 0.562388 15.3034 + 35 0.0000 0.617791 16.8109 + 36 0.0000 0.640546 17.4301 + 37 0.0000 0.669465 18.2171 + 38 0.0000 0.682707 18.5774 + 39 0.0000 0.697818 18.9886 + 40 0.0000 0.732051 19.9201 + 41 0.0000 0.757376 20.6092 + 42 0.0000 0.763537 20.7769 + 43 0.0000 0.779945 21.2234 + 44 0.0000 0.799444 21.7540 + 45 0.0000 0.845339 23.0028 + 46 0.0000 0.851692 23.1757 + 47 0.0000 0.870228 23.6801 + 48 0.0000 0.918271 24.9874 + 49 0.0000 0.938368 25.5343 + 50 0.0000 0.953498 25.9460 + 51 0.0000 1.007342 27.4112 + 52 0.0000 1.028948 27.9991 + 53 0.0000 1.076886 29.3035 + 54 0.0000 1.078525 29.3482 + 55 0.0000 1.089942 29.6588 + 56 0.0000 1.179361 32.0921 + 57 0.0000 1.221642 33.2426 + 58 0.0000 1.237724 33.6802 + 59 0.0000 1.260011 34.2866 + 60 0.0000 1.337476 36.3946 + 61 0.0000 1.413759 38.4704 + 62 0.0000 1.464195 39.8428 + 63 0.0000 1.506389 40.9909 + 64 0.0000 1.539729 41.8981 + 65 0.0000 1.556541 42.3556 + 66 0.0000 1.595757 43.4228 + 67 0.0000 1.606993 43.7285 + 68 0.0000 1.657238 45.0957 + 69 0.0000 1.771298 48.1995 + 70 0.0000 1.786668 48.6177 + 71 0.0000 1.822023 49.5798 + 72 0.0000 1.906622 51.8818 + 73 0.0000 1.919668 52.2368 + 74 0.0000 1.988827 54.1187 + 75 0.0000 1.997425 54.3527 + 76 0.0000 2.040879 55.5351 + 77 0.0000 2.131509 58.0013 + 78 0.0000 2.145733 58.3884 + 79 0.0000 2.178031 59.2672 + 80 0.0000 2.286935 62.2307 + 81 0.0000 2.330541 63.4172 + 82 0.0000 2.344308 63.7919 + 83 0.0000 2.386414 64.9376 + 84 0.0000 2.435723 66.2794 + 85 0.0000 2.458040 66.8867 + 86 0.0000 2.476341 67.3847 + 87 0.0000 2.506398 68.2026 + 88 0.0000 2.516679 68.4823 + 89 0.0000 2.561525 69.7026 + 90 0.0000 2.575940 70.0949 + 91 0.0000 2.650479 72.1232 + 92 0.0000 2.651915 72.1623 + 93 0.0000 2.694417 73.3188 + 94 0.0000 2.756962 75.0207 + 95 0.0000 2.784554 75.7716 + 96 0.0000 2.917919 79.4006 + 97 0.0000 2.959622 80.5354 + 98 0.0000 2.981056 81.1187 + 99 0.0000 3.068164 83.4890 + 100 0.0000 3.145448 85.5920 + 101 0.0000 3.149532 85.7031 + 102 0.0000 3.217708 87.5583 + 103 0.0000 3.515159 95.6523 + 104 0.0000 3.761306 102.3503 + 105 0.0000 3.836376 104.3931 + 106 0.0000 4.025352 109.5354 + 107 0.0000 4.154511 113.0500 + 108 0.0000 4.173237 113.5596 + 109 0.0000 4.240864 115.3998 + 110 0.0000 4.359941 118.6400 + 111 0.0000 4.406017 119.8938 + 112 0.0000 4.521632 123.0399 + 113 0.0000 4.569871 124.3525 + 114 0.0000 4.702255 127.9549 + 115 0.0000 4.849408 131.9591 + 116 0.0000 4.890958 133.0897 + 117 0.0000 4.893542 133.1600 + 118 0.0000 4.948327 134.6508 + 119 0.0000 4.999090 136.0322 + 120 0.0000 5.065082 137.8279 + 121 0.0000 5.105476 138.9271 + 122 0.0000 5.202627 141.5707 + 123 0.0000 5.218448 142.0012 + 124 0.0000 5.231617 142.3595 + 125 0.0000 5.303767 144.3228 + 126 0.0000 5.391129 146.7001 + 127 0.0000 5.485523 149.2687 + 128 0.0000 5.555910 151.1840 + 129 0.0000 5.659927 154.0144 + 130 0.0000 5.790505 157.5677 + 131 0.0000 5.920075 161.0934 + 132 0.0000 6.187205 168.3624 + 133 0.0000 6.423176 174.7835 + 134 0.0000 6.520159 177.4226 + 135 0.0000 6.570508 178.7926 + 136 0.0000 6.674763 181.6295 + 137 0.0000 6.699455 182.3014 + 138 0.0000 6.764345 184.0672 + 139 0.0000 6.835615 186.0066 + 140 0.0000 6.955449 189.2674 + 141 0.0000 7.103012 193.2828 + 142 0.0000 7.115808 193.6310 + 143 0.0000 7.161359 194.8705 + 144 0.0000 7.163129 194.9186 + 145 0.0000 7.228811 196.7059 + 146 0.0000 7.291783 198.4195 + 147 0.0000 7.317796 199.1273 + 148 0.0000 7.415614 201.7891 + 149 0.0000 7.422361 201.9727 + 150 0.0000 7.466079 203.1623 + 151 0.0000 7.495566 203.9647 + 152 0.0000 7.614161 207.1918 + 153 0.0000 7.696464 209.4314 + 154 0.0000 7.861724 213.9284 + 155 0.0000 7.950560 216.3457 + 156 0.0000 8.299300 225.8354 + 157 0.0000 8.326174 226.5667 + 158 0.0000 14.229212 387.1966 + 159 0.0000 15.097127 410.8137 + 160 0.0000 15.629487 425.3000 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.275516 0.000000 + 1 N : 0.330813 0.000000 + 2 O : -0.305083 0.000000 + 3 H : 0.249786 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.799528 s : 3.799528 + pz : 1.580155 p : 4.432776 + px : 1.470471 + py : 1.382150 + dz2 : 0.010400 d : 0.037688 + dxz : 0.007587 + dyz : 0.001429 + dx2y2 : 0.016630 + dxy : 0.001641 + f0 : 0.000468 f : 0.005524 + f+1 : 0.001386 + f-1 : 0.000325 + f+2 : 0.000935 + f-2 : 0.001287 + f+3 : 0.000306 + f-3 : 0.000817 + 1 N s : 3.867596 s : 3.867596 + pz : 0.708074 p : 2.623400 + px : 0.723506 + py : 1.191820 + dz2 : 0.031389 d : 0.144828 + dxz : 0.028036 + dyz : 0.024339 + dx2y2 : 0.035645 + dxy : 0.025420 + f0 : 0.002908 f : 0.033362 + f+1 : 0.003199 + f-1 : 0.005431 + f+2 : 0.003088 + f-2 : 0.005638 + f+3 : 0.005290 + f-3 : 0.007808 + 2 O s : 3.855964 s : 3.855964 + pz : 1.455534 p : 4.382339 + px : 1.546862 + py : 1.379944 + dz2 : 0.010893 d : 0.059359 + dxz : 0.002773 + dyz : 0.017493 + dx2y2 : 0.011120 + dxy : 0.017079 + f0 : 0.000376 f : 0.007421 + f+1 : 0.000231 + f-1 : 0.001774 + f+2 : 0.001074 + f-2 : 0.000924 + f+3 : 0.001307 + f-3 : 0.001734 + 3 H s : 0.646916 s : 0.646916 + pz : 0.031609 p : 0.082297 + px : 0.030577 + py : 0.020111 + dz2 : -0.000140 d : 0.021001 + dxz : -0.000931 + dyz : 0.010788 + dx2y2 : 0.000620 + dxy : 0.010664 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.603456 0.000000 + 1 N : -0.285199 0.000000 + 2 O : 0.245579 0.000000 + 3 H : -0.563835 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.105306 s : 3.105306 + pz : 1.328998 p : 3.893769 + px : 1.279114 + py : 1.285657 + dz2 : 0.045948 d : 0.302270 + dxz : 0.087547 + dyz : 0.041876 + dx2y2 : 0.064736 + dxy : 0.062163 + f0 : 0.008688 f : 0.095199 + f+1 : 0.017565 + f-1 : 0.005769 + f+2 : 0.015382 + f-2 : 0.022965 + f+3 : 0.007105 + f-3 : 0.017725 + 1 N s : 2.997915 s : 2.997915 + pz : 0.760846 p : 2.829600 + px : 0.801325 + py : 1.267429 + dz2 : 0.184779 d : 0.982401 + dxz : 0.203657 + dyz : 0.158100 + dx2y2 : 0.248323 + dxy : 0.187542 + f0 : 0.042710 f : 0.475283 + f+1 : 0.052277 + f-1 : 0.061007 + f+2 : 0.063940 + f-2 : 0.086730 + f+3 : 0.071320 + f-3 : 0.097298 + 2 O s : 3.296880 s : 3.296880 + pz : 1.261043 p : 4.023130 + px : 1.324430 + py : 1.437657 + dz2 : 0.045881 d : 0.318792 + dxz : 0.042436 + dyz : 0.057344 + dx2y2 : 0.113764 + dxy : 0.059366 + f0 : 0.008394 f : 0.115619 + f+1 : 0.004844 + f-1 : 0.019957 + f+2 : 0.015472 + f-2 : 0.018837 + f+3 : 0.017758 + f-3 : 0.030357 + 3 H s : 0.608921 s : 0.608921 + pz : 0.139542 p : 0.540959 + px : 0.137794 + py : 0.263624 + dz2 : 0.039214 d : 0.413955 + dxz : 0.029249 + dyz : 0.119297 + dx2y2 : 0.108164 + dxy : 0.118031 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2755 8.0000 -0.2755 1.8043 1.8043 -0.0000 + 1 N 6.6692 7.0000 0.3308 2.4996 2.4996 -0.0000 + 2 O 8.3051 8.0000 -0.3051 1.6597 1.6597 0.0000 + 3 H 0.7502 1.0000 0.2498 1.0144 1.0144 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8256 B( 0-O , 3-H ) : 0.9207 B( 1-N , 2-O ) : 1.5910 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.516 sec +Sum of individual times .... 1.206 sec ( 79.5%) + +Fock matrix formation .... 1.004 sec ( 66.2%) +Diagonalization .... 0.073 sec ( 4.8%) +Density matrix formation .... 0.009 sec ( 0.6%) +Population analysis .... 0.061 sec ( 4.0%) +Initial guess .... 0.013 sec ( 0.9%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.008 sec ( 0.5%) +DIIS solution .... 0.047 sec ( 3.1%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.409 sec +Reference energy ... -204.724364039 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 9.117 sec +AO-integral generation ... 0.183 sec +Half transformation ... 0.104 sec +K-integral sorting ... 6.987 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.059 s ( 0.000 ms/b) + 377910 b 0 skpd 0.048 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.064 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.072 s ( 0.000 ms/b) +: 159120 b 0 skpd 0.032 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.072 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.068 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.037 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.061 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.053 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.663 sec +AO-integral generation ... 0.518 sec +Half transformation ... 0.050 sec +J-integral sorting ... 0.072 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.229 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.382 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090635276 +EMP2(bb)= -0.090635276 +EMP2(ab)= -0.514863700 + +Initial guess performed in 0.201 sec +E(0) ... -204.724364039 +E(MP2) ... -0.696134252 +Initial E(tot) ... -205.420498291 + ... 0.186397358 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.420498291 -0.696134252 -0.000000000 0.031160661 5.59 0.000001002 + *** Turning on DIIS *** + 1 -205.391519141 -0.667155102 0.028979150 0.012493311 4.22 0.058366880 + 2 -205.410911786 -0.686547747 -0.019392645 0.007074930 4.42 0.061625520 + 3 -205.414582126 -0.690218087 -0.003670340 0.002560821 5.02 0.076115904 + 4 -205.416166288 -0.691802249 -0.001584162 0.001556835 5.79 0.083167344 + 5 -205.416710581 -0.692346542 -0.000544293 0.000713982 4.98 0.088624553 + 6 -205.416807447 -0.692443407 -0.000096866 0.000452415 5.10 0.090998636 + 7 -205.416845412 -0.692481373 -0.000037965 0.000202248 4.85 0.091928817 + 8 -205.416853365 -0.692489326 -0.000007953 0.000108918 5.21 0.092252013 + 9 -205.416849665 -0.692485626 0.000003700 0.000028044 5.88 0.092349135 + 10 -205.416853788 -0.692489748 -0.000004122 0.000007854 4.53 0.092383792 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.724364039 +E(CORR) ... -0.692489748 +E(TOT) ... -205.416853788 +Singles norm **1/2 ... 0.092383792 ( 0.046191896, 0.046191896) +T1 diagnostic ... 0.021775069 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.065576 + 10a-> 13a 10b-> 13b 0.058094 + 8a-> 13a -1a-> -1a 0.052973 + 8b-> 13b -1b-> -1b 0.052973 + 8a-> 13a 10b-> 13b 0.037257 + 10a-> 13a 8b-> 13b 0.037257 + 11a-> 13a 11b-> 13b 0.029090 + 10a-> 13a 10b-> 22b 0.026828 + 10a-> 22a 10b-> 13b 0.026828 + 5a-> 13a 5b-> 13b 0.025100 + 8a-> 22a 8b-> 13b 0.025023 + 8a-> 13a 8b-> 22b 0.025023 + 11b-> 26b -1b-> -1b 0.023509 + 11a-> 26a -1a-> -1a 0.023509 + 10a-> 13a -1a-> -1a 0.022834 + 10b-> 13b -1b-> -1b 0.022834 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034629139 + alpha-alpha-alpha ... -0.000913746 ( 2.6%) + alpha-alpha-beta ... -0.016400824 ( 47.4%) + alpha-beta -beta ... -0.016400824 ( 47.4%) + beta -beta -beta ... -0.000913746 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034629139 + +Final correlation energy ... -0.727118888 +E(CCSD) ... -205.416853788 +E(CCSD(T)) ... -205.451482927 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.207382908 sqrt= 1.098809769 +W(HF) = 0.828237664 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.184685 0.000000 + 1 N : 0.137693 -0.000000 + 2 O : -0.184622 0.000000 + 3 H : 0.231614 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.787280 s : 3.787280 + pz : 1.528873 p : 4.321016 + px : 1.434316 + py : 1.357826 + dz2 : 0.017047 d : 0.067231 + dxz : 0.011936 + dyz : 0.008687 + dx2y2 : 0.020291 + dxy : 0.009270 + f0 : 0.001037 f : 0.009158 + f+1 : 0.001838 + f-1 : 0.000970 + f+2 : 0.001281 + f-2 : 0.001705 + f+3 : 0.000917 + f-3 : 0.001410 + 1 N s : 3.917103 s : 3.917103 + pz : 0.800292 p : 2.741343 + px : 0.799084 + py : 1.141968 + dz2 : 0.038225 d : 0.171490 + dxz : 0.034296 + dyz : 0.026932 + dx2y2 : 0.043491 + dxy : 0.028545 + f0 : 0.002969 f : 0.032371 + f+1 : 0.003223 + f-1 : 0.005257 + f+2 : 0.002748 + f-2 : 0.005591 + f+3 : 0.004897 + f-3 : 0.007686 + 2 O s : 3.843729 s : 3.843729 + pz : 1.403032 p : 4.247840 + px : 1.491223 + py : 1.353585 + dz2 : 0.015975 d : 0.082910 + dxz : 0.009501 + dyz : 0.019685 + dx2y2 : 0.018047 + dxy : 0.019701 + f0 : 0.000863 f : 0.010143 + f+1 : 0.000778 + f-1 : 0.002003 + f+2 : 0.001440 + f-2 : 0.001386 + f+3 : 0.001608 + f-3 : 0.002066 + 3 H s : 0.664774 s : 0.664774 + pz : 0.036168 p : 0.083945 + px : 0.034431 + py : 0.013346 + dz2 : -0.000058 d : 0.019667 + dxz : -0.000266 + dyz : 0.009852 + dx2y2 : 0.000177 + dxy : 0.009962 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.619418 -0.000000 + 1 N : -0.334586 0.000000 + 2 O : 0.281459 0.000000 + 3 H : -0.566291 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.114352 s : 3.114352 + pz : 1.297926 p : 3.829591 + px : 1.260221 + py : 1.271444 + dz2 : 0.053795 d : 0.333948 + dxz : 0.093800 + dyz : 0.047312 + dx2y2 : 0.071745 + dxy : 0.067295 + f0 : 0.009880 f : 0.102691 + f+1 : 0.019754 + f-1 : 0.006863 + f+2 : 0.016621 + f-2 : 0.022810 + f+3 : 0.008187 + f-3 : 0.018576 + 1 N s : 3.003440 s : 3.003440 + pz : 0.814598 p : 2.882309 + px : 0.842504 + py : 1.225207 + dz2 : 0.183111 d : 0.985686 + dxz : 0.211477 + dyz : 0.156794 + dx2y2 : 0.248439 + dxy : 0.185865 + f0 : 0.041831 f : 0.463151 + f+1 : 0.048347 + f-1 : 0.059326 + f+2 : 0.063929 + f-2 : 0.084488 + f+3 : 0.071586 + f-3 : 0.093644 + 2 O s : 3.298876 s : 3.298876 + pz : 1.231561 p : 3.941834 + px : 1.291635 + py : 1.418638 + dz2 : 0.054466 d : 0.353172 + dxz : 0.047553 + dyz : 0.065794 + dx2y2 : 0.118101 + dxy : 0.067259 + f0 : 0.009232 f : 0.124660 + f+1 : 0.006135 + f-1 : 0.022323 + f+2 : 0.017370 + f-2 : 0.019258 + f+3 : 0.019582 + f-3 : 0.030759 + 3 H s : 0.614761 s : 0.614761 + pz : 0.141246 p : 0.548105 + px : 0.139190 + py : 0.267669 + dz2 : 0.038912 d : 0.403424 + dxz : 0.029277 + dyz : 0.114042 + dx2y2 : 0.107524 + dxy : 0.113670 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.1847 8.0000 -0.1847 2.1815 1.7332 0.4483 + 1 N 6.8623 7.0000 0.1377 2.7902 2.3226 0.4675 + 2 O 8.1846 8.0000 -0.1846 2.0699 1.5726 0.4973 + 3 H 0.7684 1.0000 0.2316 1.0349 0.9610 0.0739 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7857 B( 0-O , 2-O ) : 0.1004 B( 0-O , 3-H ) : 0.8471 +B( 1-N , 2-O ) : 1.4476 + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 81.580 sec + +Fock Matrix Formation ... 0.409 sec ( 0.5%) +Initial Guess ... 0.201 sec ( 0.2%) +DIIS Solver ... 3.375 sec ( 4.1%) +State Vector Update ... 0.190 sec ( 0.2%) +Sigma-vector construction ... 52.020 sec ( 63.8%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (0-ext) ... 0.073 sec ( 0.1% of sigma) + (2-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (2-ext) ... 0.976 sec ( 1.9% of sigma) + (4-ext) ... 30.622 sec ( 58.9% of sigma) + ... 2.524 sec ( 4.9% of sigma) + ... 0.003 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.136 sec ( 0.3% of sigma) + Fock-dressing ... 3.012 sec ( 5.8% of sigma) + (ik|jl)-dressing ... 0.086 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 11.849 sec ( 22.8% of sigma) + Pair energies ... 0.016 sec ( 0.0% of sigma) +Total Time for computing (T) ... 13.680 sec ( 16.8% of ALL) + I/O of integral and amplitudes ... 1.847 sec ( 13.5% of (T)) + External N**7 contributions ... 5.516 sec ( 40.3% of (T)) + Internal N**7 contributions ... 0.568 sec ( 4.2% of (T)) + N**6 triples energy contributions ... 2.589 sec ( 18.9% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.451482926914 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.023.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.023.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.396576, -0.305990 -0.320281) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.60754 -0.26733 -0.50179 +Nuclear contribution : -0.86993 0.70611 0.70065 + ----------------------------------------- +Total Dipole Moment : -0.26239 0.43878 0.19886 + ----------------------------------------- +Magnitude (a.u.) : 0.54856 +Magnitude (Debye) : 1.39433 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.782206 0.440332 0.380164 +Rotational constants in MHz : 83408.449654 13200.823155 11397.044627 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.176263 0.519471 -0.000000 +x,y,z [Debye]: -0.448024 1.320390 -0.000000 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.396576, -0.305990 -0.320281) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.63734 -0.18397 -0.53172 +Nuclear contribution : -0.86993 0.70611 0.70065 + ----------------------------------------- +Total Dipole Moment : -0.23260 0.52214 0.16893 + ----------------------------------------- +Magnitude (a.u.) : 0.59604 +Magnitude (Debye) : 1.51501 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.782206 0.440332 0.380164 +Rotational constants in MHz : 83408.449654 13200.823155 11397.044627 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.110367 0.585733 0.000000 +x,y,z [Debye]: -0.280531 1.488815 0.000000 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 24 * + * * + * Dihedral ( 2, 1, 0, 3) : 8.18181818 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0309098609 RMS(Int)= 0.0004045551 + Iter 1: RMS(Cart)= 0.0000875684 RMS(Int)= 0.0000034375 + Iter 2: RMS(Cart)= 0.0000007441 RMS(Int)= 0.0000000293 + Iter 3: RMS(Cart)= 0.0000000063 RMS(Int)= 0.0000000002 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.3974 0.000000 + 2. B(O 2,N 1) 1.1883 0.000000 + 3. B(H 3,O 0) 0.9801 0.000000 + 4. A(N 1,O 0,H 3) 104.4180 0.000000 + 5. A(O 0,N 1,O 2) 113.0338 0.000000 + 6. D(O 2,N 1,O 0,H 3) 8.1818 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.594353 -0.383368 0.572439 + N 0.418662 -0.604586 -0.364363 + O 0.907608 0.400993 -0.766665 + H -0.731916 0.586962 0.558589 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.123164 -0.724461 1.081754 + 1 N 7.0000 0 14.007 0.791156 -1.142502 -0.688546 + 2 O 8.0000 0 15.999 1.715130 0.757767 -1.448787 + 3 H 1.0000 0 1.008 -1.383120 1.109197 1.055580 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.395806464753 0.00000000 0.00000000 + O 2 1 0 1.187160635644 113.21728847 0.00000000 + H 1 2 3 0.978366128175 104.63159938 0.00000000 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.637691954341 0.00000000 0.00000000 + O 2 1 0 2.243408478339 113.21728847 0.00000000 + H 1 2 3 1.848844040956 104.63159938 0.00000000 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2245 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2720 + la=0 lb=0: 557 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.098707151921 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 70.0987071519 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.436e-04 +Time for diagonalization ... 0.004 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.003 sec +Total time needed ... 0.008 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7196351830 0.000000000000 0.00175262 0.00005579 0.0111689 0.7000 + 1 -204.7203659673 -0.000730784329 0.00155735 0.00005134 0.0093827 0.7000 + ***Turning on DIIS*** + 2 -204.7210045292 -0.000638561951 0.00412502 0.00014067 0.0077479 0.0000 + 3 -204.7242207124 -0.003216183128 0.00198720 0.00006163 0.0036617 0.0000 + 4 -204.7223843261 0.001836386293 0.00092868 0.00003092 0.0016256 0.0000 + 5 -204.7242927807 -0.001908454647 0.00085015 0.00003580 0.0008831 0.0000 + 6 -204.7233729305 0.000919850205 0.00051281 0.00002428 0.0005011 0.0000 + 7 -204.7232024048 0.000170525689 0.00030917 0.00001515 0.0002872 0.0000 + 8 -204.7240079564 -0.000805551524 0.00019524 0.00000844 0.0001585 0.0000 + 9 -204.7234713831 0.000536573286 0.00008544 0.00000265 0.0000726 0.0000 + 10 -204.7235126607 -0.000041277592 0.00003218 0.00000084 0.0000415 0.0000 + 11 -204.7236241473 -0.000111486591 0.00001967 0.00000049 0.0000199 0.0000 + 12 -204.7235635865 0.000060560759 0.00000646 0.00000016 0.0000060 0.0000 + 13 -204.7235799379 -0.000016351362 0.00000203 0.00000006 0.0000021 0.0000 + 14 -204.7235747419 0.000005195995 0.00000082 0.00000003 0.0000010 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 15 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72357507 Eh -5570.81169 eV + +Components: +Nuclear Repulsion : 70.09870715 Eh 1907.48280 eV +Electronic Energy : -274.82228222 Eh -7478.29449 eV +One Electron Energy: -419.77475713 Eh -11422.65186 eV +Two Electron Energy: 144.95247491 Eh 3944.35737 eV + +Virial components: +Potential Energy : -408.96480186 Eh -11128.49802 eV +Kinetic Energy : 204.24122679 Eh 5557.68633 eV +Virial Ratio : 2.00236166 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -3.2763e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.7770e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.0608e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.8804e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.665656 -562.3411 + 1 1.0000 -20.651786 -561.9637 + 2 1.0000 -15.803079 -430.0236 + 3 1.0000 -1.607873 -43.7524 + 4 1.0000 -1.407480 -38.2995 + 5 1.0000 -0.967360 -26.3232 + 6 1.0000 -0.775898 -21.1132 + 7 1.0000 -0.743771 -20.2390 + 8 1.0000 -0.689389 -18.7592 + 9 1.0000 -0.614035 -16.7088 + 10 1.0000 -0.532875 -14.5003 + 11 1.0000 -0.475706 -12.9446 + 12 0.0000 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1.028001 27.9733 + 53 0.0000 1.072066 29.1724 + 54 0.0000 1.082083 29.4450 + 55 0.0000 1.088714 29.6254 + 56 0.0000 1.179396 32.0930 + 57 0.0000 1.214673 33.0529 + 58 0.0000 1.239663 33.7329 + 59 0.0000 1.265447 34.4346 + 60 0.0000 1.339403 36.4470 + 61 0.0000 1.412991 38.4494 + 62 0.0000 1.459761 39.7221 + 63 0.0000 1.503129 40.9022 + 64 0.0000 1.540909 41.9303 + 65 0.0000 1.556784 42.3622 + 66 0.0000 1.591406 43.3044 + 67 0.0000 1.612220 43.8707 + 68 0.0000 1.657266 45.0965 + 69 0.0000 1.764299 48.0090 + 70 0.0000 1.788702 48.6731 + 71 0.0000 1.822798 49.6009 + 72 0.0000 1.904943 51.8361 + 73 0.0000 1.922589 52.3163 + 74 0.0000 1.990092 54.1532 + 75 0.0000 2.000657 54.4406 + 76 0.0000 2.039126 55.4874 + 77 0.0000 2.123857 57.7931 + 78 0.0000 2.151850 58.5548 + 79 0.0000 2.178131 59.2700 + 80 0.0000 2.287044 62.2336 + 81 0.0000 2.319436 63.1151 + 82 0.0000 2.352492 64.0146 + 83 0.0000 2.385797 64.9208 + 84 0.0000 2.435713 66.2791 + 85 0.0000 2.454356 66.7864 + 86 0.0000 2.473471 67.3066 + 87 0.0000 2.511768 68.3487 + 88 0.0000 2.520548 68.5876 + 89 0.0000 2.559476 69.6469 + 90 0.0000 2.575915 70.0942 + 91 0.0000 2.639009 71.8111 + 92 0.0000 2.661851 72.4327 + 93 0.0000 2.693720 73.2998 + 94 0.0000 2.743901 74.6653 + 95 0.0000 2.793063 76.0031 + 96 0.0000 2.905336 79.0582 + 97 0.0000 2.964451 80.6668 + 98 0.0000 2.981652 81.1349 + 99 0.0000 3.066892 83.4544 + 100 0.0000 3.145516 85.5938 + 101 0.0000 3.150228 85.7221 + 102 0.0000 3.216856 87.5351 + 103 0.0000 3.513233 95.5999 + 104 0.0000 3.749846 102.0385 + 105 0.0000 3.843985 104.6001 + 106 0.0000 4.023617 109.4882 + 107 0.0000 4.150290 112.9351 + 108 0.0000 4.171349 113.5082 + 109 0.0000 4.244024 115.4858 + 110 0.0000 4.358134 118.5909 + 111 0.0000 4.410147 120.0062 + 112 0.0000 4.519484 122.9814 + 113 0.0000 4.566358 124.2569 + 114 0.0000 4.698229 127.8453 + 115 0.0000 4.841065 131.7321 + 116 0.0000 4.885825 132.9501 + 117 0.0000 4.898695 133.3003 + 118 0.0000 4.944841 134.5560 + 119 0.0000 4.999821 136.0520 + 120 0.0000 5.064127 137.8019 + 121 0.0000 5.106488 138.9546 + 122 0.0000 5.198044 141.4460 + 123 0.0000 5.216366 141.9445 + 124 0.0000 5.230494 142.3290 + 125 0.0000 5.302446 144.2869 + 126 0.0000 5.388966 146.6412 + 127 0.0000 5.483815 149.2222 + 128 0.0000 5.553487 151.1181 + 129 0.0000 5.661649 154.0613 + 130 0.0000 5.789611 157.5433 + 131 0.0000 5.918982 161.0637 + 132 0.0000 6.188334 168.3931 + 133 0.0000 6.420351 174.7066 + 134 0.0000 6.519633 177.4082 + 135 0.0000 6.567884 178.7212 + 136 0.0000 6.677354 181.7000 + 137 0.0000 6.702202 182.3762 + 138 0.0000 6.764943 184.0835 + 139 0.0000 6.833596 185.9516 + 140 0.0000 6.950902 189.1436 + 141 0.0000 7.097983 193.1459 + 142 0.0000 7.122153 193.8036 + 143 0.0000 7.152976 194.6424 + 144 0.0000 7.166201 195.0022 + 145 0.0000 7.230210 196.7440 + 146 0.0000 7.286415 198.2734 + 147 0.0000 7.312951 198.9955 + 148 0.0000 7.406163 201.5320 + 149 0.0000 7.431180 202.2127 + 150 0.0000 7.464961 203.1319 + 151 0.0000 7.496873 204.0003 + 152 0.0000 7.612392 207.1437 + 153 0.0000 7.690729 209.2754 + 154 0.0000 7.858237 213.8335 + 155 0.0000 7.939991 216.0581 + 156 0.0000 8.300619 225.8713 + 157 0.0000 8.312075 226.1831 + 158 0.0000 14.204114 386.5136 + 159 0.0000 15.072280 410.1376 + 160 0.0000 15.590512 424.2394 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.279556 0.000000 + 1 N : 0.332114 0.000000 + 2 O : -0.305222 0.000000 + 3 H : 0.252664 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.801915 s : 3.801915 + pz : 1.544521 p : 4.434628 + px : 1.503482 + py : 1.386625 + dz2 : 0.010366 d : 0.037491 + dxz : 0.007624 + dyz : 0.002154 + dx2y2 : 0.016292 + dxy : 0.001055 + f0 : 0.000560 f : 0.005523 + f+1 : 0.001373 + f-1 : 0.000350 + f+2 : 0.001001 + f-2 : 0.001298 + f+3 : 0.000208 + f-3 : 0.000733 + 1 N s : 3.866137 s : 3.866137 + pz : 0.708842 p : 2.623641 + px : 0.723639 + py : 1.191160 + dz2 : 0.031543 d : 0.144766 + dxz : 0.028161 + dyz : 0.023215 + dx2y2 : 0.034981 + dxy : 0.026866 + f0 : 0.003793 f : 0.033342 + f+1 : 0.002699 + f-1 : 0.005317 + f+2 : 0.003134 + f-2 : 0.005715 + f+3 : 0.004854 + f-3 : 0.007832 + 2 O s : 3.856945 s : 3.856945 + pz : 1.496624 p : 4.381659 + px : 1.505547 + py : 1.379488 + dz2 : 0.009774 d : 0.059204 + dxz : 0.002793 + dyz : 0.018008 + dx2y2 : 0.011976 + dxy : 0.016653 + f0 : 0.000455 f : 0.007413 + f+1 : 0.000278 + f-1 : 0.001660 + f+2 : 0.000948 + f-2 : 0.000937 + f+3 : 0.001307 + f-3 : 0.001827 + 3 H s : 0.644619 s : 0.644619 + pz : 0.029644 p : 0.081960 + px : 0.031857 + py : 0.020459 + dz2 : -0.000080 d : 0.020757 + dxz : -0.000856 + dyz : 0.010695 + dx2y2 : 0.000908 + dxy : 0.010091 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.600764 0.000000 + 1 N : -0.283854 0.000000 + 2 O : 0.244879 0.000000 + 3 H : -0.561789 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.106879 s : 3.106879 + pz : 1.318902 p : 3.895729 + px : 1.290071 + py : 1.286757 + dz2 : 0.048328 d : 0.301693 + dxz : 0.088732 + dyz : 0.045181 + dx2y2 : 0.060214 + dxy : 0.059238 + f0 : 0.008845 f : 0.094936 + f+1 : 0.018142 + f-1 : 0.007367 + f+2 : 0.015422 + f-2 : 0.023602 + f+3 : 0.006568 + f-3 : 0.014989 + 1 N s : 2.999294 s : 2.999294 + pz : 0.767369 p : 2.829470 + px : 0.793765 + py : 1.268336 + dz2 : 0.188096 d : 0.980201 + dxz : 0.203193 + dyz : 0.157841 + dx2y2 : 0.243775 + dxy : 0.187297 + f0 : 0.049580 f : 0.474888 + f+1 : 0.051455 + f-1 : 0.061354 + f+2 : 0.059899 + f-2 : 0.087467 + f+3 : 0.068932 + f-3 : 0.096202 + 2 O s : 3.297763 s : 3.297763 + pz : 1.280640 p : 4.023251 + px : 1.304683 + py : 1.437928 + dz2 : 0.047170 d : 0.318661 + dxz : 0.042303 + dyz : 0.053278 + dx2y2 : 0.112624 + dxy : 0.063286 + f0 : 0.008422 f : 0.115446 + f+1 : 0.005217 + f-1 : 0.020266 + f+2 : 0.013036 + f-2 : 0.018808 + f+3 : 0.019621 + f-3 : 0.030077 + 3 H s : 0.608127 s : 0.608127 + pz : 0.138419 p : 0.540137 + px : 0.139497 + py : 0.262221 + dz2 : 0.038446 d : 0.413525 + dxz : 0.030171 + dyz : 0.118705 + dx2y2 : 0.109202 + dxy : 0.117002 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2796 8.0000 -0.2796 1.8045 1.8045 0.0000 + 1 N 6.6679 7.0000 0.3321 2.5030 2.5030 0.0000 + 2 O 8.3052 8.0000 -0.3052 1.6631 1.6631 0.0000 + 3 H 0.7473 1.0000 0.2527 1.0116 1.0116 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8268 B( 0-O , 3-H ) : 0.9197 B( 1-N , 2-O ) : 1.5948 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 4 sec + +Total time .... 4.291 sec +Sum of individual times .... 3.960 sec ( 92.3%) + +Fock matrix formation .... 3.456 sec ( 80.5%) +Diagonalization .... 0.223 sec ( 5.2%) +Density matrix formation .... 0.018 sec ( 0.4%) +Population analysis .... 0.061 sec ( 1.4%) +Initial guess .... 0.013 sec ( 0.3%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.007 sec ( 0.2%) +DIIS solution .... 0.189 sec ( 4.4%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.430 sec +Reference energy ... -204.723574587 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 8.141 sec +AO-integral generation ... 0.197 sec +Half transformation ... 0.110 sec +K-integral sorting ... 6.534 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: + 251940 b 0 skpd 0.031 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.036 s ( 0.000 ms/b) +: : 277134 b 0 skpd 0.045 s ( 0.000 ms/b) + 151164 b 0 skpd 0.077 s ( 0.001 ms/b) +: 159120 b 0 skpd 0.023 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.073 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.043 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.034 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.054 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.051 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.559 sec +AO-integral generation ... 0.409 sec +Half transformation ... 0.059 sec +J-integral sorting ... 0.070 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.258 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.313 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090667980 +EMP2(bb)= -0.090667980 +EMP2(ab)= -0.515143874 + +Initial guess performed in 0.175 sec +E(0) ... -204.723574587 +E(MP2) ... -0.696479834 +Initial E(tot) ... -205.420054421 + ... 0.186723826 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.420054421 -0.696479834 -0.000000000 0.030936016 4.56 0.000002272 + *** Turning on DIIS *** + 1 -205.390961538 -0.667386951 0.029092883 0.012374625 4.89 0.058437678 + 2 -205.410402332 -0.686827745 -0.019440793 0.007027276 4.02 0.061694330 + 3 -205.414086015 -0.690511428 -0.003683683 0.002541016 4.44 0.076216320 + 4 -205.415676032 -0.692101445 -0.001590018 0.001548231 5.15 0.083285560 + 5 -205.416223645 -0.692649058 -0.000547613 0.000722577 5.18 0.088771598 + 6 -205.416321439 -0.692746852 -0.000097794 0.000458663 4.48 0.091170190 + 7 -205.416359928 -0.692785341 -0.000038489 0.000206067 4.11 0.092118549 + 8 -205.416368105 -0.692793518 -0.000008177 0.000110556 3.84 0.092452009 + 9 -205.416364356 -0.692789769 0.000003749 0.000028277 4.41 0.092552832 + 10 -205.416368577 -0.692793990 -0.000004221 0.000007628 4.23 0.092589015 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.723574587 +E(CORR) ... -0.692793990 +E(TOT) ... -205.416368577 +Singles norm **1/2 ... 0.092589015 ( 0.046294508, 0.046294508) +T1 diagnostic ... 0.021823440 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.064926 + 10a-> 13a 10b-> 13b 0.057489 + 8b-> 13b -1b-> -1b 0.052656 + 8a-> 13a -1a-> -1a 0.052656 + 8a-> 13a 10b-> 13b 0.036887 + 10a-> 13a 8b-> 13b 0.036887 + 11a-> 13a 11b-> 13b 0.029102 + 10a-> 13a 10b-> 22b 0.026406 + 10a-> 22a 10b-> 13b 0.026406 + 5a-> 13a 5b-> 13b 0.025256 + 8a-> 22a 8b-> 13b 0.024647 + 8a-> 13a 8b-> 22b 0.024647 + 11b-> 26b -1b-> -1b 0.023534 + 11a-> 26a -1a-> -1a 0.023534 + 10a-> 13a -1a-> -1a 0.022994 + 10b-> 13b -1b-> -1b 0.022994 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034685870 + alpha-alpha-alpha ... -0.000914076 ( 2.6%) + alpha-alpha-beta ... -0.016428859 ( 47.4%) + alpha-beta -beta ... -0.016428859 ( 47.4%) + beta -beta -beta ... -0.000914076 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034685870 + +Final correlation energy ... -0.727479860 +E(CCSD) ... -205.416368577 +E(CCSD(T)) ... -205.451054446 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.207820933 sqrt= 1.099009069 +W(HF) = 0.827937298 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.188607 -0.000000 + 1 N : 0.138837 -0.000000 + 2 O : -0.184346 0.000000 + 3 H : 0.234116 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.789217 s : 3.789217 + pz : 1.496959 p : 4.323179 + px : 1.464370 + py : 1.361851 + dz2 : 0.017009 d : 0.067054 + dxz : 0.011888 + dyz : 0.009382 + dx2y2 : 0.020137 + dxy : 0.008637 + f0 : 0.001150 f : 0.009157 + f+1 : 0.001771 + f-1 : 0.000992 + f+2 : 0.001357 + f-2 : 0.001712 + f+3 : 0.000838 + f-3 : 0.001338 + 1 N s : 3.915899 s : 3.915899 + pz : 0.796629 p : 2.741376 + px : 0.803688 + py : 1.141059 + dz2 : 0.038671 d : 0.171516 + dxz : 0.034296 + dyz : 0.026099 + dx2y2 : 0.042699 + dxy : 0.029751 + f0 : 0.003716 f : 0.032373 + f+1 : 0.002744 + f-1 : 0.005266 + f+2 : 0.002809 + f-2 : 0.005661 + f+3 : 0.004557 + f-3 : 0.007619 + 2 O s : 3.844583 s : 3.844583 + pz : 1.441069 p : 4.246899 + px : 1.452595 + py : 1.353235 + dz2 : 0.015011 d : 0.082731 + dxz : 0.009517 + dyz : 0.020413 + dx2y2 : 0.018760 + dxy : 0.019029 + f0 : 0.000934 f : 0.010132 + f+1 : 0.000816 + f-1 : 0.001931 + f+2 : 0.001337 + f-2 : 0.001394 + f+3 : 0.001601 + f-3 : 0.002119 + 3 H s : 0.662692 s : 0.662692 + pz : 0.034112 p : 0.083753 + px : 0.035782 + py : 0.013858 + dz2 : -0.000027 d : 0.019439 + dxz : -0.000203 + dyz : 0.009776 + dx2y2 : 0.000452 + dxy : 0.009441 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.616736 0.000000 + 1 N : -0.333346 0.000000 + 2 O : 0.280961 0.000000 + 3 H : -0.564351 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.115859 s : 3.115859 + pz : 1.290294 p : 3.831600 + px : 1.269023 + py : 1.272283 + dz2 : 0.056261 d : 0.333377 + dxz : 0.094906 + dyz : 0.050385 + dx2y2 : 0.067146 + dxy : 0.064677 + f0 : 0.010292 f : 0.102428 + f+1 : 0.020187 + f-1 : 0.008370 + f+2 : 0.016655 + f-2 : 0.023403 + f+3 : 0.007551 + f-3 : 0.015968 + 1 N s : 3.004805 s : 3.004805 + pz : 0.817457 p : 2.882166 + px : 0.838830 + py : 1.225880 + dz2 : 0.187110 d : 0.983560 + dxz : 0.211155 + dyz : 0.155100 + dx2y2 : 0.243219 + dxy : 0.186976 + f0 : 0.047931 f : 0.462815 + f+1 : 0.048424 + f-1 : 0.059850 + f+2 : 0.059706 + f-2 : 0.085213 + f+3 : 0.069299 + f-3 : 0.092392 + 2 O s : 3.299761 s : 3.299761 + pz : 1.249234 p : 3.941792 + px : 1.273561 + py : 1.418997 + dz2 : 0.055178 d : 0.353005 + dxz : 0.047469 + dyz : 0.061871 + dx2y2 : 0.117468 + dxy : 0.071019 + f0 : 0.009350 f : 0.124482 + f+1 : 0.006549 + f-1 : 0.022037 + f+2 : 0.015084 + f-2 : 0.019256 + f+3 : 0.021191 + f-3 : 0.031016 + 3 H s : 0.613980 s : 0.613980 + pz : 0.139901 p : 0.547389 + px : 0.141172 + py : 0.266316 + dz2 : 0.038108 d : 0.402981 + dxz : 0.030091 + dyz : 0.113751 + dx2y2 : 0.108426 + dxy : 0.112605 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.1886 8.0000 -0.1886 2.1822 1.7332 0.4489 + 1 N 6.8612 7.0000 0.1388 2.7933 2.3246 0.4687 + 2 O 8.1843 8.0000 -0.1843 2.0732 1.5751 0.4981 + 3 H 0.7659 1.0000 0.2341 1.0326 0.9587 0.0740 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7863 B( 0-O , 2-O ) : 0.1003 B( 0-O , 3-H ) : 0.8467 +B( 1-N , 2-O ) : 1.4506 + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 74.178 sec + +Fock Matrix Formation ... 0.430 sec ( 0.6%) +Initial Guess ... 0.175 sec ( 0.2%) +DIIS Solver ... 2.499 sec ( 3.4%) +State Vector Update ... 0.136 sec ( 0.2%) +Sigma-vector construction ... 46.678 sec ( 62.9%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (0-ext) ... 0.073 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (2-ext) ... 0.962 sec ( 2.1% of sigma) + (4-ext) ... 26.978 sec ( 57.8% of sigma) + ... 1.992 sec ( 4.3% of sigma) + ... 0.003 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.125 sec ( 0.3% of sigma) + Fock-dressing ... 2.767 sec ( 5.9% of sigma) + (ik|jl)-dressing ... 0.083 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 11.167 sec ( 23.9% of sigma) + Pair energies ... 0.013 sec ( 0.0% of sigma) +Total Time for computing (T) ... 13.626 sec ( 18.4% of ALL) + I/O of integral and amplitudes ... 1.220 sec ( 9.0% of (T)) + External N**7 contributions ... 5.289 sec ( 38.8% of (T)) + Internal N**7 contributions ... 0.428 sec ( 3.1% of (T)) + N**6 triples energy contributions ... 2.123 sec ( 15.6% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.451054446436 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.003273971 -0.001152522 0.003764528 + 2 N : -0.003348092 -0.002132627 -0.002952230 + 3 O : 0.002307634 0.001826543 0.001802749 + 4 H : -0.002233513 0.001458607 -0.002615047 + +Norm of the cartesian gradient ... 0.008749758 +RMS gradient ... 0.002525838 +MAX gradient ... 0.003764528 + +------- +TIMINGS +------- + +Total numerical gradient time ... 419.368 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 615.52 cm**-1 + 7: 684.20 cm**-1 + 8: 876.91 cm**-1 + 9: 1341.40 cm**-1 + 10: 1651.60 cm**-1 + 11: 3571.78 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 0.132147 0.129179 0.216888 0.046636 -0.011093 -0.007914 + 1 0.065490 0.049912 -0.143069 0.076572 0.068936 0.060851 + 2 -0.206061 0.004400 -0.181281 -0.052504 0.005986 -0.001620 + 3 -0.022028 -0.069472 -0.360359 0.072183 -0.120508 -0.002269 + 4 -0.103587 -0.057607 0.233706 -0.006625 -0.492255 0.001279 + 5 0.109680 -0.063938 0.312077 -0.054158 0.094737 0.001996 + 6 -0.169416 -0.038580 0.140388 -0.066148 0.150841 0.000394 + 7 0.013172 0.003332 -0.046583 -0.068380 0.362789 0.000191 + 8 0.098817 0.105430 -0.110573 0.055967 -0.121338 -0.000358 + 9 0.897632 -0.472616 -0.663206 -0.693353 -0.543528 0.150879 + 10 0.190901 -0.044601 -0.237382 -0.037958 -0.012052 -0.986632 + 11 0.178090 -0.854751 0.295740 0.697607 0.514409 0.003656 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 615.52 0.010070 50.89 0.005105 (-0.003419 -0.021620 0.068017) + 7: 684.20 0.014283 72.18 0.006514 (-0.055297 -0.017967 -0.055979) + 8: 876.91 0.056108 283.55 0.019967 (-0.110922 -0.007073 0.087255) + 9: 1341.40 0.001863 9.42 0.000433 (-0.001171 0.020652 0.002358) + 10: 1651.60 0.028779 145.44 0.005438 (-0.053949 -0.018398 0.046784) + 11: 3571.78 0.006330 31.99 0.000553 ( 0.011968 -0.019095 -0.006721) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 615.52 E(vib) ... 0.10 +freq. 684.20 E(vib) ... 0.07 +freq. 876.91 E(vib) ... 0.04 +freq. 1341.40 E(vib) ... 0.01 +freq. 1651.60 E(vib) ... 0.00 +freq. 3571.78 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.45105445 Eh +Zero point energy ... 0.01991442 Eh 12.50 kcal/mol +Thermal vibrational correction ... 0.00034177 Eh 0.21 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42796571 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00317431 Eh 1.99 kcal/mol +Non-thermal (ZPE) correction 0.01991442 Eh 12.50 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02308873 Eh 14.49 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42796571 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.42702150 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.766303 0.440141 0.379965 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00044289 Eh 0.28 kcal/mol +Rotational entropy ... 0.00987471 Eh 6.20 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02811992 Eh 17.65 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00987471 Eh 6.20 kcal/mol| +| sn= 2 | S(rot)= 0.00922025 Eh 5.79 kcal/mol| +| sn= 3 | S(rot)= 0.00883742 Eh 5.55 kcal/mol| +| sn= 4 | S(rot)= 0.00856580 Eh 5.38 kcal/mol| +| sn= 5 | S(rot)= 0.00835511 Eh 5.24 kcal/mol| +| sn= 6 | S(rot)= 0.00818296 Eh 5.13 kcal/mol| +| sn= 7 | S(rot)= 0.00803742 Eh 5.04 kcal/mol| +| sn= 8 | S(rot)= 0.00791134 Eh 4.96 kcal/mol| +| sn= 9 | S(rot)= 0.00780013 Eh 4.89 kcal/mol| +| sn=10 | S(rot)= 0.00770065 Eh 4.83 kcal/mol| +| sn=11 | S(rot)= 0.00761066 Eh 4.78 kcal/mol| +| sn=12 | S(rot)= 0.00752851 Eh 4.72 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.42702150 Eh +Total entropy correction ... -0.02811992 Eh -17.65 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.45514142 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00408698 Eh -2.56 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.451054445 Eh +Current gradient norm .... 0.008749771 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.040822106 0.150176739 0.215875346 0.459664643 0.538204412 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999972103 +Lowest eigenvalues of augmented Hessian: + -0.000020123 0.149691204 0.215643182 0.459664151 0.538204018 +Length of the computed step .... 0.007469631 +The final length of the internal step .... 0.007469631 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0030494642 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0031644514 RMS(Int)= 0.0030466337 + Iter 1: RMS(Cart)= 0.0000080703 RMS(Int)= 0.0000101831 + Iter 2: RMS(Cart)= 0.0000000229 RMS(Int)= 0.0000000392 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0012321807 0.0001000000 NO + MAX gradient 0.0018852423 0.0003000000 NO + RMS step 0.0030494642 0.0020000000 NO + MAX step 0.0045497048 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0021 Max(Angles) 0.26 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.3974 0.000065 0.0003 1.3977 + 2. B(O 2,N 1) 1.1883 0.001885 -0.0016 1.1867 + 3. B(H 3,O 0) 0.9801 0.001794 -0.0021 0.9780 + 4. A(N 1,O 0,H 3) 104.42 -0.000668 0.26 104.68 + 5. A(O 0,N 1,O 2) 113.03 -0.001373 0.18 113.22 + 6. D(O 2,N 1,O 0,H 3) 8.18 0.005841 -0.00 8.18 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.594284 -0.381924 0.572018 + N 0.419225 -0.603114 -0.364670 + O 0.909879 0.399130 -0.768567 + H -0.734819 0.585908 0.561219 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.123034 -0.721733 1.080957 + 1 N 7.0000 0 14.007 0.792221 -1.139719 -0.689127 + 2 O 8.0000 0 15.999 1.719422 0.754247 -1.452380 + 3 H 1.0000 0 1.008 -1.388607 1.107205 1.060551 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.397680679685 0.00000000 0.00000000 + O 2 1 0 1.186745789432 113.21853318 0.00000000 + H 1 2 3 0.978041859884 104.67868885 8.18181841 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.641233707277 0.00000000 0.00000000 + O 2 1 0 2.242624532611 113.21853318 0.00000000 + H 1 2 3 1.848231262692 104.67868885 8.18181841 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2245 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2720 + la=0 lb=0: 557 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.119181978809 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.434e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7239091131 0.000000000000 0.00015796 0.00000433 0.0006814 0.7000 + 1 -204.7239125267 -0.000003413632 0.00012878 0.00000360 0.0005617 0.7000 + ***Turning on DIIS*** + 2 -204.7239153234 -0.000002796699 0.00031761 0.00000940 0.0004540 0.0000 + 3 -204.7236449088 0.000270414598 0.00008004 0.00000318 0.0001543 0.0000 + 4 -204.7239461120 -0.000301203233 0.00002493 0.00000096 0.0000502 0.0000 + 5 -204.7240482508 -0.000102138734 0.00001193 0.00000034 0.0000246 0.0000 + 6 -204.7238764641 0.000171786675 0.00001154 0.00000020 0.0000129 0.0000 + 7 -204.7239211732 -0.000044709162 0.00000326 0.00000008 0.0000035 0.0000 + 8 -204.7239328891 -0.000011715868 0.00000156 0.00000004 0.0000018 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + +Total Energy : -204.72391851 Eh -5570.82104 eV + Last Energy change ... 1.4375e-05 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.2449e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.213 sec +Reference energy ... -204.723924330 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.348 sec +AO-integral generation ... 0.148 sec +Half transformation ... 0.079 sec +K-integral sorting ... 5.343 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.034 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.038 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.030 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.349 sec +AO-integral generation ... 0.241 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.052 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.157 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.252 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090616766 +EMP2(bb)= -0.090616766 +EMP2(ab)= -0.514888200 + +Initial guess performed in 0.132 sec +E(0) ... -204.723924330 +E(MP2) ... -0.696121732 +Initial E(tot) ... -205.420046062 + ... 0.186433092 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.420046062 -0.696121732 -0.000000000 0.030785107 2.72 0.000002447 + *** Turning on DIIS *** + 1 -205.391098655 -0.667174325 0.028947407 0.012308990 2.71 0.058322236 + 2 -205.410490514 -0.686566184 -0.019391859 0.006983092 2.78 0.061580251 + 3 -205.414164276 -0.690239946 -0.003673763 0.002519258 2.78 0.076066859 + 4 -205.415748288 -0.691823958 -0.001584011 0.001534348 2.85 0.083116502 + 5 -205.416293949 -0.692369619 -0.000545661 0.000725737 2.84 0.088595804 + 6 -205.416391821 -0.692467491 -0.000097872 0.000458683 2.81 0.090999789 + 7 -205.416430319 -0.692505989 -0.000038498 0.000204698 2.89 0.091950386 + 8 -205.416438486 -0.692514156 -0.000008167 0.000109573 2.89 0.092283512 + 9 -205.416434737 -0.692510407 0.000003749 0.000027961 2.87 0.092383397 + 10 -205.416438929 -0.692514599 -0.000004191 0.000007583 2.77 0.092419279 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.723924330 +E(CORR) ... -0.692514599 +E(TOT) ... -205.416438929 +Singles norm **1/2 ... 0.092419279 ( 0.046209639, 0.046209639) +T1 diagnostic ... 0.021783433 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.064968 + 10a-> 13a 10b-> 13b 0.057044 + 8a-> 13a -1a-> -1a 0.052286 + 8b-> 13b -1b-> -1b 0.052286 + 10a-> 13a 8b-> 13b 0.036740 + 8a-> 13a 10b-> 13b 0.036740 + 11a-> 13a 11b-> 13b 0.029170 + 10a-> 13a 10b-> 22b 0.026316 + 10a-> 22a 10b-> 13b 0.026316 + 5a-> 13a 5b-> 13b 0.025168 + 8a-> 13a 8b-> 22b 0.024793 + 8a-> 22a 8b-> 13b 0.024793 + 11a-> 26a -1a-> -1a 0.023509 + 11b-> 26b -1b-> -1b 0.023509 + 10b-> 13b -1b-> -1b 0.023289 + 10a-> 13a -1a-> -1a 0.023289 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034625668 + alpha-alpha-alpha ... -0.000912939 ( 2.6%) + alpha-alpha-beta ... -0.016399895 ( 47.4%) + alpha-beta -beta ... -0.016399895 ( 47.4%) + beta -beta -beta ... -0.000912939 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034625668 + +Final correlation energy ... -0.727140267 +E(CCSD) ... -205.416438929 +E(CCSD(T)) ... -205.451064597 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.207502678 sqrt= 1.098864267 +W(HF) = 0.828155513 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 46.464 sec + +Fock Matrix Formation ... 0.213 sec ( 0.5%) +Initial Guess ... 0.132 sec ( 0.3%) +DIIS Solver ... 1.321 sec ( 2.8%) +State Vector Update ... 0.064 sec ( 0.1%) +Sigma-vector construction ... 29.508 sec ( 63.5%) + <0|H|D> ... 0.003 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.019 sec ( 0.1% of sigma) + (0-ext) ... 0.055 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (2-ext) ... 0.731 sec ( 2.5% of sigma) + (4-ext) ... 16.296 sec ( 55.2% of sigma) + ... 1.065 sec ( 3.6% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.085 sec ( 0.3% of sigma) + Fock-dressing ... 1.623 sec ( 5.5% of sigma) + (ik|jl)-dressing ... 0.058 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 7.519 sec ( 25.5% of sigma) + Pair energies ... 0.004 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.826 sec ( 14.7% of ALL) + I/O of integral and amplitudes ... 0.810 sec ( 11.9% of (T)) + External N**7 contributions ... 3.910 sec ( 57.3% of (T)) + Internal N**7 contributions ... 0.323 sec ( 4.7% of (T)) + N**6 triples energy contributions ... 1.704 sec ( 25.0% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.451064596673 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.003256597 0.000393407 0.003442379 + 2 N : -0.002921758 0.000073757 -0.003190638 + 3 O : 0.001887286 -0.000104391 0.002084588 + 4 H : -0.002222125 -0.000362773 -0.002336329 + +Norm of the cartesian gradient ... 0.007731661 +RMS gradient ... 0.002231938 +MAX gradient ... 0.003442379 + +------- +TIMINGS +------- + +Total numerical gradient time ... 398.748 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.451064597 Eh +Current gradient norm .... 0.007731661 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999995 +Lowest eigenvalues of augmented Hessian: + -0.000000002 0.149333742 0.214463047 0.461593192 0.538278937 +Length of the computed step .... 0.000097447 +The final length of the internal step .... 0.000097447 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0000397825 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0000455748 RMS(Int)= 0.0000397828 + Iter 1: RMS(Cart)= 0.0000000014 RMS(Int)= 0.0000000026 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000101516 0.0000050000 NO + RMS gradient 0.0000124287 0.0001000000 YES + MAX gradient 0.0000169536 0.0003000000 YES + RMS step 0.0000397825 0.0020000000 YES + MAX step 0.0000840490 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0000 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.3977 -0.000004 -0.0000 1.3977 + 2. B(O 2,N 1) 1.1867 -0.000017 0.0000 1.1868 + 3. B(H 3,O 0) 0.9780 -0.000014 0.0000 0.9781 + 4. A(N 1,O 0,H 3) 104.68 -0.000015 0.00 104.68 + 5. A(O 0,N 1,O 2) 113.22 -0.000014 0.00 113.22 + 6. D(O 2,N 1,O 0,H 3) 8.18 0.005801 0.00 8.18 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.594275 -0.381921 0.572007 + N 0.419231 -0.603114 -0.364673 + O 0.909914 0.399117 -0.768596 + H -0.734869 0.585919 0.561262 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.123017 -0.721727 1.080936 + 1 N 7.0000 0 14.007 0.792232 -1.139720 -0.689131 + 2 O 8.0000 0 15.999 1.719489 0.754221 -1.452436 + 3 H 1.0000 0 1.008 -1.388702 1.107226 1.060631 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.397672940727 0.00000000 0.00000000 + O 2 1 0 1.186755960518 113.22032545 0.00000000 + H 1 2 3 0.978057466847 104.68350450 8.18181841 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.641219082767 0.00000000 0.00000000 + O 2 1 0 2.242643753178 113.22032545 0.00000000 + H 1 2 3 1.848260755578 104.68350450 8.18181841 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2245 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2720 + la=0 lb=0: 557 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.118674439104 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 70.1186744391 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.434e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7239229683 0.000000000000 0.00000101 0.00000004 0.0000069 0.7000 + 1 -204.7239229686 -0.000000000322 0.00000089 0.00000004 0.0000055 0.7000 + ***Turning on DIIS*** + 2 -204.7239229692 -0.000000000634 0.00000231 0.00000010 0.0000044 0.0000 + 3 -204.7239264735 -0.000003504298 0.00000088 0.00000003 0.0000015 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 4 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72392282 Eh -5570.82115 eV + +Components: +Nuclear Repulsion : 70.11867444 Eh 1908.02613 eV +Electronic Energy : -274.84259726 Eh -7478.84729 eV +One Electron Energy: -419.81124361 Eh -11423.64471 eV +Two Electron Energy: 144.96864635 Eh 3944.79742 eV + +Virial components: +Potential Energy : -408.97390350 Eh -11128.74569 eV +Kinetic Energy : 204.24998068 Eh 5557.92453 eV +Virial Ratio : 2.00232040 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.6567e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.1233e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.1131e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 4.5739e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.665804 -562.3451 + 1 1.0000 -20.651289 -561.9501 + 2 1.0000 -15.802789 -430.0158 + 3 1.0000 -1.608735 -43.7759 + 4 1.0000 -1.408028 -38.3144 + 5 1.0000 -0.967436 -26.3253 + 6 1.0000 -0.776598 -21.1323 + 7 1.0000 -0.743979 -20.2447 + 8 1.0000 -0.689733 -18.7686 + 9 1.0000 -0.614228 -16.7140 + 10 1.0000 -0.533136 -14.5074 + 11 1.0000 -0.475217 -12.9313 + 12 0.0000 0.031706 0.8628 + 13 0.0000 0.077670 2.1135 + 14 0.0000 0.095205 2.5906 + 15 0.0000 0.113046 3.0761 + 16 0.0000 0.128225 3.4892 + 17 0.0000 0.138723 3.7749 + 18 0.0000 0.157802 4.2940 + 19 0.0000 0.169308 4.6071 + 20 0.0000 0.184501 5.0205 + 21 0.0000 0.195346 5.3156 + 22 0.0000 0.205751 5.5988 + 23 0.0000 0.232670 6.3313 + 24 0.0000 0.250691 6.8216 + 25 0.0000 0.301626 8.2077 + 26 0.0000 0.313886 8.5413 + 27 0.0000 0.344736 9.3807 + 28 0.0000 0.352637 9.5958 + 29 0.0000 0.400180 10.8894 + 30 0.0000 0.441857 12.0236 + 31 0.0000 0.512633 13.9495 + 32 0.0000 0.516558 14.0563 + 33 0.0000 0.535579 14.5738 + 34 0.0000 0.562592 15.3089 + 35 0.0000 0.617919 16.8144 + 36 0.0000 0.639772 17.4091 + 37 0.0000 0.666849 18.1459 + 38 0.0000 0.683810 18.6074 + 39 0.0000 0.698211 18.9993 + 40 0.0000 0.732987 19.9456 + 41 0.0000 0.756716 20.5913 + 42 0.0000 0.761679 20.7263 + 43 0.0000 0.783719 21.3261 + 44 0.0000 0.798102 21.7175 + 45 0.0000 0.845603 23.0100 + 46 0.0000 0.850767 23.1505 + 47 0.0000 0.871069 23.7030 + 48 0.0000 0.918869 25.0037 + 49 0.0000 0.937707 25.5163 + 50 0.0000 0.954571 25.9752 + 51 0.0000 1.006362 27.3845 + 52 0.0000 1.027749 27.9665 + 53 0.0000 1.071715 29.1629 + 54 0.0000 1.081656 29.4334 + 55 0.0000 1.088317 29.6146 + 56 0.0000 1.179671 32.1005 + 57 0.0000 1.214651 33.0523 + 58 0.0000 1.239591 33.7310 + 59 0.0000 1.264680 34.4137 + 60 0.0000 1.339952 36.4619 + 61 0.0000 1.412576 38.4382 + 62 0.0000 1.461137 39.7595 + 63 0.0000 1.504137 40.9296 + 64 0.0000 1.541634 41.9500 + 65 0.0000 1.557201 42.3736 + 66 0.0000 1.592070 43.3224 + 67 0.0000 1.612525 43.8790 + 68 0.0000 1.657324 45.0981 + 69 0.0000 1.764450 48.0131 + 70 0.0000 1.789712 48.7005 + 71 0.0000 1.822628 49.5962 + 72 0.0000 1.905494 51.8511 + 73 0.0000 1.921945 52.2988 + 74 0.0000 1.988882 54.1202 + 75 0.0000 1.999112 54.3986 + 76 0.0000 2.039997 55.5111 + 77 0.0000 2.123470 57.7826 + 78 0.0000 2.151433 58.5435 + 79 0.0000 2.177974 59.2657 + 80 0.0000 2.286878 62.2291 + 81 0.0000 2.320072 63.1324 + 82 0.0000 2.352535 64.0157 + 83 0.0000 2.386006 64.9265 + 84 0.0000 2.435814 66.2819 + 85 0.0000 2.454050 66.7781 + 86 0.0000 2.473586 67.3097 + 87 0.0000 2.512394 68.3657 + 88 0.0000 2.520972 68.5991 + 89 0.0000 2.560075 69.6632 + 90 0.0000 2.575849 70.0924 + 91 0.0000 2.639346 71.8203 + 92 0.0000 2.661746 72.4298 + 93 0.0000 2.691913 73.2507 + 94 0.0000 2.746163 74.7269 + 95 0.0000 2.794162 76.0330 + 96 0.0000 2.907634 79.1208 + 97 0.0000 2.965219 80.6877 + 98 0.0000 2.980847 81.1130 + 99 0.0000 3.065582 83.4187 + 100 0.0000 3.146252 85.6139 + 101 0.0000 3.151320 85.7518 + 102 0.0000 3.218278 87.5738 + 103 0.0000 3.515473 95.6609 + 104 0.0000 3.753073 102.1263 + 105 0.0000 3.844241 104.6071 + 106 0.0000 4.023422 109.4829 + 107 0.0000 4.152653 112.9994 + 108 0.0000 4.174998 113.6075 + 109 0.0000 4.245837 115.5351 + 110 0.0000 4.359106 118.6173 + 111 0.0000 4.411108 120.0324 + 112 0.0000 4.519419 122.9796 + 113 0.0000 4.568548 124.3165 + 114 0.0000 4.700683 127.9121 + 115 0.0000 4.844094 131.8145 + 116 0.0000 4.886355 132.9645 + 117 0.0000 4.900092 133.3383 + 118 0.0000 4.945047 134.5616 + 119 0.0000 5.000198 136.0623 + 120 0.0000 5.066656 137.8707 + 121 0.0000 5.107202 138.9740 + 122 0.0000 5.201432 141.5382 + 123 0.0000 5.219440 142.0282 + 124 0.0000 5.231437 142.3547 + 125 0.0000 5.302427 144.2864 + 126 0.0000 5.390931 146.6947 + 127 0.0000 5.484652 149.2450 + 128 0.0000 5.554160 151.1364 + 129 0.0000 5.664031 154.1261 + 130 0.0000 5.788995 157.5266 + 131 0.0000 5.921520 161.1327 + 132 0.0000 6.185462 168.3150 + 133 0.0000 6.421585 174.7402 + 134 0.0000 6.518528 177.3782 + 135 0.0000 6.565899 178.6672 + 136 0.0000 6.677181 181.6953 + 137 0.0000 6.702337 182.3798 + 138 0.0000 6.765419 184.0964 + 139 0.0000 6.831602 185.8974 + 140 0.0000 6.951999 189.1735 + 141 0.0000 7.100638 193.2182 + 142 0.0000 7.123737 193.8467 + 143 0.0000 7.156215 194.7305 + 144 0.0000 7.168209 195.0569 + 145 0.0000 7.230479 196.7513 + 146 0.0000 7.289600 198.3601 + 147 0.0000 7.315984 199.0780 + 148 0.0000 7.408626 201.5990 + 149 0.0000 7.432631 202.2522 + 150 0.0000 7.467647 203.2050 + 151 0.0000 7.497850 204.0269 + 152 0.0000 7.613280 207.1679 + 153 0.0000 7.691136 209.2864 + 154 0.0000 7.861023 213.9093 + 155 0.0000 7.942690 216.1316 + 156 0.0000 8.302084 225.9112 + 157 0.0000 8.316150 226.2939 + 158 0.0000 14.217147 386.8682 + 159 0.0000 15.104364 411.0106 + 160 0.0000 15.628763 425.2803 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.665804 -562.3451 + 1 1.0000 -20.651289 -561.9501 + 2 1.0000 -15.802789 -430.0158 + 3 1.0000 -1.608735 -43.7759 + 4 1.0000 -1.408028 -38.3144 + 5 1.0000 -0.967436 -26.3253 + 6 1.0000 -0.776598 -21.1323 + 7 1.0000 -0.743979 -20.2447 + 8 1.0000 -0.689733 -18.7686 + 9 1.0000 -0.614228 -16.7140 + 10 1.0000 -0.533136 -14.5074 + 11 1.0000 -0.475217 -12.9313 + 12 0.0000 0.031706 0.8628 + 13 0.0000 0.077670 2.1135 + 14 0.0000 0.095205 2.5906 + 15 0.0000 0.113046 3.0761 + 16 0.0000 0.128225 3.4892 + 17 0.0000 0.138723 3.7749 + 18 0.0000 0.157802 4.2940 + 19 0.0000 0.169308 4.6071 + 20 0.0000 0.184501 5.0205 + 21 0.0000 0.195346 5.3156 + 22 0.0000 0.205751 5.5988 + 23 0.0000 0.232670 6.3313 + 24 0.0000 0.250691 6.8216 + 25 0.0000 0.301626 8.2077 + 26 0.0000 0.313886 8.5413 + 27 0.0000 0.344736 9.3807 + 28 0.0000 0.352637 9.5958 + 29 0.0000 0.400180 10.8894 + 30 0.0000 0.441857 12.0236 + 31 0.0000 0.512633 13.9495 + 32 0.0000 0.516558 14.0563 + 33 0.0000 0.535579 14.5738 + 34 0.0000 0.562592 15.3089 + 35 0.0000 0.617919 16.8144 + 36 0.0000 0.639772 17.4091 + 37 0.0000 0.666849 18.1459 + 38 0.0000 0.683810 18.6074 + 39 0.0000 0.698211 18.9993 + 40 0.0000 0.732987 19.9456 + 41 0.0000 0.756716 20.5913 + 42 0.0000 0.761679 20.7263 + 43 0.0000 0.783719 21.3261 + 44 0.0000 0.798102 21.7175 + 45 0.0000 0.845603 23.0100 + 46 0.0000 0.850767 23.1505 + 47 0.0000 0.871069 23.7030 + 48 0.0000 0.918869 25.0037 + 49 0.0000 0.937707 25.5163 + 50 0.0000 0.954571 25.9752 + 51 0.0000 1.006362 27.3845 + 52 0.0000 1.027749 27.9665 + 53 0.0000 1.071715 29.1629 + 54 0.0000 1.081656 29.4334 + 55 0.0000 1.088317 29.6146 + 56 0.0000 1.179671 32.1005 + 57 0.0000 1.214651 33.0523 + 58 0.0000 1.239591 33.7310 + 59 0.0000 1.264680 34.4137 + 60 0.0000 1.339952 36.4619 + 61 0.0000 1.412576 38.4382 + 62 0.0000 1.461137 39.7595 + 63 0.0000 1.504137 40.9296 + 64 0.0000 1.541634 41.9500 + 65 0.0000 1.557201 42.3736 + 66 0.0000 1.592070 43.3224 + 67 0.0000 1.612525 43.8790 + 68 0.0000 1.657324 45.0981 + 69 0.0000 1.764450 48.0131 + 70 0.0000 1.789712 48.7005 + 71 0.0000 1.822628 49.5962 + 72 0.0000 1.905494 51.8511 + 73 0.0000 1.921945 52.2988 + 74 0.0000 1.988882 54.1202 + 75 0.0000 1.999112 54.3986 + 76 0.0000 2.039997 55.5111 + 77 0.0000 2.123470 57.7826 + 78 0.0000 2.151433 58.5435 + 79 0.0000 2.177974 59.2657 + 80 0.0000 2.286878 62.2291 + 81 0.0000 2.320072 63.1324 + 82 0.0000 2.352535 64.0157 + 83 0.0000 2.386006 64.9265 + 84 0.0000 2.435814 66.2819 + 85 0.0000 2.454050 66.7781 + 86 0.0000 2.473586 67.3097 + 87 0.0000 2.512394 68.3657 + 88 0.0000 2.520972 68.5991 + 89 0.0000 2.560075 69.6632 + 90 0.0000 2.575849 70.0924 + 91 0.0000 2.639346 71.8203 + 92 0.0000 2.661746 72.4298 + 93 0.0000 2.691913 73.2507 + 94 0.0000 2.746163 74.7269 + 95 0.0000 2.794162 76.0330 + 96 0.0000 2.907634 79.1208 + 97 0.0000 2.965219 80.6877 + 98 0.0000 2.980847 81.1130 + 99 0.0000 3.065582 83.4187 + 100 0.0000 3.146252 85.6139 + 101 0.0000 3.151320 85.7518 + 102 0.0000 3.218278 87.5738 + 103 0.0000 3.515473 95.6609 + 104 0.0000 3.753073 102.1263 + 105 0.0000 3.844241 104.6071 + 106 0.0000 4.023422 109.4829 + 107 0.0000 4.152653 112.9994 + 108 0.0000 4.174998 113.6075 + 109 0.0000 4.245837 115.5351 + 110 0.0000 4.359106 118.6173 + 111 0.0000 4.411108 120.0324 + 112 0.0000 4.519419 122.9796 + 113 0.0000 4.568548 124.3165 + 114 0.0000 4.700683 127.9121 + 115 0.0000 4.844094 131.8145 + 116 0.0000 4.886355 132.9645 + 117 0.0000 4.900092 133.3383 + 118 0.0000 4.945047 134.5616 + 119 0.0000 5.000198 136.0623 + 120 0.0000 5.066656 137.8707 + 121 0.0000 5.107202 138.9740 + 122 0.0000 5.201432 141.5382 + 123 0.0000 5.219440 142.0282 + 124 0.0000 5.231437 142.3547 + 125 0.0000 5.302427 144.2864 + 126 0.0000 5.390931 146.6947 + 127 0.0000 5.484652 149.2450 + 128 0.0000 5.554160 151.1364 + 129 0.0000 5.664031 154.1261 + 130 0.0000 5.788995 157.5266 + 131 0.0000 5.921520 161.1327 + 132 0.0000 6.185462 168.3150 + 133 0.0000 6.421585 174.7402 + 134 0.0000 6.518528 177.3782 + 135 0.0000 6.565899 178.6672 + 136 0.0000 6.677181 181.6953 + 137 0.0000 6.702337 182.3798 + 138 0.0000 6.765419 184.0964 + 139 0.0000 6.831602 185.8974 + 140 0.0000 6.951999 189.1735 + 141 0.0000 7.100638 193.2182 + 142 0.0000 7.123737 193.8467 + 143 0.0000 7.156215 194.7305 + 144 0.0000 7.168209 195.0569 + 145 0.0000 7.230479 196.7513 + 146 0.0000 7.289600 198.3601 + 147 0.0000 7.315984 199.0780 + 148 0.0000 7.408626 201.5990 + 149 0.0000 7.432631 202.2522 + 150 0.0000 7.467647 203.2050 + 151 0.0000 7.497850 204.0269 + 152 0.0000 7.613280 207.1679 + 153 0.0000 7.691136 209.2864 + 154 0.0000 7.861023 213.9093 + 155 0.0000 7.942690 216.1316 + 156 0.0000 8.302084 225.9112 + 157 0.0000 8.316150 226.2939 + 158 0.0000 14.217147 386.8682 + 159 0.0000 15.104364 411.0106 + 160 0.0000 15.628763 425.2803 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.277658 0.000000 + 1 N : 0.332169 0.000000 + 2 O : -0.304183 0.000000 + 3 H : 0.249672 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.800671 s : 3.800671 + pz : 1.544816 p : 4.434022 + px : 1.503204 + py : 1.386001 + dz2 : 0.010312 d : 0.037465 + dxz : 0.007599 + dyz : 0.002220 + dx2y2 : 0.016176 + dxy : 0.001158 + f0 : 0.000558 f : 0.005501 + f+1 : 0.001367 + f-1 : 0.000348 + f+2 : 0.000990 + f-2 : 0.001304 + f+3 : 0.000207 + f-3 : 0.000726 + 1 N s : 3.866285 s : 3.866285 + pz : 0.708465 p : 2.623592 + px : 0.723286 + py : 1.191840 + dz2 : 0.031545 d : 0.144629 + dxz : 0.028228 + dyz : 0.023130 + dx2y2 : 0.034940 + dxy : 0.026785 + f0 : 0.003776 f : 0.033326 + f+1 : 0.002697 + f-1 : 0.005324 + f+2 : 0.003125 + f-2 : 0.005734 + f+3 : 0.004835 + f-3 : 0.007836 + 2 O s : 3.856643 s : 3.856643 + pz : 1.494748 p : 4.380610 + px : 1.503759 + py : 1.382103 + dz2 : 0.009868 d : 0.059502 + dxz : 0.002887 + dyz : 0.018014 + dx2y2 : 0.012064 + dxy : 0.016668 + f0 : 0.000453 f : 0.007428 + f+1 : 0.000281 + f-1 : 0.001668 + f+2 : 0.000945 + f-2 : 0.000947 + f+3 : 0.001303 + f-3 : 0.001831 + 3 H s : 0.646587 s : 0.646587 + pz : 0.030094 p : 0.082691 + px : 0.032316 + py : 0.020281 + dz2 : -0.000073 d : 0.021051 + dxz : -0.000843 + dyz : 0.010811 + dx2y2 : 0.000967 + dxy : 0.010188 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.602963 0.000000 + 1 N : -0.284534 0.000000 + 2 O : 0.245345 0.000000 + 3 H : -0.563775 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.105744 s : 3.105744 + pz : 1.318246 p : 3.895091 + px : 1.289240 + py : 1.287605 + dz2 : 0.048242 d : 0.301447 + dxz : 0.088721 + dyz : 0.045104 + dx2y2 : 0.060122 + dxy : 0.059258 + f0 : 0.008834 f : 0.094754 + f+1 : 0.018104 + f-1 : 0.007344 + f+2 : 0.015381 + f-2 : 0.023561 + f+3 : 0.006586 + f-3 : 0.014943 + 1 N s : 2.998694 s : 2.998694 + pz : 0.767359 p : 2.829831 + px : 0.793899 + py : 1.268573 + dz2 : 0.188290 d : 0.981385 + dxz : 0.204063 + dyz : 0.157627 + dx2y2 : 0.244241 + dxy : 0.187164 + f0 : 0.049406 f : 0.474623 + f+1 : 0.051495 + f-1 : 0.061374 + f+2 : 0.059861 + f-2 : 0.087590 + f+3 : 0.068755 + f-3 : 0.096142 + 2 O s : 3.297436 s : 3.297436 + pz : 1.279375 p : 4.022586 + px : 1.303672 + py : 1.439539 + dz2 : 0.047217 d : 0.319006 + dxz : 0.042462 + dyz : 0.053349 + dx2y2 : 0.112539 + dxy : 0.063439 + f0 : 0.008416 f : 0.115626 + f+1 : 0.005280 + f-1 : 0.020254 + f+2 : 0.013130 + f-2 : 0.018864 + f+3 : 0.019686 + f-3 : 0.029996 + 3 H s : 0.609349 s : 0.609349 + pz : 0.138876 p : 0.541576 + px : 0.139938 + py : 0.262761 + dz2 : 0.038280 d : 0.412850 + dxz : 0.029817 + dyz : 0.118648 + dx2y2 : 0.109166 + dxy : 0.116940 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2777 8.0000 -0.2777 1.8056 1.8056 -0.0000 + 1 N 6.6678 7.0000 0.3322 2.5017 2.5017 -0.0000 + 2 O 8.3042 8.0000 -0.3042 1.6634 1.6634 -0.0000 + 3 H 0.7503 1.0000 0.2497 1.0146 1.0146 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8253 B( 0-O , 3-H ) : 0.9222 B( 1-N , 2-O ) : 1.5947 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.882 sec +Sum of individual times .... 0.643 sec ( 72.9%) + +Fock matrix formation .... 0.487 sec ( 55.2%) +Diagonalization .... 0.055 sec ( 6.2%) +Density matrix formation .... 0.004 sec ( 0.5%) +Population analysis .... 0.049 sec ( 5.5%) +Initial guess .... 0.012 sec ( 1.3%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.007 sec ( 0.8%) +DIIS solution .... 0.036 sec ( 4.1%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.217 sec +Reference energy ... -204.723922970 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.538 sec +AO-integral generation ... 0.143 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.526 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.024 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.027 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.034 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.039 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.034 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.033 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.024 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.039 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.025 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.360 sec +AO-integral generation ... 0.255 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.049 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.152 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.266 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090616951 +EMP2(bb)= -0.090616951 +EMP2(ab)= -0.514889261 + +Initial guess performed in 0.136 sec +E(0) ... -204.723922970 +E(MP2) ... -0.696123163 +Initial E(tot) ... -205.420046133 + ... 0.186434668 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.420046133 -0.696123163 -0.000000000 0.030785828 3.13 0.000001292 + *** Turning on DIIS *** + 1 -205.391097944 -0.667174973 0.028948189 0.012309586 3.03 0.058323057 + 2 -205.410490080 -0.686567110 -0.019392136 0.006983296 3.09 0.061581028 + 3 -205.414163893 -0.690240923 -0.003673813 0.002519351 3.24 0.076067865 + 4 -205.415747945 -0.691824975 -0.001584052 0.001534408 3.01 0.083117654 + 5 -205.416293625 -0.692370655 -0.000545679 0.000725692 3.40 0.088597035 + 6 -205.416391497 -0.692468527 -0.000097872 0.000458660 3.10 0.091000996 + 7 -205.416429995 -0.692507024 -0.000038498 0.000204700 3.21 0.091951541 + 8 -205.416438161 -0.692515191 -0.000008166 0.000109577 2.88 0.092284642 + 9 -205.416434413 -0.692511442 0.000003748 0.000027964 2.89 0.092384523 + 10 -205.416438604 -0.692515634 -0.000004191 0.000007585 2.82 0.092420401 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.723922970 +E(CORR) ... -0.692515634 +E(TOT) ... -205.416438604 +Singles norm **1/2 ... 0.092420401 ( 0.046210200, 0.046210200) +T1 diagnostic ... 0.021783697 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.064967 + 10a-> 13a 10b-> 13b 0.057048 + 8b-> 13b -1b-> -1b 0.052288 + 8a-> 13a -1a-> -1a 0.052288 + 8a-> 13a 10b-> 13b 0.036741 + 10a-> 13a 8b-> 13b 0.036741 + 11a-> 13a 11b-> 13b 0.029171 + 10a-> 13a 10b-> 22b 0.026318 + 10a-> 22a 10b-> 13b 0.026318 + 5a-> 13a 5b-> 13b 0.025167 + 8a-> 22a 8b-> 13b 0.024792 + 8a-> 13a 8b-> 22b 0.024792 + 11a-> 26a -1a-> -1a 0.023508 + 11b-> 26b -1b-> -1b 0.023508 + 10b-> 13b -1b-> -1b 0.023286 + 10a-> 13a -1a-> -1a 0.023286 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034625987 + alpha-alpha-alpha ... -0.000912944 ( 2.6%) + alpha-alpha-beta ... -0.016400050 ( 47.4%) + alpha-beta -beta ... -0.016400050 ( 47.4%) + beta -beta -beta ... -0.000912944 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034625987 + +Final correlation energy ... -0.727141621 +E(CCSD) ... -205.416438604 +E(CCSD(T)) ... -205.451064591 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.207504504 sqrt= 1.098865098 +W(HF) = 0.828154261 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.187369 0.000000 + 1 N : 0.139179 0.000000 + 2 O : -0.183639 -0.000000 + 3 H : 0.231829 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.788284 s : 3.788284 + pz : 1.497281 p : 4.322902 + px : 1.464185 + py : 1.361435 + dz2 : 0.016956 d : 0.067048 + dxz : 0.011875 + dyz : 0.009449 + dx2y2 : 0.020030 + dxy : 0.008738 + f0 : 0.001148 f : 0.009135 + f+1 : 0.001765 + f-1 : 0.000989 + f+2 : 0.001347 + f-2 : 0.001718 + f+3 : 0.000837 + f-3 : 0.001331 + 1 N s : 3.915978 s : 3.915978 + pz : 0.796091 p : 2.741074 + px : 0.803187 + py : 1.141796 + dz2 : 0.038671 d : 0.171432 + dxz : 0.034380 + dyz : 0.026028 + dx2y2 : 0.042675 + dxy : 0.029679 + f0 : 0.003702 f : 0.032336 + f+1 : 0.002740 + f-1 : 0.005267 + f+2 : 0.002800 + f-2 : 0.005669 + f+3 : 0.004542 + f-3 : 0.007615 + 2 O s : 3.844394 s : 3.844394 + pz : 1.439520 p : 4.246125 + px : 1.451102 + py : 1.355504 + dz2 : 0.015094 d : 0.082980 + dxz : 0.009589 + dyz : 0.020403 + dx2y2 : 0.018864 + dxy : 0.019029 + f0 : 0.000932 f : 0.010140 + f+1 : 0.000816 + f-1 : 0.001937 + f+2 : 0.001333 + f-2 : 0.001401 + f+3 : 0.001597 + f-3 : 0.002123 + 3 H s : 0.664149 s : 0.664149 + pz : 0.034521 p : 0.084360 + px : 0.036172 + py : 0.013666 + dz2 : -0.000022 d : 0.019662 + dxz : -0.000195 + dyz : 0.009867 + dx2y2 : 0.000498 + dxy : 0.009515 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.618824 0.000000 + 1 N : -0.333847 -0.000000 + 2 O : 0.281250 -0.000000 + 3 H : -0.566227 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.114723 s : 3.114723 + pz : 1.289693 p : 3.831096 + px : 1.268293 + py : 1.273110 + dz2 : 0.056150 d : 0.333121 + dxz : 0.094912 + dyz : 0.050315 + dx2y2 : 0.067035 + dxy : 0.064710 + f0 : 0.010273 f : 0.102235 + f+1 : 0.020146 + f-1 : 0.008345 + f+2 : 0.016619 + f-2 : 0.023365 + f+3 : 0.007572 + f-3 : 0.015915 + 1 N s : 3.004225 s : 3.004225 + pz : 0.817254 p : 2.882266 + px : 0.838788 + py : 1.226225 + dz2 : 0.187298 d : 0.984817 + dxz : 0.212004 + dyz : 0.154977 + dx2y2 : 0.243617 + dxy : 0.186922 + f0 : 0.047773 f : 0.462539 + f+1 : 0.048446 + f-1 : 0.059872 + f+2 : 0.059654 + f-2 : 0.085341 + f+3 : 0.069116 + f-3 : 0.092337 + 2 O s : 3.299429 s : 3.299429 + pz : 1.248215 p : 3.941390 + px : 1.272764 + py : 1.420411 + dz2 : 0.055229 d : 0.353282 + dxz : 0.047614 + dyz : 0.061920 + dx2y2 : 0.117365 + dxy : 0.071154 + f0 : 0.009339 f : 0.124649 + f+1 : 0.006614 + f-1 : 0.022035 + f+2 : 0.015158 + f-2 : 0.019322 + f+3 : 0.021233 + f-3 : 0.030946 + 3 H s : 0.615064 s : 0.615064 + pz : 0.140354 p : 0.548836 + px : 0.141601 + py : 0.266881 + dz2 : 0.037966 d : 0.402327 + dxz : 0.029757 + dyz : 0.113677 + dx2y2 : 0.108382 + dxy : 0.112544 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.1874 8.0000 -0.1874 2.1826 1.7342 0.4485 + 1 N 6.8608 7.0000 0.1392 2.7917 2.3237 0.4680 + 2 O 8.1836 8.0000 -0.1836 2.0728 1.5753 0.4974 + 3 H 0.7682 1.0000 0.2318 1.0348 0.9609 0.0739 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7849 B( 0-O , 2-O ) : 0.1004 B( 0-O , 3-H ) : 0.8489 +B( 1-N , 2-O ) : 1.4509 + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 49.026 sec + +Fock Matrix Formation ... 0.217 sec ( 0.4%) +Initial Guess ... 0.136 sec ( 0.3%) +DIIS Solver ... 1.726 sec ( 3.5%) +State Vector Update ... 0.079 sec ( 0.2%) +Sigma-vector construction ... 31.987 sec ( 65.2%) + <0|H|D> ... 0.003 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.017 sec ( 0.1% of sigma) + (0-ext) ... 0.053 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (2-ext) ... 0.725 sec ( 2.3% of sigma) + (4-ext) ... 18.020 sec ( 56.3% of sigma) + ... 1.225 sec ( 3.8% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.088 sec ( 0.3% of sigma) + Fock-dressing ... 1.634 sec ( 5.1% of sigma) + (ik|jl)-dressing ... 0.058 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 8.023 sec ( 25.1% of sigma) + Pair energies ... 0.006 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.747 sec ( 13.8% of ALL) + I/O of integral and amplitudes ... 0.696 sec ( 10.3% of (T)) + External N**7 contributions ... 3.909 sec ( 57.9% of (T)) + Internal N**7 contributions ... 0.312 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.587 sec ( 23.5% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.451064590976 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.024.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.024.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.409247, -0.304769 -0.309003) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.60217 -0.26473 -0.52038 +Nuclear contribution : -0.89323 0.70359 0.68079 + ----------------------------------------- +Total Dipole Moment : -0.29106 0.43887 0.16041 + ----------------------------------------- +Magnitude (a.u.) : 0.55050 +Magnitude (Debye) : 1.39926 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.781542 0.439449 0.379733 +Rotational constants in MHz : 83388.520450 13174.350820 11384.094617 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.173442 -0.516389 -0.079450 +x,y,z [Debye]: 0.440855 -1.312557 -0.201945 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.409247, -0.304769 -0.309003) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.64144 -0.18122 -0.54100 +Nuclear contribution : -0.89323 0.70359 0.68079 + ----------------------------------------- +Total Dipole Moment : -0.25179 0.52238 0.13979 + ----------------------------------------- +Magnitude (a.u.) : 0.59651 +Magnitude (Debye) : 1.51620 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.781542 0.439449 0.379733 +Rotational constants in MHz : 83388.520450 13174.350820 11384.094617 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.106801 -0.582733 -0.069529 +x,y,z [Debye]: 0.271466 -1.481191 -0.176729 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 25 * + * * + * Dihedral ( 2, 1, 0, 3) : 16.36363636 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0310591429 RMS(Int)= 0.0002428009 + Iter 1: RMS(Cart)= 0.0000528096 RMS(Int)= 0.0000015066 + Iter 2: RMS(Cart)= 0.0000003277 RMS(Int)= 0.0000000094 + Iter 3: RMS(Cart)= 0.0000000020 RMS(Int)= 0.0000000001 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.3992 0.000000 + 2. B(O 2,N 1) 1.1879 0.000000 + 3. B(H 3,O 0) 0.9798 0.000000 + 4. A(N 1,O 0,H 3) 104.4719 0.000000 + 5. A(O 0,N 1,O 2) 113.0386 0.000000 + 6. D(O 2,N 1,O 0,H 3) 16.3636 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.570314 -0.378358 0.596985 + N 0.397992 -0.601512 -0.388138 + O 0.926288 0.397083 -0.755392 + H -0.753966 0.582787 0.546545 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.077737 -0.714992 1.128139 + 1 N 7.0000 0 14.007 0.752097 -1.136693 -0.733475 + 2 O 8.0000 0 15.999 1.750431 0.750377 -1.427484 + 3 H 1.0000 0 1.008 -1.424789 1.101308 1.032820 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.397672940727 0.00000000 0.00000000 + O 2 1 0 1.186755960518 113.22032545 0.00000000 + H 1 2 3 0.978057466847 104.68350450 8.18181841 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.641219082767 0.00000000 0.00000000 + O 2 1 0 2.242643753178 113.22032545 0.00000000 + H 1 2 3 1.848260755578 104.68350450 8.18181841 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2245 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2720 + la=0 lb=0: 557 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.052410007856 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 70.0524100079 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.449e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7185115898 0.000000000000 0.00161737 0.00005497 0.0106643 0.7000 + 1 -204.7192419101 -0.000730320296 0.00145029 0.00005079 0.0089427 0.7000 + ***Turning on DIIS*** + 2 -204.7198800832 -0.000638173119 0.00387116 0.00013966 0.0073701 0.0000 + 3 -204.7232110514 -0.003330968178 0.00186464 0.00006221 0.0034255 0.0000 + 4 -204.7211791661 0.002031885276 0.00088832 0.00003148 0.0015726 0.0000 + 5 -204.7231885906 -0.002009424500 0.00083339 0.00003644 0.0008780 0.0000 + 6 -204.7222523069 0.000936283681 0.00051095 0.00002462 0.0005504 0.0000 + 7 -204.7219969134 0.000255393502 0.00034524 0.00001520 0.0002870 0.0000 + 8 -204.7229087322 -0.000911818742 0.00019333 0.00000871 0.0001720 0.0000 + 9 -204.7223743834 0.000534348794 0.00009371 0.00000282 0.0000809 0.0000 + 10 -204.7223606563 0.000013727053 0.00003430 0.00000096 0.0000430 0.0000 + 11 -204.7225134859 -0.000152829593 0.00002119 0.00000053 0.0000181 0.0000 + 12 -204.7224433493 0.000070136637 0.00000669 0.00000017 0.0000058 0.0000 + 13 -204.7224616262 -0.000018276979 0.00000216 0.00000006 0.0000021 0.0000 + 14 -204.7224555385 0.000006087789 0.00000082 0.00000003 0.0000011 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 15 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72245603 Eh -5570.78124 eV + +Components: +Nuclear Repulsion : 70.05241001 Eh 1906.22299 eV +Electronic Energy : -274.77486604 Eh -7477.00423 eV +One Electron Energy: -419.68849561 Eh -11420.30456 eV +Two Electron Energy: 144.91362957 Eh 3943.30033 eV + +Virial components: +Potential Energy : -408.96473815 Eh -11128.49629 eV +Kinetic Energy : 204.24228213 Eh 5557.71505 eV +Virial Ratio : 2.00235100 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -4.9038e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.8334e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.0833e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.9738e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.666362 -562.3603 + 1 1.0000 -20.650498 -561.9286 + 2 1.0000 -15.802760 -430.0150 + 3 1.0000 -1.607573 -43.7443 + 4 1.0000 -1.406809 -38.2812 + 5 1.0000 -0.966749 -26.3066 + 6 1.0000 -0.775756 -21.1094 + 7 1.0000 -0.743086 -20.2204 + 8 1.0000 -0.690522 -18.7901 + 9 1.0000 -0.612343 -16.6627 + 10 1.0000 -0.533086 -14.5060 + 11 1.0000 -0.475077 -12.9275 + 12 0.0000 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7.308639 198.8782 + 148 0.0000 7.398871 201.3335 + 149 0.0000 7.444547 202.5764 + 150 0.0000 7.473438 203.3626 + 151 0.0000 7.502883 204.1638 + 152 0.0000 7.611773 207.1269 + 153 0.0000 7.679906 208.9809 + 154 0.0000 7.857389 213.8104 + 155 0.0000 7.922583 215.5844 + 156 0.0000 8.288553 225.5430 + 157 0.0000 8.308526 226.0865 + 158 0.0000 14.181351 385.8942 + 159 0.0000 15.102177 410.9511 + 160 0.0000 15.579384 423.9366 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.666362 -562.3603 + 1 1.0000 -20.650498 -561.9286 + 2 1.0000 -15.802760 -430.0150 + 3 1.0000 -1.607573 -43.7443 + 4 1.0000 -1.406809 -38.2812 + 5 1.0000 -0.966749 -26.3066 + 6 1.0000 -0.775756 -21.1094 + 7 1.0000 -0.743086 -20.2204 + 8 1.0000 -0.690522 -18.7901 + 9 1.0000 -0.612343 -16.6627 + 10 1.0000 -0.533086 -14.5060 + 11 1.0000 -0.475077 -12.9275 + 12 0.0000 0.031544 0.8584 + 13 0.0000 0.076132 2.0717 + 14 0.0000 0.095214 2.5909 + 15 0.0000 0.112737 3.0677 + 16 0.0000 0.124789 3.3957 + 17 0.0000 0.142286 3.8718 + 18 0.0000 0.157695 4.2911 + 19 0.0000 0.169422 4.6102 + 20 0.0000 0.183935 5.0051 + 21 0.0000 0.195276 5.3137 + 22 0.0000 0.205197 5.5837 + 23 0.0000 0.233062 6.3419 + 24 0.0000 0.252028 6.8580 + 25 0.0000 0.301057 8.1922 + 26 0.0000 0.313940 8.5427 + 27 0.0000 0.344746 9.3810 + 28 0.0000 0.352187 9.5835 + 29 0.0000 0.398014 10.8305 + 30 0.0000 0.435990 11.8639 + 31 0.0000 0.512825 13.9547 + 32 0.0000 0.519985 14.1495 + 33 0.0000 0.535236 14.5645 + 34 0.0000 0.562734 15.3128 + 35 0.0000 0.617719 16.8090 + 36 0.0000 0.637123 17.3370 + 37 0.0000 0.660818 17.9818 + 38 0.0000 0.686073 18.6690 + 39 0.0000 0.699815 19.0429 + 40 0.0000 0.733764 19.9667 + 41 0.0000 0.756471 20.5846 + 42 0.0000 0.759447 20.6656 + 43 0.0000 0.790930 21.5223 + 44 0.0000 0.796164 21.6647 + 45 0.0000 0.846187 23.0259 + 46 0.0000 0.848736 23.0953 + 47 0.0000 0.872407 23.7394 + 48 0.0000 0.919170 25.0119 + 49 0.0000 0.937212 25.5028 + 50 0.0000 0.956713 26.0335 + 51 0.0000 1.003422 27.3045 + 52 0.0000 1.024920 27.8895 + 53 0.0000 1.064304 28.9612 + 54 0.0000 1.082334 29.4518 + 55 0.0000 1.086632 29.5688 + 56 0.0000 1.180574 32.1250 + 57 0.0000 1.203548 32.7502 + 58 0.0000 1.240944 33.7678 + 59 0.0000 1.274087 34.6697 + 60 0.0000 1.345257 36.6063 + 61 0.0000 1.411215 38.4011 + 62 0.0000 1.451230 39.4900 + 63 0.0000 1.499519 40.8040 + 64 0.0000 1.542704 41.9791 + 65 0.0000 1.557479 42.3811 + 66 0.0000 1.590376 43.2763 + 67 0.0000 1.621092 44.1122 + 68 0.0000 1.657446 45.1014 + 69 0.0000 1.753862 47.7250 + 70 0.0000 1.790477 48.7214 + 71 0.0000 1.823479 49.6194 + 72 0.0000 1.901182 51.7338 + 73 0.0000 1.931315 52.5537 + 74 0.0000 1.989702 54.1426 + 75 0.0000 2.007567 54.6287 + 76 0.0000 2.037328 55.4385 + 77 0.0000 2.111897 57.4676 + 78 0.0000 2.157815 58.7171 + 79 0.0000 2.177944 59.2649 + 80 0.0000 2.283441 62.1356 + 81 0.0000 2.308742 62.8241 + 82 0.0000 2.361377 64.2563 + 83 0.0000 2.385761 64.9199 + 84 0.0000 2.434168 66.2371 + 85 0.0000 2.447433 66.5980 + 86 0.0000 2.468608 67.1742 + 87 0.0000 2.522712 68.6465 + 88 0.0000 2.531958 68.8981 + 89 0.0000 2.555784 69.5464 + 90 0.0000 2.576036 70.0975 + 91 0.0000 2.628824 71.5339 + 92 0.0000 2.668876 72.6238 + 93 0.0000 2.687244 73.1236 + 94 0.0000 2.733466 74.3814 + 95 0.0000 2.802744 76.2665 + 96 0.0000 2.887435 78.5711 + 97 0.0000 2.970183 80.8228 + 98 0.0000 2.984613 81.2155 + 99 0.0000 3.062503 83.3349 + 100 0.0000 3.148186 85.6665 + 101 0.0000 3.153489 85.8108 + 102 0.0000 3.219033 87.5943 + 103 0.0000 3.515987 95.6749 + 104 0.0000 3.731757 101.5463 + 105 0.0000 3.860966 105.0622 + 106 0.0000 4.020148 109.3938 + 107 0.0000 4.146448 112.8306 + 108 0.0000 4.173004 113.5532 + 109 0.0000 4.259310 115.9017 + 110 0.0000 4.359023 118.6150 + 111 0.0000 4.420838 120.2971 + 112 0.0000 4.514246 122.8389 + 113 0.0000 4.562452 124.1506 + 114 0.0000 4.694762 127.7510 + 115 0.0000 4.830072 131.4329 + 116 0.0000 4.880867 132.8151 + 117 0.0000 4.898181 133.2863 + 118 0.0000 4.944115 134.5362 + 119 0.0000 5.002931 136.1367 + 120 0.0000 5.067817 137.9023 + 121 0.0000 5.110045 139.0514 + 122 0.0000 5.194294 141.3439 + 123 0.0000 5.219450 142.0285 + 124 0.0000 5.231060 142.3444 + 125 0.0000 5.298239 144.1724 + 126 0.0000 5.389537 146.6568 + 127 0.0000 5.483256 149.2070 + 128 0.0000 5.549138 150.9997 + 129 0.0000 5.670874 154.3123 + 130 0.0000 5.787414 157.4835 + 131 0.0000 5.922693 161.1647 + 132 0.0000 6.186978 168.3562 + 133 0.0000 6.417676 174.6339 + 134 0.0000 6.516092 177.3119 + 135 0.0000 6.558329 178.4612 + 136 0.0000 6.682958 181.8525 + 137 0.0000 6.709551 182.5762 + 138 0.0000 6.767915 184.1643 + 139 0.0000 6.824723 185.7102 + 140 0.0000 6.944017 188.9563 + 141 0.0000 7.097187 193.1243 + 142 0.0000 7.133824 194.1212 + 143 0.0000 7.150104 194.5642 + 144 0.0000 7.169936 195.1039 + 145 0.0000 7.235089 196.8768 + 146 0.0000 7.282563 198.1686 + 147 0.0000 7.308639 198.8782 + 148 0.0000 7.398871 201.3335 + 149 0.0000 7.444547 202.5764 + 150 0.0000 7.473438 203.3626 + 151 0.0000 7.502883 204.1638 + 152 0.0000 7.611773 207.1269 + 153 0.0000 7.679906 208.9809 + 154 0.0000 7.857389 213.8104 + 155 0.0000 7.922583 215.5844 + 156 0.0000 8.288553 225.5430 + 157 0.0000 8.308526 226.0865 + 158 0.0000 14.181351 385.8942 + 159 0.0000 15.102177 410.9511 + 160 0.0000 15.579384 423.9366 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.283700 0.000000 + 1 N : 0.334201 0.000000 + 2 O : -0.303738 0.000000 + 3 H : 0.253237 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.804527 s : 3.804527 + pz : 1.508347 p : 4.436684 + px : 1.533911 + py : 1.394425 + dz2 : 0.010088 d : 0.037009 + dxz : 0.007695 + dyz : 0.003070 + dx2y2 : 0.015388 + dxy : 0.000767 + f0 : 0.000674 f : 0.005481 + f+1 : 0.001338 + f-1 : 0.000389 + f+2 : 0.001027 + f-2 : 0.001269 + f+3 : 0.000151 + f-3 : 0.000633 + 1 N s : 3.862649 s : 3.862649 + pz : 0.712645 p : 2.625345 + px : 0.725047 + py : 1.187653 + dz2 : 0.031728 d : 0.144499 + dxz : 0.028477 + dyz : 0.021995 + dx2y2 : 0.034437 + dxy : 0.027861 + f0 : 0.004705 f : 0.033306 + f+1 : 0.002262 + f-1 : 0.005223 + f+2 : 0.003199 + f-2 : 0.005783 + f+3 : 0.004357 + f-3 : 0.007777 + 2 O s : 3.858858 s : 3.858858 + pz : 1.534137 p : 4.378168 + px : 1.461094 + py : 1.382937 + dz2 : 0.008816 d : 0.059301 + dxz : 0.003057 + dyz : 0.018215 + dx2y2 : 0.013111 + dxy : 0.016101 + f0 : 0.000546 f : 0.007411 + f+1 : 0.000333 + f-1 : 0.001534 + f+2 : 0.000807 + f-2 : 0.000972 + f+3 : 0.001305 + f-3 : 0.001914 + 3 H s : 0.643087 s : 0.643087 + pz : 0.028391 p : 0.082851 + px : 0.033609 + py : 0.020851 + dz2 : 0.000085 d : 0.020825 + dxz : -0.000674 + dyz : 0.010499 + dx2y2 : 0.001464 + dxy : 0.009451 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.599623 0.000000 + 1 N : -0.283978 0.000000 + 2 O : 0.244282 0.000000 + 3 H : -0.559927 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.107212 s : 3.107212 + pz : 1.307829 p : 3.897878 + px : 1.299785 + py : 1.290265 + dz2 : 0.051469 d : 0.300861 + dxz : 0.089129 + dyz : 0.048578 + dx2y2 : 0.055273 + dxy : 0.056412 + f0 : 0.009152 f : 0.094426 + f+1 : 0.018738 + f-1 : 0.009104 + f+2 : 0.015366 + f-2 : 0.023617 + f+3 : 0.006263 + f-3 : 0.012185 + 1 N s : 3.000043 s : 3.000043 + pz : 0.776901 p : 2.830383 + px : 0.789241 + py : 1.264241 + dz2 : 0.191879 d : 0.979325 + dxz : 0.204685 + dyz : 0.157707 + dx2y2 : 0.237877 + dxy : 0.187177 + f0 : 0.057035 f : 0.474226 + f+1 : 0.050918 + f-1 : 0.061560 + f+2 : 0.055731 + f-2 : 0.088586 + f+3 : 0.066502 + f-3 : 0.093893 + 2 O s : 3.299233 s : 3.299233 + pz : 1.299464 p : 4.022203 + px : 1.284369 + py : 1.438371 + dz2 : 0.048212 d : 0.318840 + dxz : 0.042878 + dyz : 0.050097 + dx2y2 : 0.109501 + dxy : 0.068152 + f0 : 0.008563 f : 0.115442 + f+1 : 0.005812 + f-1 : 0.020321 + f+2 : 0.010923 + f-2 : 0.019039 + f+3 : 0.021650 + f-3 : 0.029134 + 3 H s : 0.608498 s : 0.608498 + pz : 0.138250 p : 0.540835 + px : 0.142217 + py : 0.260368 + dz2 : 0.037549 d : 0.410594 + dxz : 0.031132 + dyz : 0.117031 + dx2y2 : 0.109904 + dxy : 0.114977 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2837 8.0000 -0.2837 1.8067 1.8067 -0.0000 + 1 N 6.6658 7.0000 0.3342 2.5074 2.5074 -0.0000 + 2 O 8.3037 8.0000 -0.3037 1.6708 1.6708 -0.0000 + 3 H 0.7468 1.0000 0.2532 1.0114 1.0114 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8260 B( 0-O , 3-H ) : 0.9228 B( 1-N , 2-O ) : 1.6029 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.484 sec +Sum of individual times .... 2.239 sec ( 90.1%) + +Fock matrix formation .... 1.836 sec ( 73.9%) +Diagonalization .... 0.179 sec ( 7.2%) +Density matrix formation .... 0.013 sec ( 0.5%) +Population analysis .... 0.051 sec ( 2.0%) +Initial guess .... 0.010 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.2%) +DIIS solution .... 0.152 sec ( 6.1%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.227 sec +Reference energy ... -204.722455456 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.354 sec +AO-integral generation ... 0.143 sec +Half transformation ... 0.079 sec +K-integral sorting ... 5.357 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.022 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.028 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.030 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.349 sec +AO-integral generation ... 0.244 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.153 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.253 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090607364 +EMP2(bb)= -0.090607364 +EMP2(ab)= -0.515093757 + +Initial guess performed in 0.131 sec +E(0) ... -204.722455456 +E(MP2) ... -0.696308485 +Initial E(tot) ... -205.418763941 + ... 0.186669754 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.418763941 -0.696308485 -0.000000000 0.029991014 2.72 0.000002312 + *** Turning on DIIS *** + 1 -205.389822617 -0.667367161 0.028941324 0.011873189 2.71 0.058224965 + 2 -205.409233649 -0.686778193 -0.019411032 0.006796399 2.78 0.061502873 + 3 -205.412921770 -0.690466314 -0.003688121 0.002439813 2.83 0.075977174 + 4 -205.414507991 -0.692052535 -0.001586221 0.001490675 2.77 0.083020868 + 5 -205.415055298 -0.692599842 -0.000547307 0.000740055 2.88 0.088516854 + 6 -205.415154451 -0.692698995 -0.000099153 0.000467593 2.83 0.090958861 + 7 -205.415193677 -0.692738221 -0.000039226 0.000211136 2.90 0.091940401 + 8 -205.415202141 -0.692746684 -0.000008463 0.000111467 2.90 0.092293059 + 9 -205.415198350 -0.692742893 0.000003791 0.000027897 2.81 0.092400049 + 10 -205.415202665 -0.692747209 -0.000004316 0.000010924 2.80 0.092438828 + 11 -205.415200439 -0.692744983 0.000002226 0.000008125 2.77 0.092429414 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.722455456 +E(CORR) ... -0.692744983 +E(TOT) ... -205.415200439 +Singles norm **1/2 ... 0.092429414 ( 0.046214707, 0.046214707) +T1 diagnostic ... 0.021785822 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.062720 + 10a-> 13a 10b-> 13b 0.055046 + 8b-> 13b -1b-> -1b 0.050901 + 8a-> 13a -1a-> -1a 0.050901 + 10a-> 13a 8b-> 13b 0.035380 + 8a-> 13a 10b-> 13b 0.035380 + 11a-> 13a 11b-> 13b 0.029399 + 5a-> 13a 5b-> 13b 0.025317 + 10a-> 13a 10b-> 22b 0.025206 + 10a-> 22a 10b-> 13b 0.025206 + 8a-> 13a 8b-> 22b 0.023812 + 8a-> 22a 8b-> 13b 0.023812 + 10a-> 13a -1a-> -1a 0.023513 + 10b-> 13b -1b-> -1b 0.023513 + 11a-> 26a -1a-> -1a 0.022781 + 11b-> 26b -1b-> -1b 0.022781 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034635656 + alpha-alpha-alpha ... -0.000911238 ( 2.6%) + alpha-alpha-beta ... -0.016406590 ( 47.4%) + alpha-beta -beta ... -0.016406590 ( 47.4%) + beta -beta -beta ... -0.000911238 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034635656 + +Final correlation energy ... -0.727380639 +E(CCSD) ... -205.415200439 +E(CCSD(T)) ... -205.449836096 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.207892625 sqrt= 1.099041685 +W(HF) = 0.827888158 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.194184 0.000000 + 1 N : 0.141479 -0.000000 + 2 O : -0.182650 0.000000 + 3 H : 0.235356 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.791337 s : 3.791337 + pz : 1.465032 p : 4.327064 + px : 1.492765 + py : 1.369267 + dz2 : 0.016698 d : 0.066667 + dxz : 0.011944 + dyz : 0.010251 + dx2y2 : 0.019509 + dxy : 0.008265 + f0 : 0.001281 f : 0.009116 + f+1 : 0.001679 + f-1 : 0.001022 + f+2 : 0.001400 + f-2 : 0.001688 + f+3 : 0.000797 + f-3 : 0.001249 + 1 N s : 3.913005 s : 3.913005 + pz : 0.794439 p : 2.741577 + px : 0.808180 + py : 1.138958 + dz2 : 0.039060 d : 0.171603 + dxz : 0.034648 + dyz : 0.025310 + dx2y2 : 0.041902 + dxy : 0.030683 + f0 : 0.004497 f : 0.032336 + f+1 : 0.002316 + f-1 : 0.005268 + f+2 : 0.002909 + f-2 : 0.005716 + f+3 : 0.004180 + f-3 : 0.007450 + 2 O s : 3.846403 s : 3.846403 + pz : 1.476064 p : 4.243443 + px : 1.411361 + py : 1.356019 + dz2 : 0.014146 d : 0.082691 + dxz : 0.009750 + dyz : 0.020875 + dx2y2 : 0.019650 + dxy : 0.018271 + f0 : 0.001018 f : 0.010113 + f+1 : 0.000858 + f-1 : 0.001840 + f+2 : 0.001224 + f-2 : 0.001417 + f+3 : 0.001596 + f-3 : 0.002161 + 3 H s : 0.660528 s : 0.660528 + pz : 0.032689 p : 0.084725 + px : 0.037481 + py : 0.014555 + dz2 : 0.000091 d : 0.019392 + dxz : -0.000060 + dyz : 0.009584 + dx2y2 : 0.000951 + dxy : 0.008825 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.615236 -0.000000 + 1 N : -0.333090 -0.000000 + 2 O : 0.280494 0.000000 + 3 H : -0.562639 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.116025 s : 3.116025 + pz : 1.281991 p : 3.834314 + px : 1.277055 + py : 1.275268 + dz2 : 0.059335 d : 0.332529 + dxz : 0.095288 + dyz : 0.053603 + dx2y2 : 0.062073 + dxy : 0.062229 + f0 : 0.010864 f : 0.101896 + f+1 : 0.020599 + f-1 : 0.009968 + f+2 : 0.016585 + f-2 : 0.023463 + f+3 : 0.007176 + f-3 : 0.013241 + 1 N s : 3.005567 s : 3.005567 + pz : 0.822192 p : 2.882262 + px : 0.837080 + py : 1.222990 + dz2 : 0.191665 d : 0.983018 + dxz : 0.212589 + dyz : 0.153770 + dx2y2 : 0.236614 + dxy : 0.188380 + f0 : 0.054637 f : 0.462243 + f+1 : 0.048818 + f-1 : 0.060271 + f+2 : 0.055278 + f-2 : 0.086300 + f+3 : 0.066903 + f-3 : 0.090036 + 2 O s : 3.301242 s : 3.301242 + pz : 1.266419 p : 3.940907 + px : 1.255231 + py : 1.419257 + dz2 : 0.055722 d : 0.352933 + dxz : 0.048066 + dyz : 0.058595 + dx2y2 : 0.115001 + dxy : 0.075549 + f0 : 0.009559 f : 0.124425 + f+1 : 0.007167 + f-1 : 0.021580 + f+2 : 0.012985 + f-2 : 0.019543 + f+3 : 0.022881 + f-3 : 0.030710 + 3 H s : 0.614102 s : 0.614102 + pz : 0.139587 p : 0.548425 + px : 0.144226 + py : 0.264612 + dz2 : 0.037200 d : 0.400112 + dxz : 0.030880 + dyz : 0.112464 + dx2y2 : 0.108881 + dxy : 0.110687 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.1942 8.0000 -0.1942 2.1831 1.7344 0.4487 + 1 N 6.8585 7.0000 0.1415 2.7960 2.3264 0.4696 + 2 O 8.1827 8.0000 -0.1827 2.0789 1.5804 0.4985 + 3 H 0.7646 1.0000 0.2354 1.0318 0.9579 0.0740 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7841 B( 0-O , 2-O ) : 0.1000 B( 0-O , 3-H ) : 0.8503 +B( 1-N , 2-O ) : 1.4575 + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 48.852 sec + +Fock Matrix Formation ... 0.227 sec ( 0.5%) +Initial Guess ... 0.131 sec ( 0.3%) +DIIS Solver ... 1.445 sec ( 3.0%) +State Vector Update ... 0.071 sec ( 0.1%) +Sigma-vector construction ... 32.179 sec ( 65.9%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.021 sec ( 0.1% of sigma) + (0-ext) ... 0.060 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.022 sec ( 0.1% of sigma) + (2-ext) ... 0.807 sec ( 2.5% of sigma) + (4-ext) ... 17.650 sec ( 54.8% of sigma) + ... 1.135 sec ( 3.5% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.007 sec ( 0.0% of sigma) + (1-ext) ... 0.093 sec ( 0.3% of sigma) + Fock-dressing ... 1.816 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.065 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 8.250 sec ( 25.6% of sigma) + Pair energies ... 0.004 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.906 sec ( 14.1% of ALL) + I/O of integral and amplitudes ... 0.821 sec ( 11.9% of (T)) + External N**7 contributions ... 3.984 sec ( 57.7% of (T)) + Internal N**7 contributions ... 0.329 sec ( 4.8% of (T)) + N**6 triples energy contributions ... 1.691 sec ( 24.5% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.449836095503 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.007414388 -0.001189677 0.005990862 + 2 N : -0.007305302 -0.001491992 -0.004809291 + 3 O : 0.004361272 0.001578758 0.003549583 + 4 H : -0.004470358 0.001102910 -0.004731153 + +Norm of the cartesian gradient ... 0.015770184 +RMS gradient ... 0.004552460 +MAX gradient ... 0.007414388 + +------- +TIMINGS +------- + +Total numerical gradient time ... 321.132 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 568.29 cm**-1 + 7: 683.78 cm**-1 + 8: 878.72 cm**-1 + 9: 1339.77 cm**-1 + 10: 1649.47 cm**-1 + 11: 3578.34 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 -0.060551 -0.183739 0.205849 0.040379 -0.012820 -0.011008 + 1 -0.026628 -0.086677 -0.126944 0.075114 0.067941 0.060345 + 2 0.162241 0.050323 -0.184168 -0.054736 0.008492 -0.003914 + 3 0.002661 0.077624 -0.326877 0.075048 -0.144982 -0.002029 + 4 0.061127 0.100159 0.216834 -0.010086 -0.500052 0.001265 + 5 -0.109926 0.060052 0.307257 -0.050956 0.079396 0.001949 + 6 0.112779 0.096085 0.126077 -0.065779 0.171711 0.000413 + 7 -0.013249 -0.004060 -0.046251 -0.064294 0.370538 0.000148 + 8 -0.042252 -0.159315 -0.096611 0.052200 -0.111409 -0.000405 + 9 -0.865935 0.312611 -0.726114 -0.639698 -0.507264 0.196351 + 10 -0.216480 0.048387 -0.264129 -0.031583 -0.010920 -0.977722 + 11 -0.376946 0.895452 0.186943 0.748335 0.530227 0.041461 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 568.29 0.015561 78.64 0.008545 (-0.008663 0.012742 -0.091146) + 7: 683.78 0.009170 46.34 0.004185 ( 0.045005 0.024013 0.039789) + 8: 878.72 0.055639 281.17 0.019759 (-0.112312 -0.007483 0.084197) + 9: 1339.77 0.001849 9.34 0.000431 (-0.000689 0.020361 0.003958) + 10: 1649.47 0.028771 145.40 0.005443 (-0.054058 -0.018367 0.046729) + 11: 3578.34 0.006714 33.93 0.000586 ( 0.013688 -0.019076 -0.005852) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 568.29 E(vib) ... 0.11 +freq. 683.78 E(vib) ... 0.07 +freq. 878.72 E(vib) ... 0.04 +freq. 1339.77 E(vib) ... 0.01 +freq. 1649.47 E(vib) ... 0.00 +freq. 3578.34 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.44983609 Eh +Zero point energy ... 0.01981634 Eh 12.43 kcal/mol +Thermal vibrational correction ... 0.00036831 Eh 0.23 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42681891 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00320085 Eh 2.01 kcal/mol +Non-thermal (ZPE) correction 0.01981634 Eh 12.43 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02301718 Eh 14.44 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42681891 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.42587470 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.766831 0.438751 0.379645 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00048263 Eh 0.30 kcal/mol +Rotational entropy ... 0.00987651 Eh 6.20 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02816145 Eh 17.67 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00987651 Eh 6.20 kcal/mol| +| sn= 2 | S(rot)= 0.00922205 Eh 5.79 kcal/mol| +| sn= 3 | S(rot)= 0.00883922 Eh 5.55 kcal/mol| +| sn= 4 | S(rot)= 0.00856760 Eh 5.38 kcal/mol| +| sn= 5 | S(rot)= 0.00835691 Eh 5.24 kcal/mol| +| sn= 6 | S(rot)= 0.00818476 Eh 5.14 kcal/mol| +| sn= 7 | S(rot)= 0.00803922 Eh 5.04 kcal/mol| +| sn= 8 | S(rot)= 0.00791314 Eh 4.97 kcal/mol| +| sn= 9 | S(rot)= 0.00780193 Eh 4.90 kcal/mol| +| sn=10 | S(rot)= 0.00770245 Eh 4.83 kcal/mol| +| sn=11 | S(rot)= 0.00761246 Eh 4.78 kcal/mol| +| sn=12 | S(rot)= 0.00753031 Eh 4.73 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.42587470 Eh +Total entropy correction ... -0.02816145 Eh -17.67 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.45403616 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00420006 Eh -2.64 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.449836094 Eh +Current gradient norm .... 0.015770185 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.034090083 0.149423396 0.218021614 0.460618274 0.537176806 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999929143 +Lowest eigenvalues of augmented Hessian: + -0.000040122 0.147736912 0.217236203 0.460609812 0.537147083 +Length of the computed step .... 0.011904995 +The final length of the internal step .... 0.011904995 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0048601939 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0050234010 RMS(Int)= 0.0048573207 + Iter 1: RMS(Cart)= 0.0000119270 RMS(Int)= 0.0000147593 + Iter 2: RMS(Cart)= 0.0000000423 RMS(Int)= 0.0000000750 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0015319131 0.0001000000 NO + MAX gradient 0.0021693928 0.0003000000 NO + RMS step 0.0048601939 0.0020000000 NO + MAX step 0.0072297742 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0038 Max(Angles) 0.34 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.3992 -0.001164 0.0038 1.4031 + 2. B(O 2,N 1) 1.1879 0.002169 -0.0024 1.1856 + 3. B(H 3,O 0) 0.9798 0.002163 -0.0026 0.9772 + 4. A(N 1,O 0,H 3) 104.47 -0.001151 0.34 104.81 + 5. A(O 0,N 1,O 2) 113.04 -0.001419 0.18 113.22 + 6. D(O 2,N 1,O 0,H 3) 16.36 0.011126 0.00 16.36 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.571493 -0.376205 0.597272 + N 0.400311 -0.600095 -0.389680 + O 0.929791 0.394529 -0.758406 + H -0.758608 0.581771 0.550813 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.079965 -0.710924 1.128681 + 1 N 7.0000 0 14.007 0.756479 -1.134015 -0.736388 + 2 O 8.0000 0 15.999 1.757050 0.745551 -1.433179 + 3 H 1.0000 0 1.008 -1.433562 1.099387 1.040886 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.403069690462 0.00000000 0.00000000 + O 2 1 0 1.185573155774 113.21796110 0.00000000 + H 1 2 3 0.977183447275 104.81024395 16.36363624 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.651417461780 0.00000000 0.00000000 + O 2 1 0 2.240408576142 113.21796110 0.00000000 + H 1 2 3 1.846609097951 104.81024395 16.36363624 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2243 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2718 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.013666341482 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.451e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7226218812 0.000000000000 0.00020256 0.00000591 0.0009130 0.7000 + 1 -204.7226295642 -0.000007682943 0.00016469 0.00000504 0.0007593 0.7000 + ***Turning on DIIS*** + 2 -204.7226359587 -0.000006394570 0.00040399 0.00001350 0.0006198 0.0000 + 3 -204.7223956634 0.000240295343 0.00016387 0.00000559 0.0002277 0.0000 + 4 -204.7227002316 -0.000304568212 0.00007111 0.00000204 0.0000727 0.0000 + 5 -204.7227385108 -0.000038279245 0.00002309 0.00000064 0.0000407 0.0000 + 6 -204.7226015231 0.000136987771 0.00002077 0.00000038 0.0000251 0.0000 + 7 -204.7226642978 -0.000062774729 0.00000598 0.00000017 0.0000075 0.0000 + 8 -204.7226619473 0.000002350519 0.00000280 0.00000010 0.0000037 0.0000 + 9 -204.7226483827 0.000013564574 0.00000234 0.00000007 0.0000021 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 10 CYCLES * + ***************************************************** + +Total Energy : -204.72266049 Eh -5570.78681 eV + Last Energy change ... -1.2102e-05 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.3305e-06 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.204 sec +Reference energy ... -204.722657538 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.382 sec +AO-integral generation ... 0.143 sec +Half transformation ... 0.079 sec +K-integral sorting ... 5.379 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.038 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.030 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.353 sec +AO-integral generation ... 0.248 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.152 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.252 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090563803 +EMP2(bb)= -0.090563803 +EMP2(ab)= -0.514960364 + +Initial guess performed in 0.133 sec +E(0) ... -204.722657538 +E(MP2) ... -0.696087970 +Initial E(tot) ... -205.418745508 + ... 0.186537588 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.418745508 -0.696087970 -0.000000000 0.029747365 2.69 0.000002484 + *** Turning on DIIS *** + 1 -205.389889328 -0.667231790 0.028856180 0.011766179 2.70 0.058187699 + 2 -205.409278776 -0.686621238 -0.019389448 0.006727536 2.77 0.061443604 + 3 -205.412962400 -0.690304863 -0.003683624 0.002402740 2.82 0.075914119 + 4 -205.414545722 -0.691888184 -0.001583321 0.001471048 2.78 0.082954497 + 5 -205.415094813 -0.692437275 -0.000549091 0.000758694 2.88 0.088490219 + 6 -205.415195421 -0.692537883 -0.000100609 0.000476132 2.83 0.090977044 + 7 -205.415235414 -0.692577876 -0.000039993 0.000211742 2.87 0.091985880 + 8 -205.415244180 -0.692586642 -0.000008766 0.000111400 2.87 0.092347793 + 9 -205.415240308 -0.692582770 0.000003873 0.000027758 2.81 0.092455791 + 10 -205.415244690 -0.692587153 -0.000004383 0.000011275 2.75 0.092495299 + 11 -205.415242437 -0.692584899 0.000002253 0.000008377 2.75 0.092485926 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.722657538 +E(CORR) ... -0.692584899 +E(TOT) ... -205.415242437 +Singles norm **1/2 ... 0.092485926 ( 0.046242963, 0.046242963) +T1 diagnostic ... 0.021799142 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.063356 + 10a-> 13a 10b-> 13b 0.053978 + 8b-> 13b -1b-> -1b 0.050360 + 8a-> 13a -1a-> -1a 0.050360 + 8a-> 13a 10b-> 13b 0.035264 + 10a-> 13a 8b-> 13b 0.035264 + 11a-> 13a 11b-> 13b 0.029397 + 5a-> 13a 5b-> 13b 0.025373 + 10a-> 22a 10b-> 13b 0.024804 + 10a-> 13a 10b-> 22b 0.024804 + 10a-> 13a -1a-> -1a 0.024560 + 10b-> 13b -1b-> -1b 0.024560 + 8a-> 22a 8b-> 13b 0.024171 + 8a-> 13a 8b-> 22b 0.024171 + 11b-> 26b -1b-> -1b 0.023293 + 11a-> 26a -1a-> -1a 0.023293 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034613847 + alpha-alpha-alpha ... -0.000910504 ( 2.6%) + alpha-alpha-beta ... -0.016396419 ( 47.4%) + alpha-beta -beta ... -0.016396419 ( 47.4%) + beta -beta -beta ... -0.000910504 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034613847 + +Final correlation energy ... -0.727198746 +E(CCSD) ... -205.415242437 +E(CCSD(T)) ... -205.449856284 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.207832651 sqrt= 1.099014400 +W(HF) = 0.827929266 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 48.366 sec + +Fock Matrix Formation ... 0.204 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.3%) +DIIS Solver ... 1.450 sec ( 3.0%) +State Vector Update ... 0.070 sec ( 0.1%) +Sigma-vector construction ... 31.998 sec ( 66.2%) + <0|H|D> ... 0.003 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (0-ext) ... 0.058 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.022 sec ( 0.1% of sigma) + (2-ext) ... 0.791 sec ( 2.5% of sigma) + (4-ext) ... 17.782 sec ( 55.6% of sigma) + ... 1.154 sec ( 3.6% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.007 sec ( 0.0% of sigma) + (1-ext) ... 0.092 sec ( 0.3% of sigma) + Fock-dressing ... 1.796 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.063 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 7.977 sec ( 24.9% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.655 sec ( 13.8% of ALL) + I/O of integral and amplitudes ... 0.634 sec ( 9.5% of (T)) + External N**7 contributions ... 3.885 sec ( 58.4% of (T)) + Internal N**7 contributions ... 0.308 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.547 sec ( 23.2% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.449856283852 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.006439263 0.001076018 0.006075365 + 2 N : -0.005714025 0.000599691 -0.005743728 + 3 O : 0.003675363 -0.000592355 0.003779501 + 4 H : -0.004400601 -0.001083354 -0.004111138 + +Norm of the cartesian gradient ... 0.014529842 +RMS gradient ... 0.004194404 +MAX gradient ... 0.006439263 + +------- +TIMINGS +------- + +Total numerical gradient time ... 322.155 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.449856284 Eh +Current gradient norm .... 0.014529842 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999988 +Lowest eigenvalues of augmented Hessian: + -0.000000007 0.147662568 0.214456491 0.462635865 0.538444285 +Length of the computed step .... 0.000158033 +The final length of the internal step .... 0.000158033 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0000645169 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0000752688 RMS(Int)= 0.0000645172 + Iter 1: RMS(Cart)= 0.0000000015 RMS(Int)= 0.0000000026 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000201895 0.0000050000 NO + RMS gradient 0.0000229787 0.0001000000 YES + MAX gradient 0.0000315155 0.0003000000 YES + RMS step 0.0000645169 0.0020000000 YES + MAX step 0.0001226188 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4031 -0.000032 0.0001 1.4031 + 2. B(O 2,N 1) 1.1856 -0.000031 0.0000 1.1856 + 3. B(H 3,O 0) 0.9772 -0.000024 0.0000 0.9772 + 4. A(N 1,O 0,H 3) 104.81 -0.000020 0.00 104.82 + 5. A(O 0,N 1,O 2) 113.22 -0.000015 0.00 113.22 + 6. D(O 2,N 1,O 0,H 3) 16.36 0.010923 0.00 16.36 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.571510 -0.376200 0.597283 + N 0.400347 -0.600103 -0.389706 + O 0.929849 0.394511 -0.758454 + H -0.758686 0.581791 0.550877 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.079997 -0.710914 1.128701 + 1 N 7.0000 0 14.007 0.756547 -1.134029 -0.736438 + 2 O 8.0000 0 15.999 1.757159 0.745518 -1.433270 + 3 H 1.0000 0 1.008 -1.433708 1.099426 1.041007 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.403134577524 0.00000000 0.00000000 + O 2 1 0 1.185581175060 113.21943480 0.00000000 + H 1 2 3 0.977207481608 104.81503258 16.36363624 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.651540080556 0.00000000 0.00000000 + O 2 1 0 2.240423730395 113.21943480 0.00000000 + H 1 2 3 1.846654516258 104.81503258 16.36363624 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2243 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2718 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.011532296475 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 70.0115322965 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.452e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7226495992 0.000000000000 0.00000251 0.00000007 0.0000119 0.7000 + 1 -204.7226495998 -0.000000000641 0.00000190 0.00000006 0.0000087 0.7000 + ***Turning on DIIS*** + 2 -204.7226496004 -0.000000000560 0.00000451 0.00000016 0.0000063 0.0000 + 3 -204.7226566436 -0.000007043202 0.00000225 0.00000007 0.0000024 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 4 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72264887 Eh -5570.78649 eV + +Components: +Nuclear Repulsion : 70.01153230 Eh 1905.11065 eV +Electronic Energy : -274.73418117 Eh -7475.89714 eV +One Electron Energy: -419.60559216 Eh -11418.04865 eV +Two Electron Energy: 144.87141100 Eh 3942.15151 eV + +Virial components: +Potential Energy : -408.97113810 Eh -11128.67044 eV +Kinetic Energy : 204.24848923 Eh 5557.88395 eV +Virial Ratio : 2.00232148 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 7.7738e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 9.5479e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.7287e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.9200e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.667310 -562.3861 + 1 1.0000 -20.649170 -561.8925 + 2 1.0000 -15.802840 -430.0171 + 3 1.0000 -1.608552 -43.7709 + 4 1.0000 -1.406419 -38.2706 + 5 1.0000 -0.966607 -26.3027 + 6 1.0000 -0.776270 -21.1234 + 7 1.0000 -0.743060 -20.2197 + 8 1.0000 -0.690473 -18.7887 + 9 1.0000 -0.612892 -16.6776 + 10 1.0000 -0.533396 -14.5144 + 11 1.0000 -0.474388 -12.9087 + 12 0.0000 0.031576 0.8592 + 13 0.0000 0.076525 2.0823 + 14 0.0000 0.095089 2.5875 + 15 0.0000 0.112812 3.0698 + 16 0.0000 0.124881 3.3982 + 17 0.0000 0.142304 3.8723 + 18 0.0000 0.157691 4.2910 + 19 0.0000 0.169390 4.6093 + 20 0.0000 0.183965 5.0060 + 21 0.0000 0.195215 5.3121 + 22 0.0000 0.205244 5.5850 + 23 0.0000 0.233022 6.3409 + 24 0.0000 0.252412 6.8685 + 25 0.0000 0.300964 8.1896 + 26 0.0000 0.312974 8.5165 + 27 0.0000 0.344133 9.3643 + 28 0.0000 0.351552 9.5662 + 29 0.0000 0.398626 10.8472 + 30 0.0000 0.435397 11.8478 + 31 0.0000 0.513287 13.9673 + 32 0.0000 0.519425 14.1343 + 33 0.0000 0.535030 14.5589 + 34 0.0000 0.563038 15.3211 + 35 0.0000 0.618037 16.8176 + 36 0.0000 0.637601 17.3500 + 37 0.0000 0.661993 18.0138 + 38 0.0000 0.685658 18.6577 + 39 0.0000 0.699202 19.0262 + 40 0.0000 0.734176 19.9779 + 41 0.0000 0.755424 20.5561 + 42 0.0000 0.759507 20.6672 + 43 0.0000 0.791092 21.5267 + 44 0.0000 0.794887 21.6300 + 45 0.0000 0.846176 23.0256 + 46 0.0000 0.848300 23.0834 + 47 0.0000 0.873175 23.7603 + 48 0.0000 0.919859 25.0306 + 49 0.0000 0.937378 25.5074 + 50 0.0000 0.957064 26.0430 + 51 0.0000 1.002927 27.2910 + 52 0.0000 1.024793 27.8860 + 53 0.0000 1.063697 28.9447 + 54 0.0000 1.081720 29.4351 + 55 0.0000 1.085824 29.5468 + 56 0.0000 1.180237 32.1159 + 57 0.0000 1.203330 32.7443 + 58 0.0000 1.240508 33.7559 + 59 0.0000 1.272932 34.6382 + 60 0.0000 1.346991 36.6535 + 61 0.0000 1.410364 38.3780 + 62 0.0000 1.453091 39.5406 + 63 0.0000 1.501408 40.8554 + 64 0.0000 1.543822 42.0095 + 65 0.0000 1.557287 42.3759 + 66 0.0000 1.590719 43.2857 + 67 0.0000 1.620660 44.1004 + 68 0.0000 1.657309 45.0977 + 69 0.0000 1.753781 47.7228 + 70 0.0000 1.790262 48.7155 + 71 0.0000 1.822690 49.5979 + 72 0.0000 1.902040 51.7572 + 73 0.0000 1.930038 52.5190 + 74 0.0000 1.988366 54.1062 + 75 0.0000 2.004689 54.5504 + 76 0.0000 2.037408 55.4407 + 77 0.0000 2.110386 57.4265 + 78 0.0000 2.157388 58.7055 + 79 0.0000 2.177885 59.2633 + 80 0.0000 2.282351 62.1059 + 81 0.0000 2.309449 62.8433 + 82 0.0000 2.360770 64.2398 + 83 0.0000 2.385915 64.9241 + 84 0.0000 2.434752 66.2530 + 85 0.0000 2.447302 66.5945 + 86 0.0000 2.467958 67.1565 + 87 0.0000 2.521206 68.6055 + 88 0.0000 2.532438 68.9111 + 89 0.0000 2.556518 69.5664 + 90 0.0000 2.575880 70.0933 + 91 0.0000 2.629165 71.5432 + 92 0.0000 2.668484 72.6132 + 93 0.0000 2.684554 73.0504 + 94 0.0000 2.735611 74.4398 + 95 0.0000 2.804024 76.3014 + 96 0.0000 2.888637 78.6038 + 97 0.0000 2.968257 80.7704 + 98 0.0000 2.982361 81.1542 + 99 0.0000 3.058027 83.2132 + 100 0.0000 3.147621 85.6511 + 101 0.0000 3.156366 85.8891 + 102 0.0000 3.219957 87.6195 + 103 0.0000 3.516390 95.6858 + 104 0.0000 3.735366 101.6445 + 105 0.0000 3.860120 105.0392 + 106 0.0000 4.019161 109.3669 + 107 0.0000 4.149737 112.9201 + 108 0.0000 4.177323 113.6708 + 109 0.0000 4.260231 115.9268 + 110 0.0000 4.360124 118.6450 + 111 0.0000 4.420139 120.2781 + 112 0.0000 4.515711 122.8787 + 113 0.0000 4.564904 124.2173 + 114 0.0000 4.696384 127.7951 + 115 0.0000 4.833218 131.5185 + 116 0.0000 4.880267 132.7988 + 117 0.0000 4.898958 133.3074 + 118 0.0000 4.944459 134.5456 + 119 0.0000 5.002565 136.1267 + 120 0.0000 5.070494 137.9752 + 121 0.0000 5.110149 139.0542 + 122 0.0000 5.198061 141.4464 + 123 0.0000 5.223255 142.1320 + 124 0.0000 5.231514 142.3567 + 125 0.0000 5.298194 144.1712 + 126 0.0000 5.389970 146.6685 + 127 0.0000 5.482257 149.1798 + 128 0.0000 5.550230 151.0294 + 129 0.0000 5.673818 154.3924 + 130 0.0000 5.785583 157.4337 + 131 0.0000 5.926113 161.2577 + 132 0.0000 6.180904 168.1910 + 133 0.0000 6.417301 174.6236 + 134 0.0000 6.514111 177.2580 + 135 0.0000 6.555384 178.3811 + 136 0.0000 6.681374 181.8094 + 137 0.0000 6.710126 182.5918 + 138 0.0000 6.768255 184.1736 + 139 0.0000 6.821233 185.6152 + 140 0.0000 6.942589 188.9174 + 141 0.0000 7.100143 193.2047 + 142 0.0000 7.135317 194.1618 + 143 0.0000 7.154277 194.6778 + 144 0.0000 7.172781 195.1813 + 145 0.0000 7.234802 196.8690 + 146 0.0000 7.283731 198.2004 + 147 0.0000 7.312451 198.9819 + 148 0.0000 7.402008 201.4189 + 149 0.0000 7.445670 202.6070 + 150 0.0000 7.474692 203.3967 + 151 0.0000 7.503730 204.1869 + 152 0.0000 7.609468 207.0642 + 153 0.0000 7.677436 208.9136 + 154 0.0000 7.859928 213.8795 + 155 0.0000 7.920232 215.5205 + 156 0.0000 8.287284 225.5085 + 157 0.0000 8.310421 226.1380 + 158 0.0000 14.183781 385.9603 + 159 0.0000 15.121923 411.4884 + 160 0.0000 15.632144 425.3723 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.667310 -562.3861 + 1 1.0000 -20.649170 -561.8925 + 2 1.0000 -15.802840 -430.0171 + 3 1.0000 -1.608552 -43.7709 + 4 1.0000 -1.406419 -38.2706 + 5 1.0000 -0.966607 -26.3027 + 6 1.0000 -0.776270 -21.1234 + 7 1.0000 -0.743060 -20.2197 + 8 1.0000 -0.690473 -18.7887 + 9 1.0000 -0.612892 -16.6776 + 10 1.0000 -0.533396 -14.5144 + 11 1.0000 -0.474388 -12.9087 + 12 0.0000 0.031576 0.8592 + 13 0.0000 0.076525 2.0823 + 14 0.0000 0.095089 2.5875 + 15 0.0000 0.112812 3.0698 + 16 0.0000 0.124881 3.3982 + 17 0.0000 0.142304 3.8723 + 18 0.0000 0.157691 4.2910 + 19 0.0000 0.169390 4.6093 + 20 0.0000 0.183965 5.0060 + 21 0.0000 0.195215 5.3121 + 22 0.0000 0.205244 5.5850 + 23 0.0000 0.233022 6.3409 + 24 0.0000 0.252412 6.8685 + 25 0.0000 0.300964 8.1896 + 26 0.0000 0.312974 8.5165 + 27 0.0000 0.344133 9.3643 + 28 0.0000 0.351552 9.5662 + 29 0.0000 0.398626 10.8472 + 30 0.0000 0.435397 11.8478 + 31 0.0000 0.513287 13.9673 + 32 0.0000 0.519425 14.1343 + 33 0.0000 0.535030 14.5589 + 34 0.0000 0.563038 15.3211 + 35 0.0000 0.618037 16.8176 + 36 0.0000 0.637601 17.3500 + 37 0.0000 0.661993 18.0138 + 38 0.0000 0.685658 18.6577 + 39 0.0000 0.699202 19.0262 + 40 0.0000 0.734176 19.9779 + 41 0.0000 0.755424 20.5561 + 42 0.0000 0.759507 20.6672 + 43 0.0000 0.791092 21.5267 + 44 0.0000 0.794887 21.6300 + 45 0.0000 0.846176 23.0256 + 46 0.0000 0.848300 23.0834 + 47 0.0000 0.873175 23.7603 + 48 0.0000 0.919859 25.0306 + 49 0.0000 0.937378 25.5074 + 50 0.0000 0.957064 26.0430 + 51 0.0000 1.002927 27.2910 + 52 0.0000 1.024793 27.8860 + 53 0.0000 1.063697 28.9447 + 54 0.0000 1.081720 29.4351 + 55 0.0000 1.085824 29.5468 + 56 0.0000 1.180237 32.1159 + 57 0.0000 1.203330 32.7443 + 58 0.0000 1.240508 33.7559 + 59 0.0000 1.272932 34.6382 + 60 0.0000 1.346991 36.6535 + 61 0.0000 1.410364 38.3780 + 62 0.0000 1.453091 39.5406 + 63 0.0000 1.501408 40.8554 + 64 0.0000 1.543822 42.0095 + 65 0.0000 1.557287 42.3759 + 66 0.0000 1.590719 43.2857 + 67 0.0000 1.620660 44.1004 + 68 0.0000 1.657309 45.0977 + 69 0.0000 1.753781 47.7228 + 70 0.0000 1.790262 48.7155 + 71 0.0000 1.822690 49.5979 + 72 0.0000 1.902040 51.7572 + 73 0.0000 1.930038 52.5190 + 74 0.0000 1.988366 54.1062 + 75 0.0000 2.004689 54.5504 + 76 0.0000 2.037408 55.4407 + 77 0.0000 2.110386 57.4265 + 78 0.0000 2.157388 58.7055 + 79 0.0000 2.177885 59.2633 + 80 0.0000 2.282351 62.1059 + 81 0.0000 2.309449 62.8433 + 82 0.0000 2.360770 64.2398 + 83 0.0000 2.385915 64.9241 + 84 0.0000 2.434752 66.2530 + 85 0.0000 2.447302 66.5945 + 86 0.0000 2.467958 67.1565 + 87 0.0000 2.521206 68.6055 + 88 0.0000 2.532438 68.9111 + 89 0.0000 2.556518 69.5664 + 90 0.0000 2.575880 70.0933 + 91 0.0000 2.629165 71.5432 + 92 0.0000 2.668484 72.6132 + 93 0.0000 2.684554 73.0504 + 94 0.0000 2.735611 74.4398 + 95 0.0000 2.804024 76.3014 + 96 0.0000 2.888637 78.6038 + 97 0.0000 2.968257 80.7704 + 98 0.0000 2.982361 81.1542 + 99 0.0000 3.058027 83.2132 + 100 0.0000 3.147621 85.6511 + 101 0.0000 3.156366 85.8891 + 102 0.0000 3.219957 87.6195 + 103 0.0000 3.516390 95.6858 + 104 0.0000 3.735366 101.6445 + 105 0.0000 3.860120 105.0392 + 106 0.0000 4.019161 109.3669 + 107 0.0000 4.149737 112.9201 + 108 0.0000 4.177323 113.6708 + 109 0.0000 4.260231 115.9268 + 110 0.0000 4.360124 118.6450 + 111 0.0000 4.420139 120.2781 + 112 0.0000 4.515711 122.8787 + 113 0.0000 4.564904 124.2173 + 114 0.0000 4.696384 127.7951 + 115 0.0000 4.833218 131.5185 + 116 0.0000 4.880267 132.7988 + 117 0.0000 4.898958 133.3074 + 118 0.0000 4.944459 134.5456 + 119 0.0000 5.002565 136.1267 + 120 0.0000 5.070494 137.9752 + 121 0.0000 5.110149 139.0542 + 122 0.0000 5.198061 141.4464 + 123 0.0000 5.223255 142.1320 + 124 0.0000 5.231514 142.3567 + 125 0.0000 5.298194 144.1712 + 126 0.0000 5.389970 146.6685 + 127 0.0000 5.482257 149.1798 + 128 0.0000 5.550230 151.0294 + 129 0.0000 5.673818 154.3924 + 130 0.0000 5.785583 157.4337 + 131 0.0000 5.926113 161.2577 + 132 0.0000 6.180904 168.1910 + 133 0.0000 6.417301 174.6236 + 134 0.0000 6.514111 177.2580 + 135 0.0000 6.555384 178.3811 + 136 0.0000 6.681374 181.8094 + 137 0.0000 6.710126 182.5918 + 138 0.0000 6.768255 184.1736 + 139 0.0000 6.821233 185.6152 + 140 0.0000 6.942589 188.9174 + 141 0.0000 7.100143 193.2047 + 142 0.0000 7.135317 194.1618 + 143 0.0000 7.154277 194.6778 + 144 0.0000 7.172781 195.1813 + 145 0.0000 7.234802 196.8690 + 146 0.0000 7.283731 198.2004 + 147 0.0000 7.312451 198.9819 + 148 0.0000 7.402008 201.4189 + 149 0.0000 7.445670 202.6070 + 150 0.0000 7.474692 203.3967 + 151 0.0000 7.503730 204.1869 + 152 0.0000 7.609468 207.0642 + 153 0.0000 7.677436 208.9136 + 154 0.0000 7.859928 213.8795 + 155 0.0000 7.920232 215.5205 + 156 0.0000 8.287284 225.5085 + 157 0.0000 8.310421 226.1380 + 158 0.0000 14.183781 385.9603 + 159 0.0000 15.121923 411.4884 + 160 0.0000 15.632144 425.3723 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.283902 0.000000 + 1 N : 0.335764 0.000000 + 2 O : -0.301262 0.000000 + 3 H : 0.249401 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.804032 s : 3.804032 + pz : 1.510051 p : 4.437625 + px : 1.534045 + py : 1.393529 + dz2 : 0.009942 d : 0.036818 + dxz : 0.007687 + dyz : 0.003105 + dx2y2 : 0.015214 + dxy : 0.000871 + f0 : 0.000665 f : 0.005427 + f+1 : 0.001328 + f-1 : 0.000385 + f+2 : 0.001012 + f-2 : 0.001266 + f+3 : 0.000151 + f-3 : 0.000620 + 1 N s : 3.862589 s : 3.862589 + pz : 0.712057 p : 2.624325 + px : 0.724917 + py : 1.187351 + dz2 : 0.031515 d : 0.144105 + dxz : 0.028635 + dyz : 0.021887 + dx2y2 : 0.034338 + dxy : 0.027731 + f0 : 0.004653 f : 0.033218 + f+1 : 0.002251 + f-1 : 0.005222 + f+2 : 0.003188 + f-2 : 0.005803 + f+3 : 0.004339 + f-3 : 0.007763 + 2 O s : 3.858575 s : 3.858575 + pz : 1.530704 p : 4.375361 + px : 1.458779 + py : 1.385878 + dz2 : 0.008932 d : 0.059881 + dxz : 0.003202 + dyz : 0.018291 + dx2y2 : 0.013291 + dxy : 0.016166 + f0 : 0.000546 f : 0.007445 + f+1 : 0.000333 + f-1 : 0.001544 + f+2 : 0.000806 + f-2 : 0.000988 + f+3 : 0.001302 + f-3 : 0.001927 + 3 H s : 0.645682 s : 0.645682 + pz : 0.029001 p : 0.083745 + px : 0.034180 + py : 0.020565 + dz2 : 0.000089 d : 0.021172 + dxz : -0.000665 + dyz : 0.010645 + dx2y2 : 0.001551 + dxy : 0.009551 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.601514 0.000000 + 1 N : -0.282502 0.000000 + 2 O : 0.244799 0.000000 + 3 H : -0.563810 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.107051 s : 3.107051 + pz : 1.307590 p : 3.898945 + px : 1.299097 + py : 1.292257 + dz2 : 0.051026 d : 0.299020 + dxz : 0.088912 + dyz : 0.048046 + dx2y2 : 0.054970 + dxy : 0.056066 + f0 : 0.009038 f : 0.093471 + f+1 : 0.018572 + f-1 : 0.008991 + f+2 : 0.015229 + f-2 : 0.023340 + f+3 : 0.006250 + f-3 : 0.012050 + 1 N s : 3.000960 s : 3.000960 + pz : 0.776074 p : 2.830484 + px : 0.789318 + py : 1.265092 + dz2 : 0.191219 d : 0.978360 + dxz : 0.205374 + dyz : 0.156914 + dx2y2 : 0.238235 + dxy : 0.186619 + f0 : 0.056505 f : 0.472699 + f+1 : 0.050769 + f-1 : 0.061458 + f+2 : 0.055539 + f-2 : 0.088434 + f+3 : 0.066257 + f-3 : 0.093737 + 2 O s : 3.298967 s : 3.298967 + pz : 1.297033 p : 4.020939 + px : 1.283129 + py : 1.440777 + dz2 : 0.048291 d : 0.319635 + dxz : 0.043067 + dyz : 0.050214 + dx2y2 : 0.109565 + dxy : 0.068497 + f0 : 0.008553 f : 0.115659 + f+1 : 0.005874 + f-1 : 0.020303 + f+2 : 0.011034 + f-2 : 0.019074 + f+3 : 0.021775 + f-3 : 0.029046 + 3 H s : 0.610554 s : 0.610554 + pz : 0.139048 p : 0.543408 + px : 0.143076 + py : 0.261284 + dz2 : 0.037289 d : 0.409848 + dxz : 0.030610 + dyz : 0.116993 + dx2y2 : 0.109943 + dxy : 0.115013 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2839 8.0000 -0.2839 1.8091 1.8091 0.0000 + 1 N 6.6642 7.0000 0.3358 2.5077 2.5077 -0.0000 + 2 O 8.3013 8.0000 -0.3013 1.6737 1.6737 -0.0000 + 3 H 0.7506 1.0000 0.2494 1.0149 1.0149 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8242 B( 0-O , 3-H ) : 0.9265 B( 1-N , 2-O ) : 1.6052 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.878 sec +Sum of individual times .... 0.652 sec ( 74.2%) + +Fock matrix formation .... 0.501 sec ( 57.1%) +Diagonalization .... 0.055 sec ( 6.3%) +Density matrix formation .... 0.004 sec ( 0.5%) +Population analysis .... 0.045 sec ( 5.1%) +Initial guess .... 0.009 sec ( 1.1%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.6%) +DIIS solution .... 0.037 sec ( 4.3%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.204 sec +Reference energy ... -204.722649604 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.354 sec +AO-integral generation ... 0.142 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.357 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.024 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.037 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.030 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.353 sec +AO-integral generation ... 0.247 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.158 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.249 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090564632 +EMP2(bb)= -0.090564632 +EMP2(ab)= -0.514966390 + +Initial guess performed in 0.132 sec +E(0) ... -204.722649604 +E(MP2) ... -0.696095653 +Initial E(tot) ... -205.418745257 + ... 0.186545376 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.418745257 -0.696095653 -0.000000000 0.029747727 2.74 0.000001863 + *** Turning on DIIS *** + 1 -205.389885598 -0.667235995 0.028859658 0.011766633 2.73 0.058191842 + 2 -205.409276416 -0.686626812 -0.019390817 0.006727700 2.78 0.061447199 + 3 -205.412960316 -0.690310712 -0.003683900 0.002402738 2.87 0.075919045 + 4 -205.414543821 -0.691894218 -0.001583506 0.001471107 2.84 0.082960156 + 5 -205.415093034 -0.692443431 -0.000549213 0.000758927 2.92 0.088496992 + 6 -205.415193670 -0.692544066 -0.000100636 0.000476281 2.83 0.090984514 + 7 -205.415233678 -0.692584075 -0.000040008 0.000211801 2.85 0.091993767 + 8 -205.415242450 -0.692592846 -0.000008771 0.000111434 2.91 0.092355841 + 9 -205.415238576 -0.692588972 0.000003874 0.000027770 2.83 0.092463882 + 10 -205.415242961 -0.692593357 -0.000004385 0.000011256 2.84 0.092503407 + 11 -205.415240707 -0.692591103 0.000002254 0.000008363 2.80 0.092494031 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.722649604 +E(CORR) ... -0.692591103 +E(TOT) ... -205.415240707 +Singles norm **1/2 ... 0.092494031 ( 0.046247015, 0.046247015) +T1 diagnostic ... 0.021801052 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.063367 + 10a-> 13a 10b-> 13b 0.053973 + 8a-> 13a -1a-> -1a 0.050363 + 8b-> 13b -1b-> -1b 0.050363 + 8a-> 13a 10b-> 13b 0.035267 + 10a-> 13a 8b-> 13b 0.035267 + 11a-> 13a 11b-> 13b 0.029397 + 5a-> 13a 5b-> 13b 0.025376 + 10a-> 22a 10b-> 13b 0.024800 + 10a-> 13a 10b-> 22b 0.024800 + 10b-> 13b -1b-> -1b 0.024568 + 10a-> 13a -1a-> -1a 0.024568 + 8a-> 13a 8b-> 22b 0.024173 + 8a-> 22a 8b-> 13b 0.024173 + 11b-> 26b -1b-> -1b 0.023304 + 11a-> 26a -1a-> -1a 0.023304 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034615583 + alpha-alpha-alpha ... -0.000910529 ( 2.6%) + alpha-alpha-beta ... -0.016397262 ( 47.4%) + alpha-beta -beta ... -0.016397262 ( 47.4%) + beta -beta -beta ... -0.000910529 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034615583 + +Final correlation energy ... -0.727206686 +E(CCSD) ... -205.415240707 +E(CCSD(T)) ... -205.449856289 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.207843328 sqrt= 1.099019258 +W(HF) = 0.827921947 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.195230 -0.000000 + 1 N : 0.143280 0.000000 + 2 O : -0.180522 -0.000000 + 3 H : 0.232473 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.791260 s : 3.791260 + pz : 1.466656 p : 4.328394 + px : 1.493099 + py : 1.368640 + dz2 : 0.016557 d : 0.066511 + dxz : 0.011964 + dyz : 0.010285 + dx2y2 : 0.019345 + dxy : 0.008359 + f0 : 0.001274 f : 0.009066 + f+1 : 0.001671 + f-1 : 0.001018 + f+2 : 0.001385 + f-2 : 0.001686 + f+3 : 0.000797 + f-3 : 0.001236 + 1 N s : 3.912783 s : 3.912783 + pz : 0.793848 p : 2.740414 + px : 0.807831 + py : 1.138735 + dz2 : 0.038877 d : 0.171293 + dxz : 0.034816 + dyz : 0.025215 + dx2y2 : 0.041820 + dxy : 0.030566 + f0 : 0.004451 f : 0.032230 + f+1 : 0.002306 + f-1 : 0.005260 + f+2 : 0.002897 + f-2 : 0.005721 + f+3 : 0.004166 + f-3 : 0.007428 + 2 O s : 3.846276 s : 3.846276 + pz : 1.473043 p : 4.240964 + px : 1.409448 + py : 1.358473 + dz2 : 0.014242 d : 0.083152 + dxz : 0.009865 + dyz : 0.020905 + dx2y2 : 0.019833 + dxy : 0.018307 + f0 : 0.001016 f : 0.010130 + f+1 : 0.000854 + f-1 : 0.001847 + f+2 : 0.001219 + f-2 : 0.001429 + f+3 : 0.001592 + f-3 : 0.002172 + 3 H s : 0.662391 s : 0.662391 + pz : 0.033282 p : 0.085503 + px : 0.037972 + py : 0.014249 + dz2 : 0.000090 d : 0.019632 + dxz : -0.000058 + dyz : 0.009696 + dx2y2 : 0.001015 + dxy : 0.008890 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.617064 -0.000000 + 1 N : -0.331592 0.000000 + 2 O : 0.280785 -0.000000 + 3 H : -0.566257 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.115828 s : 3.115828 + pz : 1.281751 p : 3.835508 + px : 1.276555 + py : 1.277202 + dz2 : 0.058818 d : 0.330682 + dxz : 0.095128 + dyz : 0.053093 + dx2y2 : 0.061742 + dxy : 0.061901 + f0 : 0.010719 f : 0.100919 + f+1 : 0.020425 + f-1 : 0.009855 + f+2 : 0.016456 + f-2 : 0.023201 + f+3 : 0.007166 + f-3 : 0.013097 + 1 N s : 3.006500 s : 3.006500 + pz : 0.821292 p : 2.882126 + px : 0.836934 + py : 1.223900 + dz2 : 0.191085 d : 0.982208 + dxz : 0.213197 + dyz : 0.153108 + dx2y2 : 0.236898 + dxy : 0.187919 + f0 : 0.054145 f : 0.460758 + f+1 : 0.048650 + f-1 : 0.060170 + f+2 : 0.055093 + f-2 : 0.086154 + f+3 : 0.066649 + f-3 : 0.089897 + 2 O s : 3.300959 s : 3.300959 + pz : 1.264327 p : 3.940021 + px : 1.254295 + py : 1.421400 + dz2 : 0.055804 d : 0.353605 + dxz : 0.048224 + dyz : 0.058681 + dx2y2 : 0.115026 + dxy : 0.075870 + f0 : 0.009546 f : 0.124629 + f+1 : 0.007229 + f-1 : 0.021574 + f+2 : 0.013073 + f-2 : 0.019593 + f+3 : 0.022980 + f-3 : 0.030634 + 3 H s : 0.615904 s : 0.615904 + pz : 0.140385 p : 0.551014 + px : 0.145069 + py : 0.265559 + dz2 : 0.036973 d : 0.399340 + dxz : 0.030392 + dyz : 0.112375 + dx2y2 : 0.108898 + dxy : 0.110702 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.1952 8.0000 -0.1952 2.1854 1.7364 0.4490 + 1 N 6.8567 7.0000 0.1433 2.7960 2.3266 0.4695 + 2 O 8.1805 8.0000 -0.1805 2.0808 1.5831 0.4977 + 3 H 0.7675 1.0000 0.2325 1.0342 0.9603 0.0740 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7823 B( 0-O , 2-O ) : 0.1006 B( 0-O , 3-H ) : 0.8536 +B( 1-N , 2-O ) : 1.4600 + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 48.981 sec + +Fock Matrix Formation ... 0.204 sec ( 0.4%) +Initial Guess ... 0.132 sec ( 0.3%) +DIIS Solver ... 1.457 sec ( 3.0%) +State Vector Update ... 0.070 sec ( 0.1%) +Sigma-vector construction ... 32.425 sec ( 66.2%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (0-ext) ... 0.058 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.022 sec ( 0.1% of sigma) + (2-ext) ... 0.793 sec ( 2.4% of sigma) + (4-ext) ... 18.094 sec ( 55.8% of sigma) + ... 1.194 sec ( 3.7% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.007 sec ( 0.0% of sigma) + (1-ext) ... 0.092 sec ( 0.3% of sigma) + Fock-dressing ... 1.777 sec ( 5.5% of sigma) + (ik|jl)-dressing ... 0.063 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 8.056 sec ( 24.8% of sigma) + Pair energies ... 0.004 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.796 sec ( 13.9% of ALL) + I/O of integral and amplitudes ... 0.671 sec ( 9.9% of (T)) + External N**7 contributions ... 3.919 sec ( 57.7% of (T)) + Internal N**7 contributions ... 0.312 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.552 sec ( 22.8% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.449856289288 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.025.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.025.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.425110, -0.302523 -0.300741) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.60828 -0.25604 -0.54902 +Nuclear contribution : -0.92322 0.69860 0.66718 + ----------------------------------------- +Total Dipole Moment : -0.31494 0.44255 0.11816 + ----------------------------------------- +Magnitude (a.u.) : 0.55588 +Magnitude (Debye) : 1.41293 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.779309 0.436922 0.378499 +Rotational constants in MHz : 83321.589627 13098.597483 11347.101583 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.165095 -0.506714 -0.158067 +x,y,z [Debye]: 0.419637 -1.287965 -0.401774 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.425110, -0.302523 -0.300741) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.65840 -0.17317 -0.56226 +Nuclear contribution : -0.92322 0.69860 0.66718 + ----------------------------------------- +Total Dipole Moment : -0.26482 0.52542 0.10492 + ----------------------------------------- +Magnitude (a.u.) : 0.59767 +Magnitude (Debye) : 1.51916 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.779309 0.436922 0.378499 +Rotational constants in MHz : 83321.589627 13098.597483 11347.101583 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.096219 -0.573325 -0.138753 +x,y,z [Debye]: 0.244569 -1.457276 -0.352683 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 26 * + * * + * Dihedral ( 2, 1, 0, 3) : 24.54545455 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0314922990 RMS(Int)= 0.0000937359 + Iter 1: RMS(Cart)= 0.0000206720 RMS(Int)= 0.0000003809 + Iter 2: RMS(Cart)= 0.0000000840 RMS(Int)= 0.0000000015 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4046 0.000000 + 2. B(O 2,N 1) 1.1868 0.000000 + 3. B(H 3,O 0) 0.9790 0.000000 + 4. A(N 1,O 0,H 3) 104.6081 0.000000 + 5. A(O 0,N 1,O 2) 113.0418 0.000000 + 6. D(O 2,N 1,O 0,H 3) 24.5455 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.546609 -0.370547 0.620334 + N 0.378798 -0.595599 -0.412133 + O 0.948991 0.389626 -0.747771 + H -0.781179 0.576520 0.539570 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.032941 -0.700232 1.172261 + 1 N 7.0000 0 14.007 0.715824 -1.125520 -0.778818 + 2 O 8.0000 0 15.999 1.793334 0.736287 -1.413082 + 3 H 1.0000 0 1.008 -1.476215 1.089464 1.019639 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.403134577524 0.00000000 0.00000000 + O 2 1 0 1.185581175060 113.21943480 0.00000000 + H 1 2 3 0.977207481608 104.81503258 16.36363624 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.651540080556 0.00000000 0.00000000 + O 2 1 0 2.240423730395 113.21943480 0.00000000 + H 1 2 3 1.846654516258 104.81503258 16.36363624 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2243 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2718 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.937099384833 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.9370993848 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.472e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7166778711 0.000000000000 0.00166619 0.00005384 0.0117129 0.7000 + 1 -204.7174096754 -0.000731804247 0.00149845 0.00004999 0.0097986 0.7000 + ***Turning on DIIS*** + 2 -204.7180488909 -0.000639215542 0.00400755 0.00013802 0.0080552 0.0000 + 3 -204.7214442924 -0.003395401491 0.00189599 0.00006265 0.0036612 0.0000 + 4 -204.7193038177 0.002140474718 0.00089250 0.00003212 0.0015580 0.0000 + 5 -204.7213505513 -0.002046733654 0.00081308 0.00003726 0.0008756 0.0000 + 6 -204.7204676835 0.000882867864 0.00050803 0.00002499 0.0006055 0.0000 + 7 -204.7200968041 0.000370879325 0.00037424 0.00001544 0.0003194 0.0000 + 8 -204.7210801204 -0.000983316310 0.00019351 0.00000915 0.0001801 0.0000 + 9 -204.7205609971 0.000519123355 0.00010352 0.00000310 0.0000821 0.0000 + 10 -204.7205292833 0.000031713742 0.00003524 0.00000107 0.0000455 0.0000 + 11 -204.7207038880 -0.000174604620 0.00002278 0.00000058 0.0000183 0.0000 + 12 -204.7206221738 0.000081714142 0.00000700 0.00000018 0.0000063 0.0000 + 13 -204.7206425477 -0.000020373871 0.00000232 0.00000007 0.0000022 0.0000 + 14 -204.7206354902 0.000007057460 0.00000087 0.00000003 0.0000012 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 15 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72063595 Eh -5570.73171 eV + +Components: +Nuclear Repulsion : 69.93709938 Eh 1903.08523 eV +Electronic Energy : -274.65773533 Eh -7473.81694 eV +One Electron Energy: -419.46944482 Eh -11414.34389 eV +Two Electron Energy: 144.81170948 Eh 3940.52695 eV + +Virial components: +Potential Energy : -408.96268865 Eh -11128.44052 eV +Kinetic Energy : 204.24205270 Eh 5557.70880 eV +Virial Ratio : 2.00234322 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -4.5952e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.2641e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.2076e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.3072e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.668051 -562.4063 + 1 1.0000 -20.647897 -561.8578 + 2 1.0000 -15.802503 -430.0080 + 3 1.0000 -1.607203 -43.7342 + 4 1.0000 -1.405080 -38.2342 + 5 1.0000 -0.965667 -26.2771 + 6 1.0000 -0.775394 -21.0996 + 7 1.0000 -0.741842 -20.1865 + 8 1.0000 -0.691940 -18.8286 + 9 1.0000 -0.610012 -16.5993 + 10 1.0000 -0.533480 -14.5167 + 11 1.0000 -0.473947 -12.8968 + 12 0.0000 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7.305590 198.7952 + 148 0.0000 7.394114 201.2041 + 149 0.0000 7.453607 202.8230 + 150 0.0000 7.490275 203.8207 + 151 0.0000 7.510729 204.3773 + 152 0.0000 7.603460 206.9007 + 153 0.0000 7.667793 208.6512 + 154 0.0000 7.853060 213.6926 + 155 0.0000 7.897823 214.9107 + 156 0.0000 8.250894 224.5183 + 157 0.0000 8.320266 226.4060 + 158 0.0000 14.141823 384.8186 + 159 0.0000 15.132197 411.7680 + 160 0.0000 15.584136 424.0659 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.668051 -562.4063 + 1 1.0000 -20.647897 -561.8578 + 2 1.0000 -15.802503 -430.0080 + 3 1.0000 -1.607203 -43.7342 + 4 1.0000 -1.405080 -38.2342 + 5 1.0000 -0.965667 -26.2771 + 6 1.0000 -0.775394 -21.0996 + 7 1.0000 -0.741842 -20.1865 + 8 1.0000 -0.691940 -18.8286 + 9 1.0000 -0.610012 -16.5993 + 10 1.0000 -0.533480 -14.5167 + 11 1.0000 -0.473947 -12.8968 + 12 0.0000 0.031294 0.8515 + 13 0.0000 0.074620 2.0305 + 14 0.0000 0.095090 2.5875 + 15 0.0000 0.112355 3.0573 + 16 0.0000 0.121534 3.3071 + 17 0.0000 0.145763 3.9664 + 18 0.0000 0.157430 4.2839 + 19 0.0000 0.169683 4.6173 + 20 0.0000 0.183086 4.9820 + 21 0.0000 0.194967 5.3053 + 22 0.0000 0.204632 5.5683 + 23 0.0000 0.233618 6.3571 + 24 0.0000 0.254656 6.9296 + 25 0.0000 0.300017 8.1639 + 26 0.0000 0.313513 8.5311 + 27 0.0000 0.344152 9.3649 + 28 0.0000 0.350866 9.5476 + 29 0.0000 0.394456 10.7337 + 30 0.0000 0.429063 11.6754 + 31 0.0000 0.513844 13.9824 + 32 0.0000 0.523290 14.2394 + 33 0.0000 0.534669 14.5491 + 34 0.0000 0.563175 15.3248 + 35 0.0000 0.617191 16.7946 + 36 0.0000 0.634373 17.2622 + 37 0.0000 0.656377 17.8609 + 38 0.0000 0.687946 18.7200 + 39 0.0000 0.701431 19.0869 + 40 0.0000 0.733415 19.9572 + 41 0.0000 0.753305 20.4985 + 42 0.0000 0.760758 20.7013 + 43 0.0000 0.791278 21.5318 + 44 0.0000 0.799635 21.7592 + 45 0.0000 0.844914 22.9913 + 46 0.0000 0.847594 23.0642 + 47 0.0000 0.875107 23.8129 + 48 0.0000 0.919550 25.0222 + 49 0.0000 0.938686 25.5429 + 50 0.0000 0.959612 26.1124 + 51 0.0000 0.997166 27.1343 + 52 0.0000 1.021251 27.7896 + 53 0.0000 1.053780 28.6748 + 54 0.0000 1.076590 29.2955 + 55 0.0000 1.087314 29.5873 + 56 0.0000 1.180432 32.1212 + 57 0.0000 1.195184 32.5226 + 58 0.0000 1.240882 33.7661 + 59 0.0000 1.278838 34.7990 + 60 0.0000 1.353802 36.8388 + 61 0.0000 1.410503 38.3817 + 62 0.0000 1.441460 39.2241 + 63 0.0000 1.500773 40.8381 + 64 0.0000 1.540425 41.9171 + 65 0.0000 1.556149 42.3450 + 66 0.0000 1.596471 43.4422 + 67 0.0000 1.628470 44.3129 + 68 0.0000 1.656691 45.0809 + 69 0.0000 1.745386 47.4944 + 70 0.0000 1.787316 48.6353 + 71 0.0000 1.820394 49.5354 + 72 0.0000 1.897835 51.6427 + 73 0.0000 1.944383 52.9093 + 74 0.0000 1.987774 54.0901 + 75 0.0000 2.016923 54.8833 + 76 0.0000 2.034451 55.3602 + 77 0.0000 2.099833 57.1394 + 78 0.0000 2.159383 58.7598 + 79 0.0000 2.177395 59.2499 + 80 0.0000 2.272453 61.8366 + 81 0.0000 2.306561 62.7647 + 82 0.0000 2.364676 64.3461 + 83 0.0000 2.388238 64.9873 + 84 0.0000 2.427057 66.0436 + 85 0.0000 2.445333 66.5409 + 86 0.0000 2.465742 67.0963 + 87 0.0000 2.525770 68.7297 + 88 0.0000 2.543120 69.2018 + 89 0.0000 2.552441 69.4555 + 90 0.0000 2.577014 70.1241 + 91 0.0000 2.622613 71.3649 + 92 0.0000 2.672397 72.7196 + 93 0.0000 2.676579 72.8334 + 94 0.0000 2.736895 74.4747 + 95 0.0000 2.804658 76.3186 + 96 0.0000 2.869637 78.0868 + 97 0.0000 2.968242 80.7700 + 98 0.0000 2.986138 81.2570 + 99 0.0000 3.053282 83.0840 + 100 0.0000 3.149460 85.7012 + 101 0.0000 3.159547 85.9757 + 102 0.0000 3.221588 87.6639 + 103 0.0000 3.518588 95.7457 + 104 0.0000 3.712561 101.0239 + 105 0.0000 3.876303 105.4796 + 106 0.0000 4.016734 109.3009 + 107 0.0000 4.144227 112.7701 + 108 0.0000 4.174071 113.5822 + 109 0.0000 4.281608 116.5085 + 110 0.0000 4.364646 118.7680 + 111 0.0000 4.425728 120.4302 + 112 0.0000 4.511829 122.7731 + 113 0.0000 4.559135 124.0604 + 114 0.0000 4.689410 127.6053 + 115 0.0000 4.818277 131.1120 + 116 0.0000 4.875042 132.6566 + 117 0.0000 4.879475 132.7773 + 118 0.0000 4.953984 134.8048 + 119 0.0000 5.005712 136.2123 + 120 0.0000 5.071950 138.0148 + 121 0.0000 5.110523 139.0644 + 122 0.0000 5.189016 141.2003 + 123 0.0000 5.226888 142.2308 + 124 0.0000 5.233132 142.4008 + 125 0.0000 5.290705 143.9674 + 126 0.0000 5.388567 146.6304 + 127 0.0000 5.481312 149.1541 + 128 0.0000 5.544717 150.8794 + 129 0.0000 5.681143 154.5918 + 130 0.0000 5.785796 157.4395 + 131 0.0000 5.930380 161.3738 + 132 0.0000 6.183087 168.2504 + 133 0.0000 6.413516 174.5206 + 134 0.0000 6.510519 177.1602 + 135 0.0000 6.547363 178.1628 + 136 0.0000 6.686586 181.9513 + 137 0.0000 6.718530 182.8205 + 138 0.0000 6.771602 184.2647 + 139 0.0000 6.812391 185.3746 + 140 0.0000 6.932482 188.6424 + 141 0.0000 7.099118 193.1768 + 142 0.0000 7.134157 194.1303 + 143 0.0000 7.160238 194.8400 + 144 0.0000 7.172643 195.1775 + 145 0.0000 7.240874 197.0342 + 146 0.0000 7.276916 198.0150 + 147 0.0000 7.305590 198.7952 + 148 0.0000 7.394114 201.2041 + 149 0.0000 7.453607 202.8230 + 150 0.0000 7.490275 203.8207 + 151 0.0000 7.510729 204.3773 + 152 0.0000 7.603460 206.9007 + 153 0.0000 7.667793 208.6512 + 154 0.0000 7.853060 213.6926 + 155 0.0000 7.897823 214.9107 + 156 0.0000 8.250894 224.5183 + 157 0.0000 8.320266 226.4060 + 158 0.0000 14.141823 384.8186 + 159 0.0000 15.132197 411.7680 + 160 0.0000 15.584136 424.0659 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.291503 0.000000 + 1 N : 0.337639 0.000000 + 2 O : -0.299581 0.000000 + 3 H : 0.253445 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.809045 s : 3.809045 + pz : 1.474035 p : 4.440915 + px : 1.560759 + py : 1.406121 + dz2 : 0.009672 d : 0.036160 + dxz : 0.007836 + dyz : 0.003992 + dx2y2 : 0.013982 + dxy : 0.000678 + f0 : 0.000789 f : 0.005383 + f+1 : 0.001287 + f-1 : 0.000442 + f+2 : 0.001013 + f-2 : 0.001188 + f+3 : 0.000145 + f-3 : 0.000519 + 1 N s : 3.857329 s : 3.857329 + pz : 0.719927 p : 2.627845 + px : 0.728331 + py : 1.179586 + dz2 : 0.031647 d : 0.143991 + dxz : 0.029059 + dyz : 0.020958 + dx2y2 : 0.034098 + dxy : 0.028228 + f0 : 0.005547 f : 0.033196 + f+1 : 0.001925 + f-1 : 0.005155 + f+2 : 0.003268 + f-2 : 0.005832 + f+3 : 0.003872 + f-3 : 0.007597 + 2 O s : 3.861860 s : 3.861860 + pz : 1.567631 p : 4.370742 + px : 1.415894 + py : 1.387216 + dz2 : 0.007942 d : 0.059564 + dxz : 0.003503 + dyz : 0.018103 + dx2y2 : 0.014553 + dxy : 0.015462 + f0 : 0.000644 f : 0.007415 + f+1 : 0.000387 + f-1 : 0.001393 + f+2 : 0.000662 + f-2 : 0.001019 + f+3 : 0.001311 + f-3 : 0.001999 + 3 H s : 0.641426 s : 0.641426 + pz : 0.027504 p : 0.084181 + px : 0.035300 + py : 0.021377 + dz2 : 0.000305 d : 0.020948 + dxz : -0.000397 + dyz : 0.010133 + dx2y2 : 0.002263 + dxy : 0.008643 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.597600 0.000000 + 1 N : -0.282647 0.000000 + 2 O : 0.243542 0.000000 + 3 H : -0.558495 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.108397 s : 3.108397 + pz : 1.297011 p : 3.902481 + px : 1.308917 + py : 1.296553 + dz2 : 0.055082 d : 0.298416 + dxz : 0.088570 + dyz : 0.051484 + dx2y2 : 0.049835 + dxy : 0.053445 + f0 : 0.009570 f : 0.093105 + f+1 : 0.019153 + f-1 : 0.010834 + f+2 : 0.015135 + f-2 : 0.022845 + f+3 : 0.006145 + f-3 : 0.009422 + 1 N s : 3.002246 s : 3.002246 + pz : 0.787934 p : 2.831713 + px : 0.788382 + py : 1.255397 + dz2 : 0.194996 d : 0.976417 + dxz : 0.207108 + dyz : 0.157145 + dx2y2 : 0.230115 + dxy : 0.187052 + f0 : 0.064357 f : 0.472272 + f+1 : 0.050571 + f-1 : 0.061547 + f+2 : 0.051360 + f-2 : 0.089584 + f+3 : 0.064508 + f-3 : 0.090344 + 2 O s : 3.301533 s : 3.301533 + pz : 1.317332 p : 4.020044 + px : 1.265176 + py : 1.437536 + dz2 : 0.049003 d : 0.319407 + dxz : 0.044068 + dyz : 0.047580 + dx2y2 : 0.104754 + dxy : 0.074002 + f0 : 0.008807 f : 0.115474 + f+1 : 0.006553 + f-1 : 0.020100 + f+2 : 0.009089 + f-2 : 0.019427 + f+3 : 0.023770 + f-3 : 0.027726 + 3 H s : 0.609653 s : 0.609653 + pz : 0.138703 p : 0.542681 + px : 0.146042 + py : 0.257936 + dz2 : 0.036514 d : 0.406161 + dxz : 0.032494 + dyz : 0.114303 + dx2y2 : 0.110567 + dxy : 0.112284 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2915 8.0000 -0.2915 1.8100 1.8100 -0.0000 + 1 N 6.6624 7.0000 0.3376 2.5147 2.5147 -0.0000 + 2 O 8.2996 8.0000 -0.2996 1.6840 1.6840 0.0000 + 3 H 0.7466 1.0000 0.2534 1.0112 1.0112 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8239 B( 0-O , 3-H ) : 0.9279 B( 1-N , 2-O ) : 1.6167 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.373 sec +Sum of individual times .... 2.126 sec ( 89.6%) + +Fock matrix formation .... 1.718 sec ( 72.4%) +Diagonalization .... 0.179 sec ( 7.5%) +Density matrix formation .... 0.013 sec ( 0.5%) +Population analysis .... 0.055 sec ( 2.3%) +Initial guess .... 0.010 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.2%) +DIIS solution .... 0.153 sec ( 6.4%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.206 sec +Reference energy ... -204.720635513 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.380 sec +AO-integral generation ... 0.142 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.382 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.024 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.025 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.038 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.349 sec +AO-integral generation ... 0.244 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.147 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.252 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090516212 +EMP2(bb)= -0.090516212 +EMP2(ab)= -0.515097841 + +Initial guess performed in 0.132 sec +E(0) ... -204.720635513 +E(MP2) ... -0.696130265 +Initial E(tot) ... -205.416765777 + ... 0.186693388 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.416765777 -0.696130265 -0.000000000 0.028549851 2.74 0.000002493 + *** Turning on DIIS *** + 1 -205.388024116 -0.667388603 0.028741661 0.011033913 2.71 0.057926992 + 2 -205.407406461 -0.686770948 -0.019382345 0.006440003 2.79 0.061219052 + 3 -205.411105057 -0.690469544 -0.003698596 0.002279366 2.83 0.075625523 + 4 -205.412686721 -0.692051208 -0.001581664 0.001401152 2.84 0.082628680 + 5 -205.413234948 -0.692599436 -0.000548228 0.000775806 2.89 0.088153786 + 6 -205.413336746 -0.692701233 -0.000101797 0.000486031 2.84 0.090680739 + 7 -205.413377513 -0.692742000 -0.000040767 0.000220404 2.92 0.091728556 + 8 -205.413386596 -0.692751084 -0.000009084 0.000113265 2.90 0.092118240 + 9 -205.413382723 -0.692747211 0.000003873 0.000027391 2.83 0.092236763 + 10 -205.413387234 -0.692751721 -0.000004510 0.000016872 2.79 0.092280588 + 11 -205.413384832 -0.692749319 0.000002402 0.000012450 2.80 0.092270636 + 12 -205.413385756 -0.692750243 -0.000000924 0.000008896 2.80 0.092278472 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.720635513 +E(CORR) ... -0.692750243 +E(TOT) ... -205.413385756 +Singles norm **1/2 ... 0.092278472 ( 0.046139236, 0.046139236) +T1 diagnostic ... 0.021750244 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.060090 + 10a-> 13a 10b-> 13b 0.050691 + 8b-> 13b -1b-> -1b 0.048215 + 8a-> 13a -1a-> -1a 0.048215 + 8a-> 13a 10b-> 13b 0.033149 + 10a-> 13a 8b-> 13b 0.033149 + 11a-> 13a 11b-> 13b 0.029840 + 5a-> 13a 5b-> 13b 0.025538 + 10b-> 13b -1b-> -1b 0.024740 + 10a-> 13a -1a-> -1a 0.024740 + 10a-> 22a 10b-> 13b 0.023009 + 10a-> 13a 10b-> 22b 0.023009 + 8a-> 13a 8b-> 22b 0.022765 + 8a-> 22a 8b-> 13b 0.022765 + 9a-> 13a 9b-> 13b 0.022118 + 11a-> 26a -1a-> -1a 0.021959 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034581300 + alpha-alpha-alpha ... -0.000906947 ( 2.6%) + alpha-alpha-beta ... -0.016383703 ( 47.4%) + alpha-beta -beta ... -0.016383703 ( 47.4%) + beta -beta -beta ... -0.000906947 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034581300 + +Final correlation energy ... -0.727331543 +E(CCSD) ... -205.413385756 +E(CCSD(T)) ... -205.447967056 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.208167144 sqrt= 1.099166568 +W(HF) = 0.827700045 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.204494 0.000000 + 1 N : 0.145992 -0.000000 + 2 O : -0.178209 0.000000 + 3 H : 0.236710 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.795140 s : 3.795140 + pz : 1.435044 p : 4.334363 + px : 1.518811 + py : 1.380509 + dz2 : 0.016204 d : 0.065969 + dxz : 0.012133 + dyz : 0.011118 + dx2y2 : 0.018462 + dxy : 0.008052 + f0 : 0.001408 f : 0.009022 + f+1 : 0.001579 + f-1 : 0.001062 + f+2 : 0.001404 + f-2 : 0.001622 + f+3 : 0.000800 + f-3 : 0.001146 + 1 N s : 3.908545 s : 3.908545 + pz : 0.794876 p : 2.741613 + px : 0.812853 + py : 1.133885 + dz2 : 0.039153 d : 0.171628 + dxz : 0.035392 + dyz : 0.024772 + dx2y2 : 0.041151 + dxy : 0.031161 + f0 : 0.005230 f : 0.032222 + f+1 : 0.001977 + f-1 : 0.005266 + f+2 : 0.003032 + f-2 : 0.005749 + f+3 : 0.003820 + f-3 : 0.007148 + 2 O s : 3.849231 s : 3.849231 + pz : 1.507267 p : 4.236188 + px : 1.369690 + py : 1.359231 + dz2 : 0.013324 d : 0.082705 + dxz : 0.010152 + dyz : 0.021036 + dx2y2 : 0.020696 + dxy : 0.017497 + f0 : 0.001107 f : 0.010085 + f+1 : 0.000897 + f-1 : 0.001730 + f+2 : 0.001108 + f-2 : 0.001448 + f+3 : 0.001601 + f-3 : 0.002194 + 3 H s : 0.657726 s : 0.657726 + pz : 0.031653 p : 0.086248 + px : 0.039066 + py : 0.015529 + dz2 : 0.000254 d : 0.019316 + dxz : 0.000151 + dyz : 0.009228 + dx2y2 : 0.001657 + dxy : 0.008026 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.612602 0.000000 + 1 N : -0.331220 -0.000000 + 2 O : 0.280003 -0.000000 + 3 H : -0.561386 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.116914 s : 3.116914 + pz : 1.273986 p : 3.839900 + px : 1.285117 + py : 1.280797 + dz2 : 0.062711 d : 0.330052 + dxz : 0.094793 + dyz : 0.056398 + dx2y2 : 0.056471 + dxy : 0.059678 + f0 : 0.011499 f : 0.100533 + f+1 : 0.020836 + f-1 : 0.011536 + f+2 : 0.016317 + f-2 : 0.022830 + f+3 : 0.007016 + f-3 : 0.010501 + 1 N s : 3.007792 s : 3.007792 + pz : 0.827960 p : 2.882266 + px : 0.837723 + py : 1.216583 + dz2 : 0.195707 d : 0.980683 + dxz : 0.214725 + dyz : 0.152258 + dx2y2 : 0.228192 + dxy : 0.189801 + f0 : 0.061318 f : 0.460478 + f+1 : 0.049349 + f-1 : 0.060465 + f+2 : 0.050666 + f-2 : 0.087241 + f+3 : 0.064839 + f-3 : 0.086600 + 2 O s : 3.303563 s : 3.303563 + pz : 1.282696 p : 3.939015 + px : 1.238154 + py : 1.418165 + dz2 : 0.056098 d : 0.353048 + dxz : 0.049239 + dyz : 0.055784 + dx2y2 : 0.110997 + dxy : 0.080929 + f0 : 0.009841 f : 0.124371 + f+1 : 0.007907 + f-1 : 0.020948 + f+2 : 0.011061 + f-2 : 0.020003 + f+3 : 0.024653 + f-3 : 0.029958 + 3 H s : 0.614791 s : 0.614791 + pz : 0.139978 p : 0.550844 + px : 0.148450 + py : 0.262417 + dz2 : 0.036184 d : 0.395750 + dxz : 0.032014 + dyz : 0.110143 + dx2y2 : 0.109175 + dxy : 0.108234 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2045 8.0000 -0.2045 2.1847 1.7358 0.4488 + 1 N 6.8540 7.0000 0.1460 2.8008 2.3293 0.4715 + 2 O 8.1782 8.0000 -0.1782 2.0888 1.5899 0.4989 + 3 H 0.7633 1.0000 0.2367 1.0307 0.9567 0.0740 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7798 B( 0-O , 3-H ) : 0.8562 B( 1-N , 2-O ) : 1.4695 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 51.813 sec + +Fock Matrix Formation ... 0.206 sec ( 0.4%) +Initial Guess ... 0.132 sec ( 0.3%) +DIIS Solver ... 1.601 sec ( 3.1%) +State Vector Update ... 0.077 sec ( 0.1%) +Sigma-vector construction ... 35.015 sec ( 67.6%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.022 sec ( 0.1% of sigma) + (0-ext) ... 0.064 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.024 sec ( 0.1% of sigma) + (2-ext) ... 0.865 sec ( 2.5% of sigma) + (4-ext) ... 19.324 sec ( 55.2% of sigma) + ... 1.246 sec ( 3.6% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.007 sec ( 0.0% of sigma) + (1-ext) ... 0.099 sec ( 0.3% of sigma) + Fock-dressing ... 1.973 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.068 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 8.881 sec ( 25.4% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.863 sec ( 13.2% of ALL) + I/O of integral and amplitudes ... 0.837 sec ( 12.2% of (T)) + External N**7 contributions ... 3.923 sec ( 57.2% of (T)) + Internal N**7 contributions ... 0.311 sec ( 4.5% of (T)) + N**6 triples energy contributions ... 1.711 sec ( 24.9% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.447967055903 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.010964960 -0.000904662 0.007200494 + 2 N : -0.010633856 -0.000506350 -0.005818890 + 3 O : 0.006156807 0.000998662 0.004704887 + 4 H : -0.006487911 0.000412349 -0.006086491 + +Norm of the cartesian gradient ... 0.021457833 +RMS gradient ... 0.006194343 +MAX gradient ... 0.010964960 + +------- +TIMINGS +------- + +Total numerical gradient time ... 333.382 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 489.12 cm**-1 + 7: 676.43 cm**-1 + 8: 873.87 cm**-1 + 9: 1332.13 cm**-1 + 10: 1647.86 cm**-1 + 11: 3593.35 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 -0.025424 -0.230702 0.188790 0.034042 -0.015937 -0.014461 + 1 -0.004574 -0.112923 -0.114701 0.073317 0.065849 0.059636 + 2 0.138181 0.100728 -0.189792 -0.055243 0.013639 -0.005736 + 3 -0.005697 0.091834 -0.293835 0.076006 -0.178186 -0.001698 + 4 0.041687 0.130833 0.205731 -0.016895 -0.516310 0.001185 + 5 -0.110192 0.053317 0.309233 -0.048650 0.067588 0.001760 + 6 0.083296 0.139690 0.115285 -0.063322 0.201018 0.000447 + 7 -0.015551 -0.004760 -0.046723 -0.056897 0.386822 0.000094 + 8 -0.014475 -0.203882 -0.091240 0.048147 -0.106023 -0.000446 + 9 -0.839394 0.168425 -0.743200 -0.591421 -0.461587 0.246018 + 10 -0.259847 0.049838 -0.296681 -0.025855 -0.010244 -0.964492 + 11 -0.432243 0.896399 0.163487 0.788653 0.527145 0.073651 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 489.12 0.018992 95.98 0.012117 (-0.013744 0.003495 -0.109159) + 7: 676.43 0.006340 32.04 0.002925 ( 0.039899 0.026417 0.025204) + 8: 873.87 0.055075 278.33 0.019668 (-0.112129 -0.007141 0.083927) + 9: 1332.13 0.001786 9.02 0.000418 (-0.001200 0.019602 0.005710) + 10: 1647.86 0.028929 146.20 0.005478 (-0.054335 -0.018452 0.046752) + 11: 3593.35 0.007360 37.19 0.000639 ( 0.015684 -0.019068 -0.005436) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 489.12 E(vib) ... 0.15 +freq. 676.43 E(vib) ... 0.08 +freq. 873.87 E(vib) ... 0.04 +freq. 1332.13 E(vib) ... 0.01 +freq. 1647.86 E(vib) ... 0.00 +freq. 3593.35 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.44796706 Eh +Zero point energy ... 0.01962130 Eh 12.31 kcal/mol +Thermal vibrational correction ... 0.00042685 Eh 0.27 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42508636 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00325939 Eh 2.05 kcal/mol +Non-thermal (ZPE) correction 0.01962130 Eh 12.31 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02288069 Eh 14.36 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42508636 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.42414215 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.766229 0.435750 0.378506 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00057382 Eh 0.36 kcal/mol +Rotational entropy ... 0.00988127 Eh 6.20 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02825741 Eh 17.73 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00988127 Eh 6.20 kcal/mol| +| sn= 2 | S(rot)= 0.00922681 Eh 5.79 kcal/mol| +| sn= 3 | S(rot)= 0.00884398 Eh 5.55 kcal/mol| +| sn= 4 | S(rot)= 0.00857236 Eh 5.38 kcal/mol| +| sn= 5 | S(rot)= 0.00836167 Eh 5.25 kcal/mol| +| sn= 6 | S(rot)= 0.00818953 Eh 5.14 kcal/mol| +| sn= 7 | S(rot)= 0.00804398 Eh 5.05 kcal/mol| +| sn= 8 | S(rot)= 0.00791790 Eh 4.97 kcal/mol| +| sn= 9 | S(rot)= 0.00780669 Eh 4.90 kcal/mol| +| sn=10 | S(rot)= 0.00770721 Eh 4.84 kcal/mol| +| sn=11 | S(rot)= 0.00761722 Eh 4.78 kcal/mol| +| sn=12 | S(rot)= 0.00753507 Eh 4.73 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.42414215 Eh +Total entropy correction ... -0.02825741 Eh -17.73 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.45239956 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00443251 Eh -2.78 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.447967055 Eh +Current gradient norm .... 0.021457854 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.024191782 0.145781796 0.217672586 0.463247951 0.534340622 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999855854 +Lowest eigenvalues of augmented Hessian: + -0.000069804 0.142613240 0.216386421 0.463226094 0.534251473 +Length of the computed step .... 0.016980998 +The final length of the internal step .... 0.016980998 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0069324633 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0063208834 RMS(Int)= 0.0069309979 + Iter 1: RMS(Cart)= 0.0000120993 RMS(Int)= 0.0000143923 + Iter 2: RMS(Cart)= 0.0000000422 RMS(Int)= 0.0000000762 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000004 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0018549755 0.0001000000 NO + MAX gradient 0.0024568690 0.0003000000 NO + RMS step 0.0069324633 0.0020000000 NO + MAX step 0.0133381844 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0071 Max(Angles) 0.35 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4046 -0.002210 0.0071 1.4117 + 2. B(O 2,N 1) 1.1868 0.002457 -0.0030 1.1837 + 3. B(H 3,O 0) 0.9790 0.002455 -0.0030 0.9760 + 4. A(N 1,O 0,H 3) 104.61 -0.001439 0.35 104.96 + 5. A(O 0,N 1,O 2) 113.04 -0.001277 0.15 113.19 + 6. D(O 2,N 1,O 0,H 3) 24.55 0.015262 -0.00 24.55 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.548981 -0.367915 0.621417 + N 0.382607 -0.594366 -0.414806 + O 0.953094 0.386717 -0.751383 + H -0.786719 0.575563 0.544773 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.037423 -0.695259 1.174307 + 1 N 7.0000 0 14.007 0.723022 -1.123188 -0.783870 + 2 O 8.0000 0 15.999 1.801086 0.730790 -1.419909 + 3 H 1.0000 0 1.008 -1.486683 1.087657 1.029472 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.411698379325 0.00000000 0.00000000 + O 2 1 0 1.183749685014 113.19049194 0.00000000 + H 1 2 3 0.975984292137 104.96148806 24.54545465 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.667723320624 0.00000000 0.00000000 + O 2 1 0 2.236962715792 113.19049194 0.00000000 + H 1 2 3 1.844343023149 104.96148806 24.54545465 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2243 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2717 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.849009003463 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.479e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7206273265 0.000000000000 0.00022916 0.00000763 0.0011294 0.7000 + 1 -204.7206411713 -0.000013844751 0.00018642 0.00000654 0.0008536 0.7000 + ***Turning on DIIS*** + 2 -204.7206527431 -0.000011571833 0.00047880 0.00001772 0.0007010 0.0000 + 3 -204.7204328087 0.000219934390 0.00024291 0.00000786 0.0002810 0.0000 + 4 -204.7207206823 -0.000287873645 0.00010548 0.00000300 0.0000885 0.0000 + 5 -204.7207439518 -0.000023269415 0.00003196 0.00000091 0.0000539 0.0000 + 6 -204.7206442079 0.000099743874 0.00002716 0.00000053 0.0000332 0.0000 + 7 -204.7207015945 -0.000057386571 0.00000952 0.00000026 0.0000112 0.0000 + 8 -204.7206907008 0.000010893681 0.00000520 0.00000017 0.0000059 0.0000 + 9 -204.7206838761 0.000006824647 0.00000365 0.00000011 0.0000032 0.0000 + 10 -204.7206948520 -0.000010975840 0.00000220 0.00000008 0.0000014 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + +Total Energy : -204.72069077 Eh -5570.73321 eV + Last Energy change ... 4.0846e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.1301e-06 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.208 sec +Reference energy ... -204.720692210 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.369 sec +AO-integral generation ... 0.144 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.366 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.038 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.034 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.023 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.039 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.350 sec +AO-integral generation ... 0.245 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.152 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.253 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090484281 +EMP2(bb)= -0.090484281 +EMP2(ab)= -0.515088685 + +Initial guess performed in 0.133 sec +E(0) ... -204.720692210 +E(MP2) ... -0.696057247 +Initial E(tot) ... -205.416749457 + ... 0.186716673 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.416749457 -0.696057247 -0.000000000 0.028255393 2.72 0.000001438 + *** Turning on DIIS *** + 1 -205.388027958 -0.667335748 0.028721499 0.010879780 2.73 0.057968383 + 2 -205.407415594 -0.686723384 -0.019387636 0.006355056 2.79 0.061217779 + 3 -205.411114879 -0.690422668 -0.003699284 0.002230426 2.85 0.075649188 + 4 -205.412696597 -0.692004387 -0.001581718 0.001401051 2.78 0.082663250 + 5 -205.413249611 -0.692557401 -0.000553014 0.000807286 2.91 0.088265490 + 6 -205.413353968 -0.692661758 -0.000104357 0.000501653 2.83 0.090870625 + 7 -205.413396170 -0.692703960 -0.000042202 0.000222716 2.83 0.091968361 + 8 -205.413405826 -0.692713616 -0.000009656 0.000114092 2.88 0.092375762 + 9 -205.413401807 -0.692709597 0.000004019 0.000027533 2.81 0.092496955 + 10 -205.413406471 -0.692714261 -0.000004664 0.000017296 2.77 0.092542502 + 11 -205.413404006 -0.692711796 0.000002465 0.000012723 2.78 0.092532510 + 12 -205.413404933 -0.692712722 -0.000000927 0.000009083 2.78 0.092540795 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.720692210 +E(CORR) ... -0.692712722 +E(TOT) ... -205.413404933 +Singles norm **1/2 ... 0.092540795 ( 0.046270398, 0.046270398) +T1 diagnostic ... 0.021812075 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.061275 + 10a-> 13a 10b-> 13b 0.049057 + 8a-> 13a -1a-> -1a 0.047564 + 8b-> 13b -1b-> -1b 0.047564 + 8a-> 13a 10b-> 13b 0.032999 + 10a-> 13a 8b-> 13b 0.032999 + 11a-> 13a 11b-> 13b 0.029740 + 10b-> 13b -1b-> -1b 0.026387 + 10a-> 13a -1a-> -1a 0.026387 + 5a-> 13a 5b-> 13b 0.025733 + 8a-> 13a 8b-> 22b 0.023321 + 8a-> 22a 8b-> 13b 0.023321 + 11b-> 26b -1b-> -1b 0.022444 + 11a-> 26a -1a-> -1a 0.022444 + 10a-> 13a 10b-> 22b 0.022333 + 10a-> 22a 10b-> 13b 0.022333 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034597414 + alpha-alpha-alpha ... -0.000906638 ( 2.6%) + alpha-alpha-beta ... -0.016392069 ( 47.4%) + alpha-beta -beta ... -0.016392069 ( 47.4%) + beta -beta -beta ... -0.000906638 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034597414 + +Final correlation energy ... -0.727310137 +E(CCSD) ... -205.413404933 +E(CCSD(T)) ... -205.448002347 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.208345088 sqrt= 1.099247510 +W(HF) = 0.827578156 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 51.444 sec + +Fock Matrix Formation ... 0.208 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.3%) +DIIS Solver ... 1.500 sec ( 2.9%) +State Vector Update ... 0.083 sec ( 0.2%) +Sigma-vector construction ... 34.875 sec ( 67.8%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.022 sec ( 0.1% of sigma) + (0-ext) ... 0.064 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.024 sec ( 0.1% of sigma) + (2-ext) ... 0.861 sec ( 2.5% of sigma) + (4-ext) ... 19.369 sec ( 55.5% of sigma) + ... 1.233 sec ( 3.5% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.007 sec ( 0.0% of sigma) + (1-ext) ... 0.099 sec ( 0.3% of sigma) + Fock-dressing ... 1.955 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.069 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 8.716 sec ( 25.0% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.795 sec ( 13.2% of ALL) + I/O of integral and amplitudes ... 0.690 sec ( 10.2% of (T)) + External N**7 contributions ... 3.906 sec ( 57.5% of (T)) + Internal N**7 contributions ... 0.313 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.609 sec ( 23.7% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.448002346761 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.009080160 0.001924158 0.007651506 + 2 N : -0.007980086 0.001431409 -0.007397567 + 3 O : 0.005113548 -0.001338292 0.004917661 + 4 H : -0.006213621 -0.002017276 -0.005171600 + +Norm of the cartesian gradient ... 0.019664655 +RMS gradient ... 0.005676697 +MAX gradient ... 0.009080160 + +------- +TIMINGS +------- + +Total numerical gradient time ... 336.033 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.448002347 Eh +Current gradient norm .... 0.019664655 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999900 +Lowest eigenvalues of augmented Hessian: + -0.000000039 0.141492806 0.212758920 0.465235597 0.536555656 +Length of the computed step .... 0.000446731 +The final length of the internal step .... 0.000446731 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0001823772 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001331859 RMS(Int)= 0.0001823774 + Iter 1: RMS(Cart)= 0.0000000007 RMS(Int)= 0.0000000009 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000352917 0.0000050000 NO + RMS gradient 0.0000423710 0.0001000000 YES + MAX gradient 0.0000863321 0.0003000000 YES + RMS step 0.0001823772 0.0020000000 YES + MAX step 0.0004426742 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0002 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4117 -0.000086 0.0002 1.4119 + 2. B(O 2,N 1) 1.1837 -0.000043 -0.0000 1.1837 + 3. B(H 3,O 0) 0.9760 -0.000031 0.0000 0.9760 + 4. A(N 1,O 0,H 3) 104.96 -0.000021 0.00 104.96 + 5. A(O 0,N 1,O 2) 113.19 -0.000010 -0.00 113.19 + 6. D(O 2,N 1,O 0,H 3) 24.55 0.014846 0.00 24.55 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.549056 -0.367905 0.621488 + N 0.382703 -0.594387 -0.414893 + O 0.953177 0.386697 -0.751454 + H -0.786823 0.575595 0.544858 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -1.037565 -0.695240 1.174442 + 1 N 7.0000 0 14.007 0.723203 -1.123228 -0.784034 + 2 O 8.0000 0 15.999 1.801244 0.730752 -1.420041 + 3 H 1.0000 0 1.008 -1.486880 1.087716 1.029633 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.411932632437 0.00000000 0.00000000 + O 2 1 0 1.183740191607 113.19003519 0.00000000 + H 1 2 3 0.976010775693 104.96302354 24.54545465 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.668165994852 0.00000000 0.00000000 + O 2 1 0 2.236944775853 113.19003519 0.00000000 + H 1 2 3 1.844393069815 104.96302354 24.54545465 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2243 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2717 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.843782461354 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.8437824614 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.479e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7206715776 0.000000000000 0.00000736 0.00000019 0.0000358 0.7000 + 1 -204.7206715845 -0.000000006912 0.00000609 0.00000016 0.0000269 0.7000 + ***Turning on DIIS*** + 2 -204.7206715903 -0.000000005763 0.00001593 0.00000042 0.0000201 0.0000 + 3 -204.7206822678 -0.000010677537 0.00000602 0.00000019 0.0000048 0.0000 + 4 -204.7206669159 0.000015351884 0.00000274 0.00000007 0.0000020 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72066789 Eh -5570.73258 eV + +Components: +Nuclear Repulsion : 69.84378246 Eh 1900.54594 eV +Electronic Energy : -274.56445036 Eh -7471.27853 eV +One Electron Energy: -419.28321258 Eh -11409.27625 eV +Two Electron Energy: 144.71876222 Eh 3937.99772 eV + +Virial components: +Potential Energy : -408.96677594 Eh -11128.55174 eV +Kinetic Energy : 204.24610804 Eh 5557.81915 eV +Virial Ratio : 2.00232347 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -9.7859e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.0684e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.9486e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.0710e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.669736 -562.4521 + 1 1.0000 -20.645840 -561.8019 + 2 1.0000 -15.802968 -430.0206 + 3 1.0000 -1.608489 -43.7692 + 4 1.0000 -1.403701 -38.1967 + 5 1.0000 -0.965342 -26.2683 + 6 1.0000 -0.775693 -21.1077 + 7 1.0000 -0.741711 -20.1830 + 8 1.0000 -0.691591 -18.8191 + 9 1.0000 -0.610949 -16.6248 + 10 1.0000 -0.533742 -14.5239 + 11 1.0000 -0.473090 -12.8734 + 12 0.0000 0.031402 0.8545 + 13 0.0000 0.074853 2.0369 + 14 0.0000 0.094880 2.5818 + 15 0.0000 0.112398 3.0585 + 16 0.0000 0.121710 3.3119 + 17 0.0000 0.145805 3.9676 + 18 0.0000 0.157540 4.2869 + 19 0.0000 0.169567 4.6141 + 20 0.0000 0.183196 4.9850 + 21 0.0000 0.194869 5.3027 + 22 0.0000 0.204587 5.5671 + 23 0.0000 0.233481 6.3533 + 24 0.0000 0.255100 6.9416 + 25 0.0000 0.299606 8.1527 + 26 0.0000 0.311852 8.4859 + 27 0.0000 0.343166 9.3380 + 28 0.0000 0.349895 9.5211 + 29 0.0000 0.394858 10.7446 + 30 0.0000 0.428506 11.6602 + 31 0.0000 0.514145 13.9906 + 32 0.0000 0.522669 14.2226 + 33 0.0000 0.534436 14.5427 + 34 0.0000 0.563350 15.3295 + 35 0.0000 0.617313 16.7979 + 36 0.0000 0.635054 17.2807 + 37 0.0000 0.657645 17.8954 + 38 0.0000 0.687632 18.7114 + 39 0.0000 0.700682 19.0665 + 40 0.0000 0.733968 19.9723 + 41 0.0000 0.752499 20.4766 + 42 0.0000 0.760742 20.7008 + 43 0.0000 0.790401 21.5079 + 44 0.0000 0.799371 21.7520 + 45 0.0000 0.844246 22.9731 + 46 0.0000 0.847312 23.0565 + 47 0.0000 0.875716 23.8295 + 48 0.0000 0.920117 25.0377 + 49 0.0000 0.939114 25.5546 + 50 0.0000 0.960242 26.1295 + 51 0.0000 0.996431 27.1143 + 52 0.0000 1.021722 27.8025 + 53 0.0000 1.053134 28.6572 + 54 0.0000 1.075823 29.2746 + 55 0.0000 1.086266 29.5588 + 56 0.0000 1.179040 32.0833 + 57 0.0000 1.195486 32.5308 + 58 0.0000 1.240132 33.7457 + 59 0.0000 1.277675 34.7673 + 60 0.0000 1.356250 36.9054 + 61 0.0000 1.409460 38.3534 + 62 0.0000 1.443554 39.2811 + 63 0.0000 1.503672 40.9170 + 64 0.0000 1.541942 41.9584 + 65 0.0000 1.554849 42.3096 + 66 0.0000 1.596235 43.4357 + 67 0.0000 1.627177 44.2777 + 68 0.0000 1.656623 45.0790 + 69 0.0000 1.744702 47.4758 + 70 0.0000 1.786140 48.6033 + 71 0.0000 1.819251 49.5043 + 72 0.0000 1.899218 51.6803 + 73 0.0000 1.941924 52.8424 + 74 0.0000 1.986358 54.0515 + 75 0.0000 2.014105 54.8066 + 76 0.0000 2.033294 55.3287 + 77 0.0000 2.097291 57.0702 + 78 0.0000 2.159283 58.7571 + 79 0.0000 2.177582 59.2550 + 80 0.0000 2.270583 61.7857 + 81 0.0000 2.306967 62.7758 + 82 0.0000 2.363034 64.3014 + 83 0.0000 2.388759 65.0014 + 84 0.0000 2.428538 66.0839 + 85 0.0000 2.444690 66.5234 + 86 0.0000 2.464831 67.0715 + 87 0.0000 2.522617 68.6439 + 88 0.0000 2.542915 69.1962 + 89 0.0000 2.553362 69.4805 + 90 0.0000 2.576949 70.1223 + 91 0.0000 2.622946 71.3740 + 92 0.0000 2.668927 72.6252 + 93 0.0000 2.676966 72.8439 + 94 0.0000 2.738248 74.5115 + 95 0.0000 2.805948 76.3537 + 96 0.0000 2.869369 78.0795 + 97 0.0000 2.963399 80.6382 + 98 0.0000 2.982940 81.1699 + 99 0.0000 3.046197 82.8912 + 100 0.0000 3.147620 85.6511 + 101 0.0000 3.162959 86.0685 + 102 0.0000 3.222536 87.6897 + 103 0.0000 3.517287 95.7102 + 104 0.0000 3.716533 101.1320 + 105 0.0000 3.874309 105.4253 + 106 0.0000 4.015610 109.2703 + 107 0.0000 4.148319 112.8815 + 108 0.0000 4.178577 113.7049 + 109 0.0000 4.281549 116.5069 + 110 0.0000 4.365623 118.7946 + 111 0.0000 4.422020 120.3293 + 112 0.0000 4.516457 122.8990 + 113 0.0000 4.562276 124.1458 + 114 0.0000 4.690376 127.6316 + 115 0.0000 4.821470 131.1989 + 116 0.0000 4.871661 132.5646 + 117 0.0000 4.880651 132.8093 + 118 0.0000 4.954671 134.8235 + 119 0.0000 5.004198 136.1712 + 120 0.0000 5.074283 138.0783 + 121 0.0000 5.110738 139.0703 + 122 0.0000 5.193446 141.3209 + 123 0.0000 5.230838 142.3383 + 124 0.0000 5.232632 142.3872 + 125 0.0000 5.291271 143.9828 + 126 0.0000 5.387690 146.6065 + 127 0.0000 5.478882 149.0880 + 128 0.0000 5.545693 150.9060 + 129 0.0000 5.684519 154.6836 + 130 0.0000 5.782352 157.3458 + 131 0.0000 5.933821 161.4675 + 132 0.0000 6.175012 168.0306 + 133 0.0000 6.411576 174.4678 + 134 0.0000 6.507986 177.0913 + 135 0.0000 6.544058 178.0729 + 136 0.0000 6.684296 181.8889 + 137 0.0000 6.718988 182.8330 + 138 0.0000 6.771932 184.2736 + 139 0.0000 6.808878 185.2790 + 140 0.0000 6.928967 188.5468 + 141 0.0000 7.101640 193.2455 + 142 0.0000 7.136045 194.1817 + 143 0.0000 7.163470 194.9279 + 144 0.0000 7.177113 195.2992 + 145 0.0000 7.240098 197.0131 + 146 0.0000 7.275777 197.9840 + 147 0.0000 7.310642 198.9327 + 148 0.0000 7.397428 201.2943 + 149 0.0000 7.453822 202.8288 + 150 0.0000 7.489940 203.8116 + 151 0.0000 7.511401 204.3956 + 152 0.0000 7.597714 206.7443 + 153 0.0000 7.663733 208.5408 + 154 0.0000 7.856922 213.7977 + 155 0.0000 7.889653 214.6884 + 156 0.0000 8.244652 224.3484 + 157 0.0000 8.321972 226.4524 + 158 0.0000 14.136588 384.6761 + 159 0.0000 15.137017 411.8992 + 160 0.0000 15.653186 425.9448 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.669736 -562.4521 + 1 1.0000 -20.645840 -561.8019 + 2 1.0000 -15.802968 -430.0206 + 3 1.0000 -1.608489 -43.7692 + 4 1.0000 -1.403701 -38.1967 + 5 1.0000 -0.965342 -26.2683 + 6 1.0000 -0.775693 -21.1077 + 7 1.0000 -0.741711 -20.1830 + 8 1.0000 -0.691591 -18.8191 + 9 1.0000 -0.610949 -16.6248 + 10 1.0000 -0.533742 -14.5239 + 11 1.0000 -0.473090 -12.8734 + 12 0.0000 0.031402 0.8545 + 13 0.0000 0.074853 2.0369 + 14 0.0000 0.094880 2.5818 + 15 0.0000 0.112398 3.0585 + 16 0.0000 0.121710 3.3119 + 17 0.0000 0.145805 3.9676 + 18 0.0000 0.157540 4.2869 + 19 0.0000 0.169567 4.6141 + 20 0.0000 0.183196 4.9850 + 21 0.0000 0.194869 5.3027 + 22 0.0000 0.204587 5.5671 + 23 0.0000 0.233481 6.3533 + 24 0.0000 0.255100 6.9416 + 25 0.0000 0.299606 8.1527 + 26 0.0000 0.311852 8.4859 + 27 0.0000 0.343166 9.3380 + 28 0.0000 0.349895 9.5211 + 29 0.0000 0.394858 10.7446 + 30 0.0000 0.428506 11.6602 + 31 0.0000 0.514145 13.9906 + 32 0.0000 0.522669 14.2226 + 33 0.0000 0.534436 14.5427 + 34 0.0000 0.563350 15.3295 + 35 0.0000 0.617313 16.7979 + 36 0.0000 0.635054 17.2807 + 37 0.0000 0.657645 17.8954 + 38 0.0000 0.687632 18.7114 + 39 0.0000 0.700682 19.0665 + 40 0.0000 0.733968 19.9723 + 41 0.0000 0.752499 20.4766 + 42 0.0000 0.760742 20.7008 + 43 0.0000 0.790401 21.5079 + 44 0.0000 0.799371 21.7520 + 45 0.0000 0.844246 22.9731 + 46 0.0000 0.847312 23.0565 + 47 0.0000 0.875716 23.8295 + 48 0.0000 0.920117 25.0377 + 49 0.0000 0.939114 25.5546 + 50 0.0000 0.960242 26.1295 + 51 0.0000 0.996431 27.1143 + 52 0.0000 1.021722 27.8025 + 53 0.0000 1.053134 28.6572 + 54 0.0000 1.075823 29.2746 + 55 0.0000 1.086266 29.5588 + 56 0.0000 1.179040 32.0833 + 57 0.0000 1.195486 32.5308 + 58 0.0000 1.240132 33.7457 + 59 0.0000 1.277675 34.7673 + 60 0.0000 1.356250 36.9054 + 61 0.0000 1.409460 38.3534 + 62 0.0000 1.443554 39.2811 + 63 0.0000 1.503672 40.9170 + 64 0.0000 1.541942 41.9584 + 65 0.0000 1.554849 42.3096 + 66 0.0000 1.596235 43.4357 + 67 0.0000 1.627177 44.2777 + 68 0.0000 1.656623 45.0790 + 69 0.0000 1.744702 47.4758 + 70 0.0000 1.786140 48.6033 + 71 0.0000 1.819251 49.5043 + 72 0.0000 1.899218 51.6803 + 73 0.0000 1.941924 52.8424 + 74 0.0000 1.986358 54.0515 + 75 0.0000 2.014105 54.8066 + 76 0.0000 2.033294 55.3287 + 77 0.0000 2.097291 57.0702 + 78 0.0000 2.159283 58.7571 + 79 0.0000 2.177582 59.2550 + 80 0.0000 2.270583 61.7857 + 81 0.0000 2.306967 62.7758 + 82 0.0000 2.363034 64.3014 + 83 0.0000 2.388759 65.0014 + 84 0.0000 2.428538 66.0839 + 85 0.0000 2.444690 66.5234 + 86 0.0000 2.464831 67.0715 + 87 0.0000 2.522617 68.6439 + 88 0.0000 2.542915 69.1962 + 89 0.0000 2.553362 69.4805 + 90 0.0000 2.576949 70.1223 + 91 0.0000 2.622946 71.3740 + 92 0.0000 2.668927 72.6252 + 93 0.0000 2.676966 72.8439 + 94 0.0000 2.738248 74.5115 + 95 0.0000 2.805948 76.3537 + 96 0.0000 2.869369 78.0795 + 97 0.0000 2.963399 80.6382 + 98 0.0000 2.982940 81.1699 + 99 0.0000 3.046197 82.8912 + 100 0.0000 3.147620 85.6511 + 101 0.0000 3.162959 86.0685 + 102 0.0000 3.222536 87.6897 + 103 0.0000 3.517287 95.7102 + 104 0.0000 3.716533 101.1320 + 105 0.0000 3.874309 105.4253 + 106 0.0000 4.015610 109.2703 + 107 0.0000 4.148319 112.8815 + 108 0.0000 4.178577 113.7049 + 109 0.0000 4.281549 116.5069 + 110 0.0000 4.365623 118.7946 + 111 0.0000 4.422020 120.3293 + 112 0.0000 4.516457 122.8990 + 113 0.0000 4.562276 124.1458 + 114 0.0000 4.690376 127.6316 + 115 0.0000 4.821470 131.1989 + 116 0.0000 4.871661 132.5646 + 117 0.0000 4.880651 132.8093 + 118 0.0000 4.954671 134.8235 + 119 0.0000 5.004198 136.1712 + 120 0.0000 5.074283 138.0783 + 121 0.0000 5.110738 139.0703 + 122 0.0000 5.193446 141.3209 + 123 0.0000 5.230838 142.3383 + 124 0.0000 5.232632 142.3872 + 125 0.0000 5.291271 143.9828 + 126 0.0000 5.387690 146.6065 + 127 0.0000 5.478882 149.0880 + 128 0.0000 5.545693 150.9060 + 129 0.0000 5.684519 154.6836 + 130 0.0000 5.782352 157.3458 + 131 0.0000 5.933821 161.4675 + 132 0.0000 6.175012 168.0306 + 133 0.0000 6.411576 174.4678 + 134 0.0000 6.507986 177.0913 + 135 0.0000 6.544058 178.0729 + 136 0.0000 6.684296 181.8889 + 137 0.0000 6.718988 182.8330 + 138 0.0000 6.771932 184.2736 + 139 0.0000 6.808878 185.2790 + 140 0.0000 6.928967 188.5468 + 141 0.0000 7.101640 193.2455 + 142 0.0000 7.136045 194.1817 + 143 0.0000 7.163470 194.9279 + 144 0.0000 7.177113 195.2992 + 145 0.0000 7.240098 197.0131 + 146 0.0000 7.275777 197.9840 + 147 0.0000 7.310642 198.9327 + 148 0.0000 7.397428 201.2943 + 149 0.0000 7.453822 202.8288 + 150 0.0000 7.489940 203.8116 + 151 0.0000 7.511401 204.3956 + 152 0.0000 7.597714 206.7443 + 153 0.0000 7.663733 208.5408 + 154 0.0000 7.856922 213.7977 + 155 0.0000 7.889653 214.6884 + 156 0.0000 8.244652 224.3484 + 157 0.0000 8.321972 226.4524 + 158 0.0000 14.136588 384.6761 + 159 0.0000 15.137017 411.8992 + 160 0.0000 15.653186 425.9448 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.293798 0.000000 + 1 N : 0.340484 0.000000 + 2 O : -0.295831 0.000000 + 3 H : 0.249145 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.809439 s : 3.809439 + pz : 1.476986 p : 4.443251 + px : 1.561185 + py : 1.405079 + dz2 : 0.009461 d : 0.035807 + dxz : 0.007843 + dyz : 0.003970 + dx2y2 : 0.013770 + dxy : 0.000764 + f0 : 0.000771 f : 0.005300 + f+1 : 0.001278 + f-1 : 0.000435 + f+2 : 0.000995 + f-2 : 0.001176 + f+3 : 0.000145 + f-3 : 0.000501 + 1 N s : 3.857122 s : 3.857122 + pz : 0.719084 p : 2.625931 + px : 0.728541 + py : 1.178306 + dz2 : 0.031242 d : 0.143422 + dxz : 0.029307 + dyz : 0.020846 + dx2y2 : 0.033975 + dxy : 0.028053 + f0 : 0.005453 f : 0.033042 + f+1 : 0.001913 + f-1 : 0.005144 + f+2 : 0.003254 + f-2 : 0.005852 + f+3 : 0.003862 + f-3 : 0.007565 + 2 O s : 3.861482 s : 3.861482 + pz : 1.562955 p : 4.366507 + px : 1.413734 + py : 1.389817 + dz2 : 0.008056 d : 0.060375 + dxz : 0.003680 + dyz : 0.018250 + dx2y2 : 0.014826 + dxy : 0.015562 + f0 : 0.000646 f : 0.007467 + f+1 : 0.000384 + f-1 : 0.001404 + f+2 : 0.000663 + f-2 : 0.001040 + f+3 : 0.001309 + f-3 : 0.002021 + 3 H s : 0.644416 s : 0.644416 + pz : 0.028207 p : 0.085145 + px : 0.035895 + py : 0.021043 + dz2 : 0.000308 d : 0.021294 + dxz : -0.000392 + dyz : 0.010284 + dx2y2 : 0.002375 + dxy : 0.008719 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.599151 0.000000 + 1 N : -0.278962 0.000000 + 2 O : 0.244286 0.000000 + 3 H : -0.564476 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.109255 s : 3.109255 + pz : 1.296995 p : 3.905061 + px : 1.308602 + py : 1.299464 + dz2 : 0.054262 d : 0.295068 + dxz : 0.088166 + dyz : 0.050476 + dx2y2 : 0.049355 + dxy : 0.052809 + f0 : 0.009338 f : 0.091465 + f+1 : 0.018890 + f-1 : 0.010593 + f+2 : 0.014911 + f-2 : 0.022373 + f+3 : 0.006103 + f-3 : 0.009256 + 1 N s : 3.004570 s : 3.004570 + pz : 0.786015 p : 2.831445 + px : 0.788687 + py : 1.256743 + dz2 : 0.193471 d : 0.973334 + dxz : 0.207512 + dyz : 0.155784 + dx2y2 : 0.230338 + dxy : 0.186229 + f0 : 0.063437 f : 0.469614 + f+1 : 0.050267 + f-1 : 0.061281 + f+2 : 0.051038 + f-2 : 0.089170 + f+3 : 0.064264 + f-3 : 0.090157 + 2 O s : 3.301159 s : 3.301159 + pz : 1.313829 p : 4.018172 + px : 1.264120 + py : 1.440222 + dz2 : 0.049127 d : 0.320642 + dxz : 0.044279 + dyz : 0.047706 + dx2y2 : 0.105009 + dxy : 0.074521 + f0 : 0.008799 f : 0.115741 + f+1 : 0.006608 + f-1 : 0.020084 + f+2 : 0.009198 + f-2 : 0.019434 + f+3 : 0.023945 + f-3 : 0.027673 + 3 H s : 0.612357 s : 0.612357 + pz : 0.139848 p : 0.546400 + px : 0.147349 + py : 0.259203 + dz2 : 0.036238 d : 0.405719 + dxz : 0.031950 + dyz : 0.114310 + dx2y2 : 0.110745 + dxy : 0.112475 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2938 8.0000 -0.2938 1.8133 1.8133 -0.0000 + 1 N 6.6595 7.0000 0.3405 2.5165 2.5165 0.0000 + 2 O 8.2958 8.0000 -0.2958 1.6892 1.6892 -0.0000 + 3 H 0.7509 1.0000 0.2491 1.0149 1.0149 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8221 B( 0-O , 3-H ) : 0.9323 B( 1-N , 2-O ) : 1.6210 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.045 sec +Sum of individual times .... 0.808 sec ( 77.4%) + +Fock matrix formation .... 0.626 sec ( 59.9%) +Diagonalization .... 0.066 sec ( 6.3%) +Density matrix formation .... 0.005 sec ( 0.5%) +Population analysis .... 0.057 sec ( 5.4%) +Initial guess .... 0.009 sec ( 0.9%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.5%) +DIIS solution .... 0.046 sec ( 4.4%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.222 sec +Reference energy ... -204.720671611 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.367 sec +AO-integral generation ... 0.143 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.371 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.024 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.038 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.348 sec +AO-integral generation ... 0.244 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.049 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.150 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.252 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090486323 +EMP2(bb)= -0.090486323 +EMP2(ab)= -0.515104615 + +Initial guess performed in 0.132 sec +E(0) ... -204.720671611 +E(MP2) ... -0.696077260 +Initial E(tot) ... -205.416748871 + ... 0.186736493 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.416748871 -0.696077260 -0.000000000 0.028253121 2.73 0.000001473 + *** Turning on DIIS *** + 1 -205.388018469 -0.667346858 0.028730403 0.010878758 2.73 0.057977531 + 2 -205.407409554 -0.686737943 -0.019391085 0.006354424 2.80 0.061225125 + 3 -205.411109508 -0.690437897 -0.003699955 0.002229857 2.85 0.075659769 + 4 -205.412691642 -0.692020031 -0.001582133 0.001402787 2.85 0.082675546 + 5 -205.413244974 -0.692573363 -0.000553333 0.000808201 2.91 0.088281085 + 6 -205.413349420 -0.692677809 -0.000104446 0.000502203 2.77 0.090888702 + 7 -205.413391674 -0.692720063 -0.000042254 0.000222892 2.81 0.091988073 + 8 -205.413401351 -0.692729740 -0.000009677 0.000114188 2.85 0.092396123 + 9 -205.413397327 -0.692725716 0.000004024 0.000027564 2.82 0.092517476 + 10 -205.413401999 -0.692730388 -0.000004671 0.000017285 2.76 0.092563098 + 11 -205.413399530 -0.692727919 0.000002468 0.000012714 2.78 0.092553096 + 12 -205.413400458 -0.692728847 -0.000000927 0.000009077 2.78 0.092561395 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.720671611 +E(CORR) ... -0.692728847 +E(TOT) ... -205.413400458 +Singles norm **1/2 ... 0.092561395 ( 0.046280697, 0.046280697) +T1 diagnostic ... 0.021816930 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.061310 + 10a-> 13a 10b-> 13b 0.049027 + 8a-> 13a -1a-> -1a 0.047561 + 8b-> 13b -1b-> -1b 0.047561 + 8a-> 13a 10b-> 13b 0.033002 + 10a-> 13a 8b-> 13b 0.033002 + 11a-> 13a 11b-> 13b 0.029736 + 10a-> 13a -1a-> -1a 0.026427 + 10b-> 13b -1b-> -1b 0.026427 + 5a-> 13a 5b-> 13b 0.025744 + 8a-> 22a 8b-> 13b 0.023330 + 8a-> 13a 8b-> 22b 0.023330 + 11b-> 26b -1b-> -1b 0.022456 + 11a-> 26a -1a-> -1a 0.022456 + 10a-> 13a 10b-> 22b 0.022316 + 10a-> 22a 10b-> 13b 0.022316 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034601923 + alpha-alpha-alpha ... -0.000906699 ( 2.6%) + alpha-alpha-beta ... -0.016394262 ( 47.4%) + alpha-beta -beta ... -0.016394262 ( 47.4%) + beta -beta -beta ... -0.000906699 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034601923 + +Final correlation energy ... -0.727330770 +E(CCSD) ... -205.413400458 +E(CCSD(T)) ... -205.448002381 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.208372496 sqrt= 1.099259976 +W(HF) = 0.827559385 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.207766 -0.000000 + 1 N : 0.149027 0.000000 + 2 O : -0.174740 -0.000000 + 3 H : 0.233479 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.796034 s : 3.796034 + pz : 1.437800 p : 4.337123 + px : 1.519549 + py : 1.379774 + dz2 : 0.016007 d : 0.065663 + dxz : 0.012181 + dyz : 0.011095 + dx2y2 : 0.018259 + dxy : 0.008121 + f0 : 0.001393 f : 0.008946 + f+1 : 0.001572 + f-1 : 0.001055 + f+2 : 0.001385 + f-2 : 0.001612 + f+3 : 0.000800 + f-3 : 0.001128 + 1 N s : 3.908081 s : 3.908081 + pz : 0.794302 p : 2.739697 + px : 0.812715 + py : 1.132681 + dz2 : 0.038803 d : 0.171142 + dxz : 0.035627 + dyz : 0.024671 + dx2y2 : 0.041044 + dxy : 0.030996 + f0 : 0.005147 f : 0.032053 + f+1 : 0.001968 + f-1 : 0.005248 + f+2 : 0.003017 + f-2 : 0.005750 + f+3 : 0.003813 + f-3 : 0.007110 + 2 O s : 3.849044 s : 3.849044 + pz : 1.502919 p : 4.232241 + px : 1.368023 + py : 1.361299 + dz2 : 0.013416 d : 0.083344 + dxz : 0.010294 + dyz : 0.021115 + dx2y2 : 0.020956 + dxy : 0.017563 + f0 : 0.001107 f : 0.010111 + f+1 : 0.000891 + f-1 : 0.001737 + f+2 : 0.001105 + f-2 : 0.001463 + f+3 : 0.001598 + f-3 : 0.002211 + 3 H s : 0.659857 s : 0.659857 + pz : 0.032369 p : 0.087131 + px : 0.039583 + py : 0.015179 + dz2 : 0.000250 d : 0.019533 + dxz : 0.000148 + dyz : 0.009339 + dx2y2 : 0.001738 + dxy : 0.008059 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.614121 -0.000000 + 1 N : -0.327662 -0.000000 + 2 O : 0.280509 0.000000 + 3 H : -0.566968 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.117696 s : 3.117696 + pz : 1.273935 p : 3.842612 + px : 1.285055 + py : 1.283621 + dz2 : 0.061782 d : 0.326708 + dxz : 0.094478 + dyz : 0.055429 + dx2y2 : 0.055964 + dxy : 0.059054 + f0 : 0.011206 f : 0.098863 + f+1 : 0.020573 + f-1 : 0.011303 + f+2 : 0.016103 + f-2 : 0.022380 + f+3 : 0.006977 + f-3 : 0.010322 + 1 N s : 3.010120 s : 3.010120 + pz : 0.826182 p : 2.881838 + px : 0.837730 + py : 1.217926 + dz2 : 0.194325 d : 0.977789 + dxz : 0.214976 + dyz : 0.151050 + dx2y2 : 0.228365 + dxy : 0.189073 + f0 : 0.060458 f : 0.457915 + f+1 : 0.049029 + f-1 : 0.060198 + f+2 : 0.050372 + f-2 : 0.086834 + f+3 : 0.064580 + f-3 : 0.086445 + 2 O s : 3.303163 s : 3.303163 + pz : 1.279518 p : 3.937582 + px : 1.237488 + py : 1.420576 + dz2 : 0.056218 d : 0.354116 + dxz : 0.049405 + dyz : 0.055877 + dx2y2 : 0.111191 + dxy : 0.081425 + f0 : 0.009832 f : 0.124630 + f+1 : 0.007960 + f-1 : 0.020942 + f+2 : 0.011150 + f-2 : 0.020028 + f+3 : 0.024803 + f-3 : 0.029915 + 3 H s : 0.617156 s : 0.617156 + pz : 0.141120 p : 0.554593 + px : 0.149747 + py : 0.263725 + dz2 : 0.035944 d : 0.395219 + dxz : 0.031508 + dyz : 0.110074 + dx2y2 : 0.109312 + dxy : 0.108381 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2078 8.0000 -0.2078 2.1886 1.7386 0.4500 + 1 N 6.8510 7.0000 0.1490 2.8025 2.3307 0.4718 + 2 O 8.1747 8.0000 -0.1747 2.0928 1.5948 0.4980 + 3 H 0.7665 1.0000 0.2335 1.0331 0.9591 0.0740 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7777 B( 0-O , 2-O ) : 0.1009 B( 0-O , 3-H ) : 0.8601 +B( 1-N , 2-O ) : 1.4740 + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 51.478 sec + +Fock Matrix Formation ... 0.222 sec ( 0.4%) +Initial Guess ... 0.132 sec ( 0.3%) +DIIS Solver ... 1.482 sec ( 2.9%) +State Vector Update ... 0.077 sec ( 0.1%) +Sigma-vector construction ... 34.876 sec ( 67.7%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.023 sec ( 0.1% of sigma) + (0-ext) ... 0.063 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.024 sec ( 0.1% of sigma) + (2-ext) ... 0.862 sec ( 2.5% of sigma) + (4-ext) ... 19.385 sec ( 55.6% of sigma) + ... 1.261 sec ( 3.6% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.007 sec ( 0.0% of sigma) + (1-ext) ... 0.100 sec ( 0.3% of sigma) + Fock-dressing ... 1.959 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.069 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 8.691 sec ( 24.9% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.774 sec ( 13.2% of ALL) + I/O of integral and amplitudes ... 0.649 sec ( 9.6% of (T)) + External N**7 contributions ... 3.898 sec ( 57.5% of (T)) + Internal N**7 contributions ... 0.310 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.571 sec ( 23.2% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.448002380957 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.026.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.026.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.443478, -0.299247 -0.295098) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.62478 -0.24285 -0.58669 +Nuclear contribution : -0.95850 0.69113 0.65895 + ----------------------------------------- +Total Dipole Moment : -0.33372 0.44828 0.07226 + ----------------------------------------- +Magnitude (a.u.) : 0.56351 +Magnitude (Debye) : 1.43233 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.774811 0.433025 0.376587 +Rotational constants in MHz : 83186.745142 12981.765899 11289.796646 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.151361 0.489275 0.235041 +x,y,z [Debye]: 0.384729 1.243639 0.597426 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.443478, -0.299247 -0.295098) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.68700 -0.16125 -0.59504 +Nuclear contribution : -0.95850 0.69113 0.65895 + ----------------------------------------- +Total Dipole Moment : -0.27150 0.52989 0.06391 + ----------------------------------------- +Magnitude (a.u.) : 0.59881 +Magnitude (Debye) : 1.52206 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.774811 0.433025 0.376587 +Rotational constants in MHz : 83186.745142 12981.765899 11289.796646 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.078323 0.556314 0.207263 +x,y,z [Debye]: 0.199081 1.414037 0.526820 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 27 * + * * + * Dihedral ( 2, 1, 0, 3) : 32.72727273 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0321696388 RMS(Int)= 0.0000289422 + Iter 1: RMS(Cart)= 0.0000065200 RMS(Int)= 0.0000000658 + Iter 2: RMS(Cart)= 0.0000000148 RMS(Int)= 0.0000000001 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4133 0.000000 + 2. B(O 2,N 1) 1.1850 0.000000 + 3. B(H 3,O 0) 0.9779 0.000000 + 4. A(N 1,O 0,H 3) 104.7632 0.000000 + 5. A(O 0,N 1,O 2) 113.0185 0.000000 + 6. D(O 2,N 1,O 0,H 3) 32.7273 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.523620 -0.360151 0.642430 + N 0.361171 -0.587060 -0.436084 + O 0.974780 0.379054 -0.743168 + H -0.812329 0.568157 0.536823 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.989499 -0.680588 1.214016 + 1 N 7.0000 0 14.007 0.682513 -1.109383 -0.824080 + 2 O 8.0000 0 15.999 1.842067 0.716309 -1.404385 + 3 H 1.0000 0 1.008 -1.535079 1.073662 1.014448 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.411932632437 0.00000000 0.00000000 + O 2 1 0 1.183740191607 113.19003519 0.00000000 + H 1 2 3 0.976010775693 104.96302354 24.54545465 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.668165994852 0.00000000 0.00000000 + O 2 1 0 2.236944775853 113.19003519 0.00000000 + H 1 2 3 1.844393069815 104.96302354 24.54545465 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2243 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2717 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.762449796312 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.7624497963 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.504e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7143172738 0.000000000000 0.00167408 0.00005271 0.0127180 0.7000 + 1 -204.7150536381 -0.000736364327 0.00151178 0.00004909 0.0106191 0.7000 + ***Turning on DIIS*** + 2 -204.7156962960 -0.000642657828 0.00405386 0.00013596 0.0087123 0.0000 + 3 -204.7190852386 -0.003388942662 0.00191848 0.00006272 0.0038846 0.0000 + 4 -204.7169554961 0.002129742505 0.00091152 0.00003263 0.0016238 0.0000 + 5 -204.7189754649 -0.002019968769 0.00082860 0.00003813 0.0008705 0.0000 + 6 -204.7181799933 0.000795471617 0.00050306 0.00002538 0.0006613 0.0000 + 7 -204.7177161480 0.000463845322 0.00039631 0.00001578 0.0003488 0.0000 + 8 -204.7187269835 -0.001010835563 0.00021360 0.00000961 0.0001947 0.0000 + 9 -204.7182185127 0.000508470865 0.00011451 0.00000340 0.0000825 0.0000 + 10 -204.7181972630 0.000021249627 0.00003651 0.00000117 0.0000459 0.0000 + 11 -204.7183804440 -0.000183181006 0.00002464 0.00000063 0.0000203 0.0000 + 12 -204.7182876415 0.000092802534 0.00000731 0.00000020 0.0000067 0.0000 + 13 -204.7183098535 -0.000022211971 0.00000246 0.00000007 0.0000024 0.0000 + 14 -204.7183017256 0.000008127846 0.00000092 0.00000004 0.0000013 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 15 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71830205 Eh -5570.66821 eV + +Components: +Nuclear Repulsion : 69.76244980 Eh 1898.33277 eV +Electronic Energy : -274.48075185 Eh -7469.00097 eV +One Electron Energy: -419.13563029 Eh -11405.26033 eV +Two Electron Energy: 144.65487844 Eh 3936.25936 eV + +Virial components: +Potential Energy : -408.95873201 Eh -11128.33285 eV +Kinetic Energy : 204.24042996 Eh 5557.66465 eV +Virial Ratio : 2.00233975 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -3.2728e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.7733e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.4104e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.8032e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.670636 -562.4766 + 1 1.0000 -20.644202 -561.7573 + 2 1.0000 -15.802369 -430.0043 + 3 1.0000 -1.606983 -43.7282 + 4 1.0000 -1.402263 -38.1575 + 5 1.0000 -0.964241 -26.2383 + 6 1.0000 -0.774784 -21.0829 + 7 1.0000 -0.740223 -20.1425 + 8 1.0000 -0.693461 -18.8700 + 9 1.0000 -0.607401 -16.5282 + 10 1.0000 -0.533967 -14.5300 + 11 1.0000 -0.472412 -12.8550 + 12 0.0000 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0.0000 4.806810 130.7999 + 116 0.0000 4.850947 132.0010 + 117 0.0000 4.870454 132.5318 + 118 0.0000 4.964978 135.1039 + 119 0.0000 5.006051 136.2216 + 120 0.0000 5.073986 138.0702 + 121 0.0000 5.108064 138.9975 + 122 0.0000 5.183898 141.0610 + 123 0.0000 5.233312 142.4057 + 124 0.0000 5.239751 142.5809 + 125 0.0000 5.281533 143.7178 + 126 0.0000 5.386223 146.5666 + 127 0.0000 5.479130 149.0947 + 128 0.0000 5.540366 150.7610 + 129 0.0000 5.689504 154.8193 + 130 0.0000 5.784322 157.3994 + 131 0.0000 5.941285 161.6706 + 132 0.0000 6.177832 168.1073 + 133 0.0000 6.409450 174.4100 + 134 0.0000 6.504179 176.9877 + 135 0.0000 6.537797 177.9025 + 136 0.0000 6.687833 181.9852 + 137 0.0000 6.723827 182.9646 + 138 0.0000 6.774990 184.3569 + 139 0.0000 6.802687 185.1105 + 140 0.0000 6.917509 188.2350 + 141 0.0000 7.100043 193.2020 + 142 0.0000 7.129873 194.0137 + 143 0.0000 7.169872 195.1021 + 144 0.0000 7.179160 195.3549 + 145 0.0000 7.245247 197.1532 + 146 0.0000 7.271604 197.8704 + 147 0.0000 7.305736 198.7992 + 148 0.0000 7.391695 201.1382 + 149 0.0000 7.459438 202.9816 + 150 0.0000 7.506667 204.2668 + 151 0.0000 7.522606 204.7005 + 152 0.0000 7.580753 206.2828 + 153 0.0000 7.665118 208.5785 + 154 0.0000 7.830936 213.0906 + 155 0.0000 7.885515 214.5758 + 156 0.0000 8.204032 223.2431 + 157 0.0000 8.334335 226.7888 + 158 0.0000 14.094833 383.5399 + 159 0.0000 15.145869 412.1401 + 160 0.0000 15.618931 425.0127 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.670636 -562.4766 + 1 1.0000 -20.644202 -561.7573 + 2 1.0000 -15.802369 -430.0043 + 3 1.0000 -1.606983 -43.7282 + 4 1.0000 -1.402263 -38.1575 + 5 1.0000 -0.964241 -26.2383 + 6 1.0000 -0.774784 -21.0829 + 7 1.0000 -0.740223 -20.1425 + 8 1.0000 -0.693461 -18.8700 + 9 1.0000 -0.607401 -16.5282 + 10 1.0000 -0.533967 -14.5300 + 11 1.0000 -0.472412 -12.8550 + 12 0.0000 0.031029 0.8443 + 13 0.0000 0.072814 1.9814 + 14 0.0000 0.094860 2.5813 + 15 0.0000 0.111792 3.0420 + 16 0.0000 0.118759 3.2316 + 17 0.0000 0.148799 4.0490 + 18 0.0000 0.157127 4.2756 + 19 0.0000 0.170122 4.6292 + 20 0.0000 0.182129 4.9560 + 21 0.0000 0.194348 5.2885 + 22 0.0000 0.204086 5.5535 + 23 0.0000 0.234181 6.3724 + 24 0.0000 0.258063 7.0222 + 25 0.0000 0.298399 8.1198 + 26 0.0000 0.312901 8.5145 + 27 0.0000 0.343181 9.3384 + 28 0.0000 0.348917 9.4945 + 29 0.0000 0.388265 10.5652 + 30 0.0000 0.423926 11.5356 + 31 0.0000 0.514822 14.0090 + 32 0.0000 0.526108 14.3161 + 33 0.0000 0.534353 14.5405 + 34 0.0000 0.563264 15.3272 + 35 0.0000 0.614913 16.7326 + 36 0.0000 0.633007 17.2250 + 37 0.0000 0.652818 17.7641 + 38 0.0000 0.690097 18.7785 + 39 0.0000 0.703779 19.1508 + 40 0.0000 0.732640 19.9362 + 41 0.0000 0.748771 20.3751 + 42 0.0000 0.763884 20.7863 + 43 0.0000 0.787715 21.4348 + 44 0.0000 0.806202 21.9379 + 45 0.0000 0.840639 22.8749 + 46 0.0000 0.848659 23.0932 + 47 0.0000 0.877684 23.8830 + 48 0.0000 0.919569 25.0227 + 49 0.0000 0.940987 25.6056 + 50 0.0000 0.963164 26.2090 + 51 0.0000 0.988825 26.9073 + 52 0.0000 1.018346 27.7106 + 53 0.0000 1.040559 28.3151 + 54 0.0000 1.069524 29.1032 + 55 0.0000 1.087640 29.5962 + 56 0.0000 1.175276 31.9809 + 57 0.0000 1.194540 32.5051 + 58 0.0000 1.239462 33.7275 + 59 0.0000 1.279456 34.8158 + 60 0.0000 1.359347 36.9897 + 61 0.0000 1.411310 38.4037 + 62 0.0000 1.435698 39.0673 + 63 0.0000 1.510030 41.0900 + 64 0.0000 1.533915 41.7399 + 65 0.0000 1.553564 42.2746 + 66 0.0000 1.606412 43.7127 + 67 0.0000 1.632905 44.4336 + 68 0.0000 1.655007 45.0350 + 69 0.0000 1.739306 47.3289 + 70 0.0000 1.780849 48.4594 + 71 0.0000 1.813517 49.3483 + 72 0.0000 1.898337 51.6564 + 73 0.0000 1.956684 53.2441 + 74 0.0000 1.983779 53.9814 + 75 0.0000 2.022925 55.0466 + 76 0.0000 2.034886 55.3721 + 77 0.0000 2.089308 56.8530 + 78 0.0000 2.157976 58.7215 + 79 0.0000 2.176077 59.2141 + 80 0.0000 2.262017 61.5526 + 81 0.0000 2.306624 62.7664 + 82 0.0000 2.361783 64.2674 + 83 0.0000 2.393056 65.1184 + 84 0.0000 2.418584 65.8130 + 85 0.0000 2.446886 66.5831 + 86 0.0000 2.466193 67.1085 + 87 0.0000 2.520418 68.5840 + 88 0.0000 2.540438 69.1288 + 89 0.0000 2.556198 69.5577 + 90 0.0000 2.576582 70.1124 + 91 0.0000 2.621100 71.3238 + 92 0.0000 2.662145 72.4406 + 93 0.0000 2.682795 73.0026 + 94 0.0000 2.749348 74.8136 + 95 0.0000 2.802492 76.2597 + 96 0.0000 2.852552 77.6219 + 97 0.0000 2.961495 80.5864 + 98 0.0000 2.983254 81.1785 + 99 0.0000 3.040376 82.7328 + 100 0.0000 3.148502 85.6751 + 101 0.0000 3.165492 86.1374 + 102 0.0000 3.223780 87.7235 + 103 0.0000 3.519445 95.7690 + 104 0.0000 3.697183 100.6055 + 105 0.0000 3.884864 105.7125 + 106 0.0000 4.015546 109.2686 + 107 0.0000 4.144512 112.7779 + 108 0.0000 4.175992 113.6345 + 109 0.0000 4.306713 117.1916 + 110 0.0000 4.372796 118.9898 + 111 0.0000 4.415870 120.1619 + 112 0.0000 4.517172 122.9185 + 113 0.0000 4.563122 124.1688 + 114 0.0000 4.683574 127.4465 + 115 0.0000 4.806810 130.7999 + 116 0.0000 4.850947 132.0010 + 117 0.0000 4.870454 132.5318 + 118 0.0000 4.964978 135.1039 + 119 0.0000 5.006051 136.2216 + 120 0.0000 5.073986 138.0702 + 121 0.0000 5.108064 138.9975 + 122 0.0000 5.183898 141.0610 + 123 0.0000 5.233312 142.4057 + 124 0.0000 5.239751 142.5809 + 125 0.0000 5.281533 143.7178 + 126 0.0000 5.386223 146.5666 + 127 0.0000 5.479130 149.0947 + 128 0.0000 5.540366 150.7610 + 129 0.0000 5.689504 154.8193 + 130 0.0000 5.784322 157.3994 + 131 0.0000 5.941285 161.6706 + 132 0.0000 6.177832 168.1073 + 133 0.0000 6.409450 174.4100 + 134 0.0000 6.504179 176.9877 + 135 0.0000 6.537797 177.9025 + 136 0.0000 6.687833 181.9852 + 137 0.0000 6.723827 182.9646 + 138 0.0000 6.774990 184.3569 + 139 0.0000 6.802687 185.1105 + 140 0.0000 6.917509 188.2350 + 141 0.0000 7.100043 193.2020 + 142 0.0000 7.129873 194.0137 + 143 0.0000 7.169872 195.1021 + 144 0.0000 7.179160 195.3549 + 145 0.0000 7.245247 197.1532 + 146 0.0000 7.271604 197.8704 + 147 0.0000 7.305736 198.7992 + 148 0.0000 7.391695 201.1382 + 149 0.0000 7.459438 202.9816 + 150 0.0000 7.506667 204.2668 + 151 0.0000 7.522606 204.7005 + 152 0.0000 7.580753 206.2828 + 153 0.0000 7.665118 208.5785 + 154 0.0000 7.830936 213.0906 + 155 0.0000 7.885515 214.5758 + 156 0.0000 8.204032 223.2431 + 157 0.0000 8.334335 226.7888 + 158 0.0000 14.094833 383.5399 + 159 0.0000 15.145869 412.1401 + 160 0.0000 15.618931 425.0127 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.302326 0.000000 + 1 N : 0.341309 0.000000 + 2 O : -0.292397 0.000000 + 3 H : 0.253415 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.815191 s : 3.815191 + pz : 1.442401 p : 4.446884 + px : 1.582466 + py : 1.422017 + dz2 : 0.009274 d : 0.035023 + dxz : 0.008015 + dyz : 0.004807 + dx2y2 : 0.012175 + dxy : 0.000752 + f0 : 0.000893 f : 0.005227 + f+1 : 0.001230 + f-1 : 0.000503 + f+2 : 0.000955 + f-2 : 0.001064 + f+3 : 0.000183 + f-3 : 0.000398 + 1 N s : 3.850922 s : 3.850922 + pz : 0.730565 p : 2.631354 + px : 0.733900 + py : 1.166888 + dz2 : 0.031277 d : 0.143398 + dxz : 0.029952 + dyz : 0.020226 + dx2y2 : 0.034056 + dxy : 0.027886 + f0 : 0.006257 f : 0.033017 + f+1 : 0.001726 + f-1 : 0.005119 + f+2 : 0.003310 + f-2 : 0.005870 + f+3 : 0.003461 + f-3 : 0.007273 + 2 O s : 3.865528 s : 3.865528 + pz : 1.597014 p : 4.359560 + px : 1.372009 + py : 1.390537 + dz2 : 0.007143 d : 0.059889 + dxz : 0.004083 + dyz : 0.017658 + dx2y2 : 0.016292 + dxy : 0.014714 + f0 : 0.000742 f : 0.007421 + f+1 : 0.000435 + f-1 : 0.001246 + f+2 : 0.000520 + f-2 : 0.001072 + f+3 : 0.001334 + f-3 : 0.002071 + 3 H s : 0.639923 s : 0.639923 + pz : 0.026818 p : 0.085613 + px : 0.036697 + py : 0.022098 + dz2 : 0.000548 d : 0.021049 + dxz : -0.000029 + dyz : 0.009604 + dx2y2 : 0.003289 + dxy : 0.007636 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.594800 0.000000 + 1 N : -0.279646 0.000000 + 2 O : 0.243046 0.000000 + 3 H : -0.558201 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.110472 s : 3.110472 + pz : 1.286394 p : 3.909200 + px : 1.317340 + py : 1.305467 + dz2 : 0.059030 d : 0.294433 + dxz : 0.087175 + dyz : 0.053690 + dx2y2 : 0.044020 + dxy : 0.050518 + f0 : 0.010125 f : 0.091095 + f+1 : 0.019332 + f-1 : 0.012413 + f+2 : 0.014723 + f-2 : 0.021427 + f+3 : 0.006172 + f-3 : 0.006902 + 1 N s : 3.005760 s : 3.005760 + pz : 0.799557 p : 2.833306 + px : 0.792164 + py : 1.241585 + dz2 : 0.197318 d : 0.971459 + dxz : 0.210391 + dyz : 0.155960 + dx2y2 : 0.220617 + dxy : 0.187173 + f0 : 0.071070 f : 0.469121 + f+1 : 0.050535 + f-1 : 0.061310 + f+2 : 0.046884 + f-2 : 0.090324 + f+3 : 0.063249 + f-3 : 0.085749 + 2 O s : 3.304279 s : 3.304279 + pz : 1.334153 p : 4.016779 + px : 1.248628 + py : 1.433998 + dz2 : 0.049594 d : 0.320329 + dxz : 0.045901 + dyz : 0.045461 + dx2y2 : 0.098694 + dxy : 0.080680 + f0 : 0.009144 f : 0.115568 + f+1 : 0.007423 + f-1 : 0.019616 + f+2 : 0.007542 + f-2 : 0.019914 + f+3 : 0.025847 + f-3 : 0.026080 + 3 H s : 0.611419 s : 0.611419 + pz : 0.139586 p : 0.545605 + px : 0.151064 + py : 0.254954 + dz2 : 0.035410 d : 0.401177 + dxz : 0.034603 + dyz : 0.110551 + dx2y2 : 0.111448 + dxy : 0.109165 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3023 8.0000 -0.3023 1.8131 1.8131 -0.0000 + 1 N 6.6587 7.0000 0.3413 2.5240 2.5240 0.0000 + 2 O 8.2924 8.0000 -0.2924 1.7010 1.7010 0.0000 + 3 H 0.7466 1.0000 0.2534 1.0106 1.0106 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8207 B( 0-O , 3-H ) : 0.9337 B( 1-N , 2-O ) : 1.6344 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.423 sec +Sum of individual times .... 2.170 sec ( 89.6%) + +Fock matrix formation .... 1.761 sec ( 72.7%) +Diagonalization .... 0.179 sec ( 7.4%) +Density matrix formation .... 0.013 sec ( 0.5%) +Population analysis .... 0.057 sec ( 2.3%) +Initial guess .... 0.009 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.2%) +DIIS solution .... 0.151 sec ( 6.2%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.205 sec +Reference energy ... -204.718301957 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.369 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.373 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.024 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.028 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.036 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.039 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.354 sec +AO-integral generation ... 0.250 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.049 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.151 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.250 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090405114 +EMP2(bb)= -0.090405114 +EMP2(ab)= -0.515169960 + +Initial guess performed in 0.133 sec +E(0) ... -204.718301957 +E(MP2) ... -0.695980187 +Initial E(tot) ... -205.414282144 + ... 0.186806685 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.414282144 -0.695980187 -0.000000000 0.026844168 2.73 0.000002788 + *** Turning on DIIS *** + 1 -205.385763912 -0.667461956 0.028518232 0.009992778 2.73 0.057555494 + 2 -205.405122818 -0.686820861 -0.019358905 0.006010243 2.78 0.060847811 + 3 -205.408837025 -0.690535068 -0.003714207 0.002081309 2.84 0.075152569 + 4 -205.410413039 -0.692111083 -0.001576015 0.001393916 2.80 0.082087050 + 5 -205.410961464 -0.692659508 -0.000548425 0.000820831 2.89 0.087627532 + 6 -205.411066138 -0.692764182 -0.000104674 0.000509122 2.83 0.090253900 + 7 -205.411108845 -0.692806889 -0.000042707 0.000232737 2.89 0.091388306 + 8 -205.411118739 -0.692816782 -0.000009893 0.000115472 2.89 0.091828817 + 9 -205.411114817 -0.692812860 0.000003922 0.000037445 2.82 0.091963932 + 10 -205.411119575 -0.692817618 -0.000004758 0.000023340 2.77 0.092015187 + 11 -205.411116942 -0.692814985 0.000002633 0.000017052 2.77 0.092004722 + 12 -205.411118057 -0.692816101 -0.000001116 0.000011731 2.79 0.092014888 + 13 -205.411117938 -0.692815981 0.000000119 0.000007173 2.83 0.092012038 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.718301957 +E(CORR) ... -0.692815981 +E(TOT) ... -205.411117938 +Singles norm **1/2 ... 0.092012038 ( 0.046006019, 0.046006019) +T1 diagnostic ... 0.021687445 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.057607 + 8a-> 13a -1a-> -1a 0.044979 + 8b-> 13b -1b-> -1b 0.044979 + 10a-> 13a 10b-> 13b 0.044556 + 8a-> 13a 10b-> 13b 0.030358 + 10a-> 13a 8b-> 13b 0.030358 + 11a-> 13a 11b-> 13b 0.030333 + 9a-> 13a 9b-> 13b 0.028775 + 10a-> 13a -1a-> -1a 0.026289 + 10b-> 13b -1b-> -1b 0.026289 + 8a-> 13a 9b-> 13b 0.026129 + 9a-> 13a 8b-> 13b 0.026129 + 5a-> 13a 5b-> 13b 0.025937 + 10a-> 13a 9b-> 13b 0.023902 + 9a-> 13a 10b-> 13b 0.023902 + 8a-> 13a 8b-> 22b 0.021683 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034524679 + alpha-alpha-alpha ... -0.000901309 ( 2.6%) + alpha-alpha-beta ... -0.016361031 ( 47.4%) + alpha-beta -beta ... -0.016361031 ( 47.4%) + beta -beta -beta ... -0.000901309 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034524679 + +Final correlation energy ... -0.727340660 +E(CCSD) ... -205.411117938 +E(CCSD(T)) ... -205.445642617 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.208571254 sqrt= 1.099350378 +W(HF) = 0.827423288 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.218833 0.000000 + 1 N : 0.151465 -0.000000 + 2 O : -0.170676 0.000000 + 3 H : 0.238043 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.800391 s : 3.800391 + pz : 1.407519 p : 4.344558 + px : 1.541136 + py : 1.395902 + dz2 : 0.015675 d : 0.065010 + dxz : 0.012404 + dyz : 0.011876 + dx2y2 : 0.017083 + dxy : 0.007972 + f0 : 0.001515 f : 0.008874 + f+1 : 0.001485 + f-1 : 0.001108 + f+2 : 0.001368 + f-2 : 0.001521 + f+3 : 0.000842 + f-3 : 0.001035 + 1 N s : 3.903127 s : 3.903127 + pz : 0.798363 p : 2.741753 + px : 0.817682 + py : 1.125707 + dz2 : 0.038937 d : 0.171626 + dxz : 0.036531 + dyz : 0.024556 + dx2y2 : 0.040530 + dxy : 0.031072 + f0 : 0.005860 f : 0.032029 + f+1 : 0.001762 + f-1 : 0.005268 + f+2 : 0.003150 + f-2 : 0.005763 + f+3 : 0.003519 + f-3 : 0.006707 + 2 O s : 3.852632 s : 3.852632 + pz : 1.534337 p : 4.225290 + px : 1.329570 + py : 1.361383 + dz2 : 0.012556 d : 0.082706 + dxz : 0.010682 + dyz : 0.020876 + dx2y2 : 0.021878 + dxy : 0.016714 + f0 : 0.001198 f : 0.010048 + f+1 : 0.000931 + f-1 : 0.001609 + f+2 : 0.000997 + f-2 : 0.001480 + f+3 : 0.001621 + f-3 : 0.002211 + 3 H s : 0.654732 s : 0.654732 + pz : 0.030871 p : 0.088056 + px : 0.040331 + py : 0.016854 + dz2 : 0.000439 d : 0.019169 + dxz : 0.000429 + dyz : 0.008715 + dx2y2 : 0.002566 + dxy : 0.007020 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.608888 0.000000 + 1 N : -0.327517 -0.000000 + 2 O : 0.279961 0.000000 + 3 H : -0.561332 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.118562 s : 3.118562 + pz : 1.266104 p : 3.848076 + px : 1.293187 + py : 1.288785 + dz2 : 0.066294 d : 0.326009 + dxz : 0.093510 + dyz : 0.058564 + dx2y2 : 0.050485 + dxy : 0.057157 + f0 : 0.012183 f : 0.098464 + f+1 : 0.020890 + f-1 : 0.012961 + f+2 : 0.015841 + f-2 : 0.021615 + f+3 : 0.007025 + f-3 : 0.007950 + 1 N s : 3.011329 s : 3.011329 + pz : 0.834299 p : 2.882127 + px : 0.841476 + py : 1.206352 + dz2 : 0.199046 d : 0.976447 + dxz : 0.217497 + dyz : 0.150408 + dx2y2 : 0.218125 + dxy : 0.191372 + f0 : 0.067556 f : 0.457614 + f+1 : 0.050059 + f-1 : 0.060398 + f+2 : 0.046021 + f-2 : 0.087893 + f+3 : 0.063384 + f-3 : 0.082303 + 2 O s : 3.306352 s : 3.306352 + pz : 1.297774 p : 3.935996 + px : 1.223793 + py : 1.414429 + dz2 : 0.056350 d : 0.353336 + dxz : 0.051009 + dyz : 0.053226 + dx2y2 : 0.105686 + dxy : 0.087065 + f0 : 0.010183 f : 0.124355 + f+1 : 0.008748 + f-1 : 0.020158 + f+2 : 0.009352 + f-2 : 0.020568 + f+3 : 0.026448 + f-3 : 0.028898 + 3 H s : 0.615923 s : 0.615923 + pz : 0.140862 p : 0.554574 + px : 0.153945 + py : 0.259767 + dz2 : 0.035136 d : 0.390834 + dxz : 0.033851 + dyz : 0.106788 + dx2y2 : 0.109571 + dxy : 0.105488 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2188 8.0000 -0.2188 2.1855 1.7361 0.4494 + 1 N 6.8485 7.0000 0.1515 2.8072 2.3329 0.4742 + 2 O 8.1707 8.0000 -0.1707 2.1016 1.6023 0.4993 + 3 H 0.7620 1.0000 0.2380 1.0291 0.9550 0.0740 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7734 B( 0-O , 3-H ) : 0.8631 B( 1-N , 2-O ) : 1.4852 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 54.468 sec + +Fock Matrix Formation ... 0.205 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 1.791 sec ( 3.3%) +State Vector Update ... 0.084 sec ( 0.2%) +Sigma-vector construction ... 37.471 sec ( 68.8%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.024 sec ( 0.1% of sigma) + (0-ext) ... 0.068 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.025 sec ( 0.1% of sigma) + (2-ext) ... 0.924 sec ( 2.5% of sigma) + (4-ext) ... 20.742 sec ( 55.4% of sigma) + ... 1.349 sec ( 3.6% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.107 sec ( 0.3% of sigma) + Fock-dressing ... 2.108 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.073 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.393 sec ( 25.1% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.840 sec ( 12.6% of ALL) + I/O of integral and amplitudes ... 0.668 sec ( 9.8% of (T)) + External N**7 contributions ... 3.879 sec ( 56.7% of (T)) + Internal N**7 contributions ... 0.310 sec ( 4.5% of (T)) + N**6 triples energy contributions ... 1.551 sec ( 22.7% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.445642616520 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.013416492 -0.000405319 0.007385725 + 2 N : -0.012920435 0.000580948 -0.005950997 + 3 O : 0.007502906 0.000272784 0.005167100 + 4 H : -0.007998964 -0.000448413 -0.006601827 + +Norm of the cartesian gradient ... 0.025064727 +RMS gradient ... 0.007235563 +MAX gradient ... 0.013416492 + +------- +TIMINGS +------- + +Total numerical gradient time ... 346.520 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 373.34 cm**-1 + 7: 664.17 cm**-1 + 8: 862.38 cm**-1 + 9: 1316.92 cm**-1 + 10: 1647.73 cm**-1 + 11: 3613.73 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 -0.003010 -0.272941 0.166556 0.028223 -0.019739 -0.018151 + 1 0.009530 -0.128652 -0.108924 0.071333 0.062453 0.058686 + 2 0.121444 0.149537 -0.196459 -0.054608 0.021237 -0.007146 + 3 -0.012722 0.113047 -0.264077 0.074660 -0.220951 -0.001344 + 4 0.032796 0.149253 0.202364 -0.025762 -0.538085 0.001053 + 5 -0.108676 0.039956 0.319883 -0.047281 0.058199 0.001472 + 6 0.065917 0.170664 0.110899 -0.058977 0.238853 0.000487 + 7 -0.018605 -0.005277 -0.047542 -0.047386 0.409272 0.000051 + 8 0.001531 -0.239374 -0.095882 0.044328 -0.103820 -0.000472 + 9 -0.821674 0.052460 -0.734190 -0.549347 -0.407484 0.299041 + 10 -0.311691 0.051741 -0.328590 -0.022104 -0.010101 -0.946916 + 11 -0.441713 0.870663 0.195005 0.820183 0.502035 0.100470 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 373.34 0.020714 104.68 0.017315 (-0.018708 -0.007930 -0.130007) + 7: 664.17 0.005302 26.79 0.002491 ( 0.040291 0.027220 0.011257) + 8: 862.38 0.054412 274.97 0.019690 (-0.110806 -0.006004 0.085881) + 9: 1316.92 0.001722 8.70 0.000408 (-0.002765 0.018448 0.007746) + 10: 1647.73 0.029254 147.84 0.005540 (-0.054761 -0.018559 0.046875) + 11: 3613.73 0.008192 41.40 0.000707 ( 0.017733 -0.019079 -0.005380) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 373.34 E(vib) ... 0.21 +freq. 664.17 E(vib) ... 0.08 +freq. 862.38 E(vib) ... 0.04 +freq. 1316.92 E(vib) ... 0.01 +freq. 1647.73 E(vib) ... 0.00 +freq. 3613.73 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.44564261 Eh +Zero point energy ... 0.01931492 Eh 12.12 kcal/mol +Thermal vibrational correction ... 0.00053946 Eh 0.34 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42295569 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00337201 Eh 2.12 kcal/mol +Non-thermal (ZPE) correction 0.01931492 Eh 12.12 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02268692 Eh 14.24 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42295569 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.42201148 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.763932 0.431436 0.376661 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00076702 Eh 0.48 kcal/mol +Rotational entropy ... 0.00988867 Eh 6.21 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02845801 Eh 17.86 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00988867 Eh 6.21 kcal/mol| +| sn= 2 | S(rot)= 0.00923421 Eh 5.79 kcal/mol| +| sn= 3 | S(rot)= 0.00885138 Eh 5.55 kcal/mol| +| sn= 4 | S(rot)= 0.00857976 Eh 5.38 kcal/mol| +| sn= 5 | S(rot)= 0.00836907 Eh 5.25 kcal/mol| +| sn= 6 | S(rot)= 0.00819692 Eh 5.14 kcal/mol| +| sn= 7 | S(rot)= 0.00805138 Eh 5.05 kcal/mol| +| sn= 8 | S(rot)= 0.00792530 Eh 4.97 kcal/mol| +| sn= 9 | S(rot)= 0.00781409 Eh 4.90 kcal/mol| +| sn=10 | S(rot)= 0.00771461 Eh 4.84 kcal/mol| +| sn=11 | S(rot)= 0.00762462 Eh 4.78 kcal/mol| +| sn=12 | S(rot)= 0.00754247 Eh 4.73 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.42201148 Eh +Total entropy correction ... -0.02845801 Eh -17.86 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.45046949 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00482688 Eh -3.03 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.445642615 Eh +Current gradient norm .... 0.025064698 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.012846951 0.139815273 0.214165096 0.467100715 0.529582604 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999773396 +Lowest eigenvalues of augmented Hessian: + -0.000098159 0.135297466 0.212700587 0.467059296 0.529399560 +Length of the computed step .... 0.021292294 +The final length of the internal step .... 0.021292294 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0086925425 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0068519195 RMS(Int)= 0.0086929918 + Iter 1: RMS(Cart)= 0.0000078710 RMS(Int)= 0.0000089147 + Iter 2: RMS(Cart)= 0.0000000196 RMS(Int)= 0.0000000366 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0020934891 0.0001000000 NO + MAX gradient 0.0029304849 0.0003000000 NO + RMS step 0.0086925425 0.0020000000 NO + MAX step 0.0184605701 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0098 Max(Angles) 0.30 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4133 -0.002930 0.0098 1.4231 + 2. B(O 2,N 1) 1.1850 0.002769 -0.0036 1.1814 + 3. B(H 3,O 0) 0.9779 0.002649 -0.0032 0.9747 + 4. A(N 1,O 0,H 3) 104.76 -0.001485 0.30 105.06 + 5. A(O 0,N 1,O 2) 113.02 -0.000907 0.09 113.11 + 6. D(O 2,N 1,O 0,H 3) 32.73 0.017878 0.00 32.73 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.526971 -0.357319 0.644410 + N 0.366031 -0.586130 -0.439765 + O 0.978766 0.376163 -0.746770 + H -0.817824 0.567286 0.542126 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.995832 -0.675234 1.217759 + 1 N 7.0000 0 14.007 0.691698 -1.107626 -0.831036 + 2 O 8.0000 0 15.999 1.849600 0.710846 -1.411192 + 3 H 1.0000 0 1.008 -1.545464 1.072015 1.024469 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.423110732988 0.00000000 0.00000000 + O 2 1 0 1.181399859765 113.10798646 0.00000000 + H 1 2 3 0.974654218682 105.06012011 32.72727248 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.689289543591 0.00000000 0.00000000 + O 2 1 0 2.232522189608 113.10798646 0.00000000 + H 1 2 3 1.841829548580 105.06012011 32.72727248 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2243 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2717 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.639638006315 Eh + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.514e-04 +Time for diagonalization ... 0.005 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.003 sec +Total time needed ... 0.009 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7181311603 0.000000000000 0.00028705 0.00000903 0.0014883 0.7000 + 1 -204.7181511139 -0.000019953595 0.00023727 0.00000774 0.0011617 0.7000 + ***Turning on DIIS*** + 2 -204.7181677921 -0.000016678202 0.00062255 0.00002099 0.0009025 0.0000 + 3 -204.7179398399 0.000227952213 0.00029476 0.00000950 0.0002950 0.0000 + 4 -204.7182523089 -0.000312468990 0.00012386 0.00000363 0.0000936 0.0000 + 5 -204.7182666416 -0.000014332678 0.00003881 0.00000112 0.0000618 0.0000 + 6 -204.7181759209 0.000090720673 0.00003048 0.00000063 0.0000372 0.0000 + 7 -204.7182364690 -0.000060548123 0.00001220 0.00000032 0.0000135 0.0000 + 8 -204.7182201888 0.000016280245 0.00000721 0.00000022 0.0000075 0.0000 + 9 -204.7182165781 0.000003610708 0.00000440 0.00000013 0.0000038 0.0000 + 10 -204.7182277443 -0.000011166219 0.00000284 0.00000010 0.0000017 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + +Total Energy : -204.71822303 Eh -5570.66606 eV + Last Energy change ... 4.7127e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.4831e-06 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 4 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.517 sec +Reference energy ... -204.718224524 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 9.819 sec +AO-integral generation ... 0.398 sec +Half transformation ... 0.176 sec +K-integral sorting ... 7.592 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.059 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.083 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.083 s ( 0.000 ms/b) + 151164 b 0 skpd 0.078 s ( 0.001 ms/b) +: 159120 b 0 skpd 0.036 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.080 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.085 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.050 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.085 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.060 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.814 sec +AO-integral generation ... 0.644 sec +Half transformation ... 0.058 sec +J-integral sorting ... 0.085 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.226 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.333 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090387735 +EMP2(bb)= -0.090387735 +EMP2(ab)= -0.515277649 + +Initial guess performed in 0.163 sec +E(0) ... -204.718224524 +E(MP2) ... -0.696053119 +Initial E(tot) ... -205.414277643 + ... 0.186970272 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.414277643 -0.696053119 -0.000000000 0.026538135 4.60 0.000001746 + *** Turning on DIIS *** + 1 -205.385714340 -0.667489816 0.028563304 0.010189460 4.59 0.057667158 + 2 -205.405102560 -0.686878036 -0.019388221 0.005917117 5.79 0.060899813 + 3 -205.408821798 -0.690597274 -0.003719237 0.002023944 4.93 0.075251062 + 4 -205.410400285 -0.692175761 -0.001578487 0.001475936 5.60 0.082206028 + 5 -205.410955328 -0.692730804 -0.000555043 0.000860712 6.98 0.087846327 + 6 -205.411063215 -0.692838691 -0.000107887 0.000529604 5.34 0.090573586 + 7 -205.411107858 -0.692883334 -0.000044643 0.000236395 5.77 0.091775812 + 8 -205.411118519 -0.692893995 -0.000010662 0.000117167 6.31 0.092240648 + 9 -205.411114408 -0.692889884 0.000004111 0.000037729 6.05 0.092379642 + 10 -205.411119393 -0.692894870 -0.000004985 0.000023829 6.36 0.092433593 + 11 -205.411116669 -0.692892146 0.000002724 0.000017338 6.04 0.092422969 + 12 -205.411117786 -0.692893262 -0.000001116 0.000011929 5.08 0.092433834 + 13 -205.411117647 -0.692893124 0.000000138 0.000007355 6.37 0.092430833 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.718224524 +E(CORR) ... -0.692893124 +E(TOT) ... -205.411117647 +Singles norm **1/2 ... 0.092430833 ( 0.046215416, 0.046215416) +T1 diagnostic ... 0.021786156 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.059259 + 8b-> 13b -1b-> -1b 0.044268 + 8a-> 13a -1a-> -1a 0.044268 + 10a-> 13a 10b-> 13b 0.042485 + 11a-> 13a 11b-> 13b 0.030098 + 8a-> 13a 10b-> 13b 0.030098 + 10a-> 13a 8b-> 13b 0.030098 + 9a-> 13a 9b-> 13b 0.028593 + 10a-> 13a -1a-> -1a 0.028299 + 10b-> 13b -1b-> -1b 0.028299 + 9a-> 13a 8b-> 13b 0.026631 + 8a-> 13a 9b-> 13b 0.026631 + 5a-> 13a 5b-> 13b 0.026251 + 9a-> 13a 10b-> 13b 0.023217 + 10a-> 13a 9b-> 13b 0.023217 + 8a-> 13a 8b-> 22b 0.022414 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034574931 + alpha-alpha-alpha ... -0.000901369 ( 2.6%) + alpha-alpha-beta ... -0.016386097 ( 47.4%) + alpha-beta -beta ... -0.016386097 ( 47.4%) + beta -beta -beta ... -0.000901369 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034574931 + +Final correlation energy ... -0.727468055 +E(CCSD) ... -205.411117647 +E(CCSD(T)) ... -205.445692578 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.208941804 sqrt= 1.099518896 +W(HF) = 0.827169676 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 106.746 sec + +Fock Matrix Formation ... 0.517 sec ( 0.5%) +Initial Guess ... 0.163 sec ( 0.2%) +DIIS Solver ... 4.581 sec ( 4.3%) +State Vector Update ... 0.258 sec ( 0.2%) +Sigma-vector construction ... 74.986 sec ( 70.2%) + <0|H|D> ... 0.007 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.048 sec ( 0.1% of sigma) + (0-ext) ... 0.128 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.042 sec ( 0.1% of sigma) + (2-ext) ... 1.425 sec ( 1.9% of sigma) + (4-ext) ... 44.622 sec ( 59.5% of sigma) + ... 3.660 sec ( 4.9% of sigma) + ... 0.005 sec ( 0.0% of sigma) + (1-ext) ... 0.013 sec ( 0.0% of sigma) + (1-ext) ... 0.186 sec ( 0.2% of sigma) + Fock-dressing ... 4.943 sec ( 6.6% of sigma) + (ik|jl)-dressing ... 0.122 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 16.271 sec ( 21.7% of sigma) + Pair energies ... 0.021 sec ( 0.0% of sigma) +Total Time for computing (T) ... 13.492 sec ( 12.6% of ALL) + I/O of integral and amplitudes ... 1.138 sec ( 8.4% of (T)) + External N**7 contributions ... 5.443 sec ( 40.3% of (T)) + Internal N**7 contributions ... 0.438 sec ( 3.2% of (T)) + N**6 triples energy contributions ... 2.191 sec ( 16.2% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.445692578366 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.010814990 0.002780613 0.008151432 + 2 N : -0.009421438 0.002360608 -0.008092144 + 3 O : 0.006029393 -0.002164500 0.005451506 + 4 H : -0.007422945 -0.002976722 -0.005510795 + +Norm of the cartesian gradient ... 0.022716686 +RMS gradient ... 0.006557742 +MAX gradient ... 0.010814990 + +------- +TIMINGS +------- + +Total numerical gradient time ... 642.937 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.445692578 Eh +Current gradient norm .... 0.022716686 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999628 +Lowest eigenvalues of augmented Hessian: + -0.000000123 0.132845802 0.208772286 0.469044218 0.531840312 +Length of the computed step .... 0.000862417 +The final length of the internal step .... 0.000862417 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0003520802 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0002137151 RMS(Int)= 0.0003520806 + Iter 1: RMS(Cart)= 0.0000000034 RMS(Int)= 0.0000000057 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000499636 0.0000050000 NO + RMS gradient 0.0000659959 0.0001000000 YES + MAX gradient 0.0001483682 0.0003000000 YES + RMS step 0.0003520802 0.0020000000 YES + MAX step 0.0008546120 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0005 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4231 -0.000148 0.0005 1.4236 + 2. B(O 2,N 1) 1.1814 -0.000052 -0.0000 1.1814 + 3. B(H 3,O 0) 0.9747 -0.000031 0.0000 0.9747 + 4. A(N 1,O 0,H 3) 105.06 -0.000021 -0.00 105.06 + 5. A(O 0,N 1,O 2) 113.11 -0.000003 -0.00 113.10 + 6. D(O 2,N 1,O 0,H 3) 32.73 0.017274 -0.00 32.73 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.527118 -0.357302 0.644568 + N 0.366196 -0.586166 -0.439932 + O 0.978877 0.376142 -0.746864 + H -0.817953 0.567326 0.542228 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.996109 -0.675202 1.218058 + 1 N 7.0000 0 14.007 0.692010 -1.107693 -0.831352 + 2 O 8.0000 0 15.999 1.849809 0.710805 -1.411368 + 3 H 1.0000 0 1.008 -1.545707 1.072090 1.024662 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.423562974170 0.00000000 0.00000000 + O 2 1 0 1.181364274648 113.10497671 0.00000000 + H 1 2 3 0.974676516630 105.05634375 32.72727248 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.690144155571 0.00000000 0.00000000 + O 2 1 0 2.232454943484 113.10497671 0.00000000 + H 1 2 3 1.841871685596 105.05634375 32.72727248 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2243 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2717 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 543 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.630715755787 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.6307157558 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.515e-04 +Time for diagonalization ... 0.005 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.004 sec +Total time needed ... 0.010 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7181883162 0.000000000000 0.00001399 0.00000035 0.0000660 0.7000 + 1 -204.7181883423 -0.000000026151 0.00001154 0.00000029 0.0000504 0.7000 + ***Turning on DIIS*** + 2 -204.7181883642 -0.000000021826 0.00003011 0.00000078 0.0000381 0.0000 + 3 -204.7182017212 -0.000013356981 0.00001053 0.00000034 0.0000095 0.0000 + 4 -204.7181806310 0.000021090195 0.00000471 0.00000012 0.0000030 0.0000 + 5 -204.7181864953 -0.000005864311 0.00000119 0.00000004 0.0000011 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 6 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71819396 Eh -5570.66526 eV + +Components: +Nuclear Repulsion : 69.63071576 Eh 1894.74810 eV +Electronic Energy : -274.34890972 Eh -7465.41337 eV +One Electron Energy: -418.87305966 Eh -11398.11542 eV +Two Electron Energy: 144.52414994 Eh 3932.70205 eV + +Virial components: +Potential Energy : -408.96133923 Eh -11128.40380 eV +Kinetic Energy : 204.24314527 Eh 5557.73853 eV +Virial Ratio : 2.00232590 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -7.4654e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.0724e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.5309e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.7000e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.672929 -562.5390 + 1 1.0000 -20.641569 -561.6857 + 2 1.0000 -15.803198 -430.0269 + 3 1.0000 -1.608802 -43.7777 + 4 1.0000 -1.399912 -38.0935 + 5 1.0000 -0.963801 -26.2264 + 6 1.0000 -0.774836 -21.0844 + 7 1.0000 -0.740170 -20.1411 + 8 1.0000 -0.692956 -18.8563 + 9 1.0000 -0.608754 -16.5650 + 10 1.0000 -0.534037 -14.5319 + 11 1.0000 -0.471413 -12.8278 + 12 0.0000 0.031226 0.8497 + 13 0.0000 0.072924 1.9844 + 14 0.0000 0.094568 2.5733 + 15 0.0000 0.111770 3.0414 + 16 0.0000 0.119008 3.2384 + 17 0.0000 0.148866 4.0509 + 18 0.0000 0.157383 4.2826 + 19 0.0000 0.169902 4.6233 + 20 0.0000 0.182299 4.9606 + 21 0.0000 0.194232 5.2853 + 22 0.0000 0.203950 5.5498 + 23 0.0000 0.233937 6.3658 + 24 0.0000 0.258524 7.0348 + 25 0.0000 0.297265 8.0890 + 26 0.0000 0.310994 8.4626 + 27 0.0000 0.341817 9.3013 + 28 0.0000 0.347891 9.4666 + 29 0.0000 0.388039 10.5591 + 30 0.0000 0.423975 11.5369 + 31 0.0000 0.514820 14.0090 + 32 0.0000 0.525690 14.3047 + 33 0.0000 0.534111 14.5339 + 34 0.0000 0.563220 15.3260 + 35 0.0000 0.614921 16.7329 + 36 0.0000 0.633774 17.2459 + 37 0.0000 0.653992 17.7960 + 38 0.0000 0.689953 18.7746 + 39 0.0000 0.702980 19.1291 + 40 0.0000 0.733421 19.9574 + 41 0.0000 0.748315 20.3627 + 42 0.0000 0.763838 20.7851 + 43 0.0000 0.786765 21.4090 + 44 0.0000 0.806137 21.9361 + 45 0.0000 0.839691 22.8492 + 46 0.0000 0.848198 23.0807 + 47 0.0000 0.878087 23.8940 + 48 0.0000 0.920040 25.0356 + 49 0.0000 0.941361 25.6157 + 50 0.0000 0.964015 26.2322 + 51 0.0000 0.988377 26.8951 + 52 0.0000 1.019480 27.7414 + 53 0.0000 1.040125 28.3032 + 54 0.0000 1.068639 29.0792 + 55 0.0000 1.086631 29.5687 + 56 0.0000 1.173446 31.9311 + 57 0.0000 1.194973 32.5169 + 58 0.0000 1.238555 33.7028 + 59 0.0000 1.278536 34.7907 + 60 0.0000 1.361979 37.0613 + 61 0.0000 1.410362 38.3779 + 62 0.0000 1.438035 39.1309 + 63 0.0000 1.513371 41.1809 + 64 0.0000 1.535511 41.7834 + 65 0.0000 1.551214 42.2107 + 66 0.0000 1.605313 43.6828 + 67 0.0000 1.630905 44.3792 + 68 0.0000 1.655252 45.0417 + 69 0.0000 1.737758 47.2868 + 70 0.0000 1.779219 48.4150 + 71 0.0000 1.812167 49.3116 + 72 0.0000 1.900118 51.7049 + 73 0.0000 1.953281 53.1515 + 74 0.0000 1.982064 53.9347 + 75 0.0000 2.020623 54.9840 + 76 0.0000 2.032610 55.3101 + 77 0.0000 2.086153 56.7671 + 78 0.0000 2.158442 58.7342 + 79 0.0000 2.176281 59.2196 + 80 0.0000 2.259629 61.4876 + 81 0.0000 2.306629 62.7666 + 82 0.0000 2.359438 64.2036 + 83 0.0000 2.393821 65.1392 + 84 0.0000 2.420007 65.8517 + 85 0.0000 2.446040 66.5601 + 86 0.0000 2.465936 67.1015 + 87 0.0000 2.516719 68.4834 + 88 0.0000 2.539850 69.1128 + 89 0.0000 2.556516 69.5663 + 90 0.0000 2.576739 70.1166 + 91 0.0000 2.620960 71.3199 + 92 0.0000 2.657632 72.3179 + 93 0.0000 2.684507 73.0492 + 94 0.0000 2.749562 74.8194 + 95 0.0000 2.803385 76.2840 + 96 0.0000 2.851032 77.5805 + 97 0.0000 2.954307 80.3908 + 98 0.0000 2.979507 81.0765 + 99 0.0000 3.031317 82.4863 + 100 0.0000 3.145148 85.5838 + 101 0.0000 3.168127 86.2091 + 102 0.0000 3.225537 87.7713 + 103 0.0000 3.516600 95.6915 + 104 0.0000 3.701463 100.7219 + 105 0.0000 3.881789 105.6289 + 106 0.0000 4.014823 109.2489 + 107 0.0000 4.149121 112.9033 + 108 0.0000 4.180515 113.7576 + 109 0.0000 4.305518 117.1591 + 110 0.0000 4.373537 119.0100 + 111 0.0000 4.410240 120.0087 + 112 0.0000 4.523629 123.0942 + 113 0.0000 4.567333 124.2834 + 114 0.0000 4.684025 127.4588 + 115 0.0000 4.809875 130.8833 + 116 0.0000 4.847503 131.9073 + 117 0.0000 4.870689 132.5382 + 118 0.0000 4.964833 135.1000 + 119 0.0000 5.003181 136.1435 + 120 0.0000 5.075628 138.1148 + 121 0.0000 5.108940 139.0213 + 122 0.0000 5.189006 141.2000 + 123 0.0000 5.233693 142.4160 + 124 0.0000 5.241074 142.6169 + 125 0.0000 5.283527 143.7721 + 126 0.0000 5.384618 146.5229 + 127 0.0000 5.475400 148.9932 + 128 0.0000 5.540407 150.7621 + 129 0.0000 5.693138 154.9182 + 130 0.0000 5.779750 157.2750 + 131 0.0000 5.943449 161.7295 + 132 0.0000 6.169263 167.8742 + 133 0.0000 6.406203 174.3216 + 134 0.0000 6.501339 176.9104 + 135 0.0000 6.534572 177.8147 + 136 0.0000 6.685760 181.9288 + 137 0.0000 6.723696 182.9611 + 138 0.0000 6.775510 184.3710 + 139 0.0000 6.800388 185.0480 + 140 0.0000 6.912746 188.1054 + 141 0.0000 7.101353 193.2376 + 142 0.0000 7.131669 194.0626 + 143 0.0000 7.170825 195.1281 + 144 0.0000 7.186096 195.5436 + 145 0.0000 7.244429 197.1309 + 146 0.0000 7.268318 197.7810 + 147 0.0000 7.312191 198.9748 + 148 0.0000 7.394627 201.2180 + 149 0.0000 7.458670 202.9607 + 150 0.0000 7.504786 204.2156 + 151 0.0000 7.522150 204.6881 + 152 0.0000 7.574189 206.1042 + 153 0.0000 7.659887 208.4361 + 154 0.0000 7.827739 213.0036 + 155 0.0000 7.880781 214.4470 + 156 0.0000 8.192911 222.9405 + 157 0.0000 8.335642 226.8243 + 158 0.0000 14.087153 383.3309 + 159 0.0000 15.135174 411.8490 + 160 0.0000 15.704118 427.3308 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.672929 -562.5390 + 1 1.0000 -20.641569 -561.6857 + 2 1.0000 -15.803198 -430.0269 + 3 1.0000 -1.608802 -43.7777 + 4 1.0000 -1.399912 -38.0935 + 5 1.0000 -0.963801 -26.2264 + 6 1.0000 -0.774836 -21.0844 + 7 1.0000 -0.740170 -20.1411 + 8 1.0000 -0.692956 -18.8563 + 9 1.0000 -0.608754 -16.5650 + 10 1.0000 -0.534037 -14.5319 + 11 1.0000 -0.471413 -12.8278 + 12 0.0000 0.031226 0.8497 + 13 0.0000 0.072924 1.9844 + 14 0.0000 0.094568 2.5733 + 15 0.0000 0.111770 3.0414 + 16 0.0000 0.119008 3.2384 + 17 0.0000 0.148866 4.0509 + 18 0.0000 0.157383 4.2826 + 19 0.0000 0.169902 4.6233 + 20 0.0000 0.182299 4.9606 + 21 0.0000 0.194232 5.2853 + 22 0.0000 0.203950 5.5498 + 23 0.0000 0.233937 6.3658 + 24 0.0000 0.258524 7.0348 + 25 0.0000 0.297265 8.0890 + 26 0.0000 0.310994 8.4626 + 27 0.0000 0.341817 9.3013 + 28 0.0000 0.347891 9.4666 + 29 0.0000 0.388039 10.5591 + 30 0.0000 0.423975 11.5369 + 31 0.0000 0.514820 14.0090 + 32 0.0000 0.525690 14.3047 + 33 0.0000 0.534111 14.5339 + 34 0.0000 0.563220 15.3260 + 35 0.0000 0.614921 16.7329 + 36 0.0000 0.633774 17.2459 + 37 0.0000 0.653992 17.7960 + 38 0.0000 0.689953 18.7746 + 39 0.0000 0.702980 19.1291 + 40 0.0000 0.733421 19.9574 + 41 0.0000 0.748315 20.3627 + 42 0.0000 0.763838 20.7851 + 43 0.0000 0.786765 21.4090 + 44 0.0000 0.806137 21.9361 + 45 0.0000 0.839691 22.8492 + 46 0.0000 0.848198 23.0807 + 47 0.0000 0.878087 23.8940 + 48 0.0000 0.920040 25.0356 + 49 0.0000 0.941361 25.6157 + 50 0.0000 0.964015 26.2322 + 51 0.0000 0.988377 26.8951 + 52 0.0000 1.019480 27.7414 + 53 0.0000 1.040125 28.3032 + 54 0.0000 1.068639 29.0792 + 55 0.0000 1.086631 29.5687 + 56 0.0000 1.173446 31.9311 + 57 0.0000 1.194973 32.5169 + 58 0.0000 1.238555 33.7028 + 59 0.0000 1.278536 34.7907 + 60 0.0000 1.361979 37.0613 + 61 0.0000 1.410362 38.3779 + 62 0.0000 1.438035 39.1309 + 63 0.0000 1.513371 41.1809 + 64 0.0000 1.535511 41.7834 + 65 0.0000 1.551214 42.2107 + 66 0.0000 1.605313 43.6828 + 67 0.0000 1.630905 44.3792 + 68 0.0000 1.655252 45.0417 + 69 0.0000 1.737758 47.2868 + 70 0.0000 1.779219 48.4150 + 71 0.0000 1.812167 49.3116 + 72 0.0000 1.900118 51.7049 + 73 0.0000 1.953281 53.1515 + 74 0.0000 1.982064 53.9347 + 75 0.0000 2.020623 54.9840 + 76 0.0000 2.032610 55.3101 + 77 0.0000 2.086153 56.7671 + 78 0.0000 2.158442 58.7342 + 79 0.0000 2.176281 59.2196 + 80 0.0000 2.259629 61.4876 + 81 0.0000 2.306629 62.7666 + 82 0.0000 2.359438 64.2036 + 83 0.0000 2.393821 65.1392 + 84 0.0000 2.420007 65.8517 + 85 0.0000 2.446040 66.5601 + 86 0.0000 2.465936 67.1015 + 87 0.0000 2.516719 68.4834 + 88 0.0000 2.539850 69.1128 + 89 0.0000 2.556516 69.5663 + 90 0.0000 2.576739 70.1166 + 91 0.0000 2.620960 71.3199 + 92 0.0000 2.657632 72.3179 + 93 0.0000 2.684507 73.0492 + 94 0.0000 2.749562 74.8194 + 95 0.0000 2.803385 76.2840 + 96 0.0000 2.851032 77.5805 + 97 0.0000 2.954307 80.3908 + 98 0.0000 2.979507 81.0765 + 99 0.0000 3.031317 82.4863 + 100 0.0000 3.145148 85.5838 + 101 0.0000 3.168127 86.2091 + 102 0.0000 3.225537 87.7713 + 103 0.0000 3.516600 95.6915 + 104 0.0000 3.701463 100.7219 + 105 0.0000 3.881789 105.6289 + 106 0.0000 4.014823 109.2489 + 107 0.0000 4.149121 112.9033 + 108 0.0000 4.180515 113.7576 + 109 0.0000 4.305518 117.1591 + 110 0.0000 4.373537 119.0100 + 111 0.0000 4.410240 120.0087 + 112 0.0000 4.523629 123.0942 + 113 0.0000 4.567333 124.2834 + 114 0.0000 4.684025 127.4588 + 115 0.0000 4.809875 130.8833 + 116 0.0000 4.847503 131.9073 + 117 0.0000 4.870689 132.5382 + 118 0.0000 4.964833 135.1000 + 119 0.0000 5.003181 136.1435 + 120 0.0000 5.075628 138.1148 + 121 0.0000 5.108940 139.0213 + 122 0.0000 5.189006 141.2000 + 123 0.0000 5.233693 142.4160 + 124 0.0000 5.241074 142.6169 + 125 0.0000 5.283527 143.7721 + 126 0.0000 5.384618 146.5229 + 127 0.0000 5.475400 148.9932 + 128 0.0000 5.540407 150.7621 + 129 0.0000 5.693138 154.9182 + 130 0.0000 5.779750 157.2750 + 131 0.0000 5.943449 161.7295 + 132 0.0000 6.169263 167.8742 + 133 0.0000 6.406203 174.3216 + 134 0.0000 6.501339 176.9104 + 135 0.0000 6.534572 177.8147 + 136 0.0000 6.685760 181.9288 + 137 0.0000 6.723696 182.9611 + 138 0.0000 6.775510 184.3710 + 139 0.0000 6.800388 185.0480 + 140 0.0000 6.912746 188.1054 + 141 0.0000 7.101353 193.2376 + 142 0.0000 7.131669 194.0626 + 143 0.0000 7.170825 195.1281 + 144 0.0000 7.186096 195.5436 + 145 0.0000 7.244429 197.1309 + 146 0.0000 7.268318 197.7810 + 147 0.0000 7.312191 198.9748 + 148 0.0000 7.394627 201.2180 + 149 0.0000 7.458670 202.9607 + 150 0.0000 7.504786 204.2156 + 151 0.0000 7.522150 204.6881 + 152 0.0000 7.574189 206.1042 + 153 0.0000 7.659887 208.4361 + 154 0.0000 7.827739 213.0036 + 155 0.0000 7.880781 214.4470 + 156 0.0000 8.192911 222.9405 + 157 0.0000 8.335642 226.8243 + 158 0.0000 14.087153 383.3309 + 159 0.0000 15.135174 411.8490 + 160 0.0000 15.704118 427.3308 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.306463 0.000000 + 1 N : 0.345084 0.000000 + 2 O : -0.287645 0.000000 + 3 H : 0.249024 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.816496 s : 3.816496 + pz : 1.446211 p : 4.450317 + px : 1.583194 + py : 1.420912 + dz2 : 0.009030 d : 0.034530 + dxz : 0.008032 + dyz : 0.004714 + dx2y2 : 0.011955 + dxy : 0.000798 + f0 : 0.000867 f : 0.005120 + f+1 : 0.001222 + f-1 : 0.000491 + f+2 : 0.000936 + f-2 : 0.001043 + f+3 : 0.000181 + f-3 : 0.000380 + 1 N s : 3.850685 s : 3.850685 + pz : 0.729513 p : 2.628678 + px : 0.734462 + py : 1.164704 + dz2 : 0.030732 d : 0.142744 + dxz : 0.030275 + dyz : 0.020123 + dx2y2 : 0.033936 + dxy : 0.027679 + f0 : 0.006124 f : 0.032807 + f+1 : 0.001718 + f-1 : 0.005094 + f+2 : 0.003294 + f-2 : 0.005887 + f+3 : 0.003461 + f-3 : 0.007230 + 2 O s : 3.864948 s : 3.864948 + pz : 1.591658 p : 4.354363 + px : 1.370559 + py : 1.392147 + dz2 : 0.007237 d : 0.060848 + dxz : 0.004264 + dyz : 0.017867 + dx2y2 : 0.016643 + dxy : 0.014837 + f0 : 0.000749 f : 0.007485 + f+1 : 0.000430 + f-1 : 0.001254 + f+2 : 0.000523 + f-2 : 0.001096 + f+3 : 0.001333 + f-3 : 0.002101 + 3 H s : 0.643084 s : 0.643084 + pz : 0.027540 p : 0.086550 + px : 0.037235 + py : 0.021775 + dz2 : 0.000557 d : 0.021342 + dxz : -0.000030 + dyz : 0.009731 + dx2y2 : 0.003411 + dxy : 0.007673 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.595999 0.000000 + 1 N : -0.273882 0.000000 + 2 O : 0.244140 0.000000 + 3 H : -0.566257 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.112316 s : 3.112316 + pz : 1.286399 p : 3.912960 + px : 1.317597 + py : 1.308964 + dz2 : 0.057853 d : 0.289807 + dxz : 0.086606 + dyz : 0.052260 + dx2y2 : 0.043419 + dxy : 0.049668 + f0 : 0.009778 f : 0.088917 + f+1 : 0.019010 + f-1 : 0.012028 + f+2 : 0.014429 + f-2 : 0.020827 + f+3 : 0.006099 + f-3 : 0.006747 + 1 N s : 3.009260 s : 3.009260 + pz : 0.796506 p : 2.832577 + px : 0.792835 + py : 1.243237 + dz2 : 0.195020 d : 0.966482 + dxz : 0.210406 + dyz : 0.154148 + dx2y2 : 0.220680 + dxy : 0.186228 + f0 : 0.069819 f : 0.465563 + f+1 : 0.050098 + f-1 : 0.060856 + f+2 : 0.046449 + f-2 : 0.089711 + f+3 : 0.063032 + f-3 : 0.085597 + 2 O s : 3.303632 s : 3.303632 + pz : 1.329863 p : 4.014370 + px : 1.248076 + py : 1.436431 + dz2 : 0.049763 d : 0.321966 + dxz : 0.046125 + dyz : 0.045595 + dx2y2 : 0.099161 + dxy : 0.081322 + f0 : 0.009146 f : 0.115893 + f+1 : 0.007461 + f-1 : 0.019610 + f+2 : 0.007627 + f-2 : 0.019897 + f+3 : 0.026051 + f-3 : 0.026099 + 3 H s : 0.614549 s : 0.614549 + pz : 0.141088 p : 0.550378 + px : 0.152769 + py : 0.256521 + dz2 : 0.035193 d : 0.401330 + dxz : 0.034164 + dyz : 0.110652 + dx2y2 : 0.111798 + dxy : 0.109523 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3065 8.0000 -0.3065 1.8170 1.8170 0.0000 + 1 N 6.6549 7.0000 0.3451 2.5272 2.5272 -0.0000 + 2 O 8.2876 8.0000 -0.2876 1.7080 1.7080 0.0000 + 3 H 0.7510 1.0000 0.2490 1.0141 1.0141 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8190 B( 0-O , 3-H ) : 0.9382 B( 1-N , 2-O ) : 1.6403 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 3 sec + +Total time .... 3.045 sec +Sum of individual times .... 2.510 sec ( 82.4%) + +Fock matrix formation .... 2.072 sec ( 68.0%) +Diagonalization .... 0.172 sec ( 5.7%) +Density matrix formation .... 0.012 sec ( 0.4%) +Population analysis .... 0.121 sec ( 4.0%) +Initial guess .... 0.019 sec ( 0.6%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.011 sec ( 0.4%) +DIIS solution .... 0.114 sec ( 3.7%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.495 sec +Reference energy ... -204.718188438 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 9.987 sec +AO-integral generation ... 0.364 sec +Half transformation ... 0.175 sec +K-integral sorting ... 7.629 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.066 s ( 0.000 ms/b) + 377910 b 0 skpd 0.079 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.101 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.099 s ( 0.001 ms/b) +: 159120 b 0 skpd 0.052 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.094 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.071 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.059 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.102 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.058 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.888 sec +AO-integral generation ... 0.693 sec +Half transformation ... 0.092 sec +J-integral sorting ... 0.077 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.238 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.365 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090391271 +EMP2(bb)= -0.090391271 +EMP2(ab)= -0.515305744 + +Initial guess performed in 0.173 sec +E(0) ... -204.718188438 +E(MP2) ... -0.696088286 +Initial E(tot) ... -205.414276723 + ... 0.187004907 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.414276723 -0.696088286 -0.000000000 0.026532540 5.42 0.000001124 + *** Turning on DIIS *** + 1 -205.385697898 -0.667509460 0.028578826 0.010198823 6.63 0.057683201 + 2 -205.405092082 -0.686903644 -0.019394184 0.005915434 7.21 0.060912476 + 3 -205.408812459 -0.690624021 -0.003720377 0.002022593 6.02 0.075269174 + 4 -205.410391637 -0.692203199 -0.001579177 0.001479161 5.46 0.082226907 + 5 -205.410947217 -0.692758779 -0.000555580 0.000862444 4.54 0.087872904 + 6 -205.411055262 -0.692866824 -0.000108045 0.000530641 4.69 0.090604749 + 7 -205.411100003 -0.692911566 -0.000044742 0.000236731 6.02 0.091810152 + 8 -205.411110704 -0.692922267 -0.000010701 0.000117355 5.60 0.092276249 + 9 -205.411106585 -0.692918147 0.000004120 0.000037683 6.08 0.092415539 + 10 -205.411111584 -0.692923146 -0.000004999 0.000023807 5.60 0.092469634 + 11 -205.411108854 -0.692920416 0.000002730 0.000017320 5.54 0.092458989 + 12 -205.411109971 -0.692921533 -0.000001117 0.000011920 4.73 0.092469881 + 13 -205.411109833 -0.692921395 0.000000139 0.000007360 5.32 0.092466874 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.718188438 +E(CORR) ... -0.692921395 +E(TOT) ... -205.411109833 +Singles norm **1/2 ... 0.092466874 ( 0.046233437, 0.046233437) +T1 diagnostic ... 0.021794651 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.059324 + 8a-> 13a -1a-> -1a 0.044258 + 8b-> 13b -1b-> -1b 0.044258 + 10a-> 13a 10b-> 13b 0.042424 + 10a-> 13a 8b-> 13b 0.030095 + 8a-> 13a 10b-> 13b 0.030095 + 11a-> 13a 11b-> 13b 0.030086 + 9a-> 13a 9b-> 13b 0.028600 + 10a-> 13a -1a-> -1a 0.028374 + 10b-> 13b -1b-> -1b 0.028374 + 9a-> 13a 8b-> 13b 0.026659 + 8a-> 13a 9b-> 13b 0.026659 + 5a-> 13a 5b-> 13b 0.026271 + 9a-> 13a 10b-> 13b 0.023200 + 10a-> 13a 9b-> 13b 0.023200 + 8a-> 13a 8b-> 22b 0.022433 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034582820 + alpha-alpha-alpha ... -0.000901468 ( 2.6%) + alpha-alpha-beta ... -0.016389942 ( 47.4%) + alpha-beta -beta ... -0.016389942 ( 47.4%) + beta -beta -beta ... -0.000901468 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034582820 + +Final correlation energy ... -0.727504214 +E(CCSD) ... -205.411109833 +E(CCSD(T)) ... -205.445692652 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.208989660 sqrt= 1.099540659 +W(HF) = 0.827136934 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.224034 -0.000000 + 1 N : 0.155392 -0.000000 + 2 O : -0.166056 -0.000000 + 3 H : 0.234698 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.802254 s : 3.802254 + pz : 1.411031 p : 4.348426 + px : 1.542273 + py : 1.395121 + dz2 : 0.015452 d : 0.064576 + dxz : 0.012470 + dyz : 0.011783 + dx2y2 : 0.016871 + dxy : 0.008000 + f0 : 0.001493 f : 0.008778 + f+1 : 0.001478 + f-1 : 0.001097 + f+2 : 0.001348 + f-2 : 0.001503 + f+3 : 0.000840 + f-3 : 0.001018 + 1 N s : 3.902524 s : 3.902524 + pz : 0.797909 p : 2.739256 + px : 0.817775 + py : 1.123572 + dz2 : 0.038460 d : 0.171019 + dxz : 0.036803 + dyz : 0.024463 + dx2y2 : 0.040424 + dxy : 0.030868 + f0 : 0.005742 f : 0.031809 + f+1 : 0.001759 + f-1 : 0.005237 + f+2 : 0.003133 + f-2 : 0.005759 + f+3 : 0.003520 + f-3 : 0.006661 + 2 O s : 3.852276 s : 3.852276 + pz : 1.529062 p : 4.220233 + px : 1.328653 + py : 1.362518 + dz2 : 0.012629 d : 0.083467 + dxz : 0.010830 + dyz : 0.021008 + dx2y2 : 0.022198 + dxy : 0.016802 + f0 : 0.001200 f : 0.010080 + f+1 : 0.000921 + f-1 : 0.001614 + f+2 : 0.000995 + f-2 : 0.001498 + f+3 : 0.001620 + f-3 : 0.002232 + 3 H s : 0.657007 s : 0.657007 + pz : 0.031630 p : 0.088968 + px : 0.040813 + py : 0.016526 + dz2 : 0.000438 d : 0.019327 + dxz : 0.000420 + dyz : 0.008802 + dx2y2 : 0.002654 + dxy : 0.007014 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.610057 -0.000000 + 1 N : -0.322012 0.000000 + 2 O : 0.280852 -0.000000 + 3 H : -0.568896 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.120290 s : 3.120290 + pz : 1.266070 p : 3.851995 + px : 1.293743 + py : 1.292182 + dz2 : 0.064997 d : 0.321404 + dxz : 0.093052 + dyz : 0.057187 + dx2y2 : 0.049869 + dxy : 0.056300 + f0 : 0.011747 f : 0.096254 + f+1 : 0.020583 + f-1 : 0.012593 + f+2 : 0.015560 + f-2 : 0.021036 + f+3 : 0.006956 + f-3 : 0.007780 + 1 N s : 3.014805 s : 3.014805 + pz : 0.831655 p : 2.881382 + px : 0.841790 + py : 1.207938 + dz2 : 0.196922 d : 0.971626 + dxz : 0.217275 + dyz : 0.148745 + dx2y2 : 0.218182 + dxy : 0.190502 + f0 : 0.066382 f : 0.454200 + f+1 : 0.049620 + f-1 : 0.059942 + f+2 : 0.045631 + f-2 : 0.087281 + f+3 : 0.063150 + f-3 : 0.082194 + 2 O s : 3.305677 s : 3.305677 + pz : 1.293685 p : 3.934013 + px : 1.223692 + py : 1.416636 + dz2 : 0.056507 d : 0.354777 + dxz : 0.051176 + dyz : 0.053326 + dx2y2 : 0.106074 + dxy : 0.087694 + f0 : 0.010191 f : 0.124682 + f+1 : 0.008781 + f-1 : 0.020159 + f+2 : 0.009420 + f-2 : 0.020574 + f+3 : 0.026632 + f-3 : 0.028926 + 3 H s : 0.618667 s : 0.618667 + pz : 0.142347 p : 0.559399 + px : 0.155662 + py : 0.261390 + dz2 : 0.034949 d : 0.390830 + dxz : 0.033444 + dyz : 0.106796 + dx2y2 : 0.109859 + dxy : 0.105782 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2240 8.0000 -0.2240 2.1904 1.7391 0.4514 + 1 N 6.8446 7.0000 0.1554 2.8103 2.3353 0.4749 + 2 O 8.1661 8.0000 -0.1661 2.1076 1.6093 0.4983 + 3 H 0.7653 1.0000 0.2347 1.0313 0.9571 0.0741 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7710 B( 0-O , 2-O ) : 0.1010 B( 0-O , 3-H ) : 0.8672 +B( 1-N , 2-O ) : 1.4914 + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 107.538 sec + +Fock Matrix Formation ... 0.495 sec ( 0.5%) +Initial Guess ... 0.173 sec ( 0.2%) +DIIS Solver ... 4.086 sec ( 3.8%) +State Vector Update ... 0.171 sec ( 0.2%) +Sigma-vector construction ... 74.597 sec ( 69.4%) + <0|H|D> ... 0.006 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.035 sec ( 0.0% of sigma) + (0-ext) ... 0.110 sec ( 0.1% of sigma) + (2-ext Fock) ... 0.041 sec ( 0.1% of sigma) + (2-ext) ... 1.482 sec ( 2.0% of sigma) + (4-ext) ... 43.817 sec ( 58.7% of sigma) + ... 3.564 sec ( 4.8% of sigma) + ... 0.005 sec ( 0.0% of sigma) + (1-ext) ... 0.012 sec ( 0.0% of sigma) + (1-ext) ... 0.194 sec ( 0.3% of sigma) + Fock-dressing ... 5.109 sec ( 6.8% of sigma) + (ik|jl)-dressing ... 0.120 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 16.365 sec ( 21.9% of sigma) + Pair energies ... 0.025 sec ( 0.0% of sigma) +Total Time for computing (T) ... 14.963 sec ( 13.9% of ALL) + I/O of integral and amplitudes ... 1.151 sec ( 7.7% of (T)) + External N**7 contributions ... 5.570 sec ( 37.2% of (T)) + Internal N**7 contributions ... 0.438 sec ( 2.9% of (T)) + N**6 triples energy contributions ... 2.141 sec ( 14.3% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.445692652266 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.027.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.027.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.463558, -0.294922 -0.291508) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.64972 -0.22727 -0.63171 +Nuclear contribution : -0.99743 0.68120 0.65490 + ----------------------------------------- +Total Dipole Moment : -0.34772 0.45392 0.02320 + ----------------------------------------- +Magnitude (a.u.) : 0.57227 +Magnitude (Debye) : 1.45459 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.767556 0.428153 0.374192 +Rotational constants in MHz : 82969.239882 12835.697934 11217.985236 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.133067 0.462571 0.309536 +x,y,z [Debye]: 0.338231 1.175763 0.786777 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.463558, -0.294922 -0.291508) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.72522 -0.14737 -0.63797 +Nuclear contribution : -0.99743 0.68120 0.65490 + ----------------------------------------- +Total Dipole Moment : -0.27222 0.53383 0.01693 + ----------------------------------------- +Magnitude (a.u.) : 0.59947 +Magnitude (Debye) : 1.52373 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.767556 0.428153 0.374192 +Rotational constants in MHz : 82969.239882 12835.697934 11217.985236 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.053603 0.530245 0.274462 +x,y,z [Debye]: 0.136247 1.347777 0.697628 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 28 * + * * + * Dihedral ( 2, 1, 0, 3) : 40.90909091 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0330320477 RMS(Int)= 0.0001176517 + Iter 1: RMS(Cart)= 0.0000272149 RMS(Int)= 0.0000001109 + Iter 2: RMS(Cart)= 0.0000000256 RMS(Int)= 0.0000000001 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4249 0.000000 + 2. B(O 2,N 1) 1.1827 0.000000 + 3. B(H 3,O 0) 0.9766 0.000000 + 4. A(N 1,O 0,H 3) 104.8655 0.000000 + 5. A(O 0,N 1,O 2) 112.9409 0.000000 + 6. D(O 2,N 1,O 0,H 3) 40.9091 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.501531 -0.347431 0.663316 + N 0.344971 -0.576116 -0.459783 + O 1.002590 0.365856 -0.740770 + H -0.846029 0.557690 0.537237 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.947756 -0.656549 1.253485 + 1 N 7.0000 0 14.007 0.651900 -1.088701 -0.868864 + 2 O 8.0000 0 15.999 1.894621 0.691368 -1.399852 + 3 H 1.0000 0 1.008 -1.598764 1.053881 1.015232 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.423562974170 0.00000000 0.00000000 + O 2 1 0 1.181364274648 113.10497671 0.00000000 + H 1 2 3 0.974676516630 105.05634375 32.72727248 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.690144155571 0.00000000 0.00000000 + O 2 1 0 2.232454943484 113.10497671 0.00000000 + H 1 2 3 1.841871685596 105.05634375 32.72727248 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2242 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2716 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 542 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.543802899674 Eh + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.5438028997 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.543e-04 +Time for diagonalization ... 0.005 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.006 sec +Total time needed ... 0.012 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7116473855 0.000000000000 0.00164957 0.00005164 0.0136865 0.7000 + 1 -204.7123924894 -0.000745103966 0.00149707 0.00004813 0.0114099 0.7000 + ***Turning on DIIS*** + 2 -204.7130419471 -0.000649457655 0.00402662 0.00013355 0.0093461 0.0000 + 3 -204.7163683006 -0.003326353516 0.00191248 0.00006240 0.0040887 0.0000 + 4 -204.7143498152 0.002018485364 0.00091629 0.00003294 0.0016858 0.0000 + 5 -204.7162994113 -0.001949596078 0.00084279 0.00003893 0.0008612 0.0000 + 6 -204.7155992433 0.000700168029 0.00051106 0.00002572 0.0007150 0.0000 + 7 -204.7150710430 0.000528200284 0.00041123 0.00001610 0.0003673 0.0000 + 8 -204.7160814320 -0.001010388972 0.00023116 0.00001000 0.0002100 0.0000 + 9 -204.7155794980 0.000501933967 0.00012595 0.00000372 0.0000840 0.0000 + 10 -204.7155782351 0.000001262911 0.00004157 0.00000130 0.0000457 0.0000 + 11 -204.7157628571 -0.000184621987 0.00002669 0.00000068 0.0000222 0.0000 + 12 -204.7156611462 0.000101710938 0.00000753 0.00000021 0.0000070 0.0000 + 13 -204.7156845699 -0.000023423763 0.00000254 0.00000008 0.0000026 0.0000 + 14 -204.7156757431 0.000008826819 0.00000096 0.00000004 0.0000014 0.0000 + 15 -204.7156751809 0.000000562194 0.00000061 0.00000003 0.0000011 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 16 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71567706 Eh -5570.59678 eV + +Components: +Nuclear Repulsion : 69.54380290 Eh 1892.38308 eV +Electronic Energy : -274.25947996 Eh -7462.97986 eV +One Electron Energy: -418.71603686 Eh -11393.84261 eV +Two Electron Energy: 144.45655689 Eh 3930.86275 eV + +Virial components: +Potential Energy : -408.95329559 Eh -11128.18492 eV +Kinetic Energy : 204.23761852 Eh 5557.58814 eV +Virial Ratio : 2.00234070 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.8816e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.6187e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.2370e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.6060e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.673931 -562.5663 + 1 1.0000 -20.639731 -561.6356 + 2 1.0000 -15.802406 -430.0053 + 3 1.0000 -1.607164 -43.7332 + 4 1.0000 -1.398413 -38.0527 + 5 1.0000 -0.962635 -26.1946 + 6 1.0000 -0.773896 -21.0588 + 7 1.0000 -0.738483 -20.0952 + 8 1.0000 -0.694942 -18.9103 + 9 1.0000 -0.604908 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2.5720 + 15 0.0000 0.110999 3.0204 + 16 0.0000 0.116569 3.1720 + 17 0.0000 0.151257 4.1159 + 18 0.0000 0.156834 4.2677 + 19 0.0000 0.170802 4.6477 + 20 0.0000 0.181147 4.9293 + 21 0.0000 0.193468 5.2645 + 22 0.0000 0.203626 5.5409 + 23 0.0000 0.234664 6.3855 + 24 0.0000 0.261960 7.1283 + 25 0.0000 0.296086 8.0569 + 26 0.0000 0.312388 8.5005 + 27 0.0000 0.341792 9.3006 + 28 0.0000 0.346552 9.4302 + 29 0.0000 0.379890 10.3373 + 30 0.0000 0.421423 11.4675 + 31 0.0000 0.515127 14.0173 + 32 0.0000 0.528662 14.3856 + 33 0.0000 0.534481 14.5440 + 34 0.0000 0.562912 15.3176 + 35 0.0000 0.611372 16.6363 + 36 0.0000 0.633233 17.2312 + 37 0.0000 0.649543 17.6750 + 38 0.0000 0.692775 18.8514 + 39 0.0000 0.707267 19.2457 + 40 0.0000 0.732679 19.9372 + 41 0.0000 0.744137 20.2490 + 42 0.0000 0.766597 20.8602 + 43 0.0000 0.784971 21.3601 + 44 0.0000 0.811084 22.0707 + 45 0.0000 0.835507 22.7353 + 46 0.0000 0.849949 23.1283 + 47 0.0000 0.879813 23.9409 + 48 0.0000 0.919215 25.0131 + 49 0.0000 0.941605 25.6224 + 50 0.0000 0.967569 26.3289 + 51 0.0000 0.981788 26.7158 + 52 0.0000 1.015926 27.6448 + 53 0.0000 1.025984 27.9185 + 54 0.0000 1.062544 28.9133 + 55 0.0000 1.087621 29.5957 + 56 0.0000 1.168316 31.7915 + 57 0.0000 1.198532 32.6137 + 58 0.0000 1.236227 33.6394 + 59 0.0000 1.279439 34.8153 + 60 0.0000 1.357043 36.9270 + 61 0.0000 1.411997 38.4224 + 62 0.0000 1.437806 39.1247 + 63 0.0000 1.525119 41.5006 + 64 0.0000 1.527298 41.5599 + 65 0.0000 1.549971 42.1768 + 66 0.0000 1.615373 43.9565 + 67 0.0000 1.633532 44.4507 + 68 0.0000 1.653798 45.0021 + 69 0.0000 1.735016 47.2122 + 70 0.0000 1.772430 48.2303 + 71 0.0000 1.805066 49.1183 + 72 0.0000 1.903500 51.7969 + 73 0.0000 1.964416 53.4545 + 74 0.0000 1.977321 53.8056 + 75 0.0000 2.017952 54.9113 + 76 0.0000 2.043389 55.6034 + 77 0.0000 2.082117 56.6573 + 78 0.0000 2.156803 58.6896 + 79 0.0000 2.174095 59.1601 + 80 0.0000 2.256109 61.3918 + 81 0.0000 2.306806 62.7714 + 82 0.0000 2.354873 64.0794 + 83 0.0000 2.394187 65.1491 + 84 0.0000 2.415821 65.7378 + 85 0.0000 2.450004 66.6680 + 86 0.0000 2.468662 67.1757 + 87 0.0000 2.509324 68.2822 + 88 0.0000 2.533116 68.9296 + 89 0.0000 2.557613 69.5962 + 90 0.0000 2.574764 70.0629 + 91 0.0000 2.619857 71.2899 + 92 0.0000 2.655860 72.2696 + 93 0.0000 2.691577 73.2415 + 94 0.0000 2.762645 75.1754 + 95 0.0000 2.803235 76.2799 + 96 0.0000 2.837195 77.2040 + 97 0.0000 2.950761 80.2943 + 98 0.0000 2.978651 81.0532 + 99 0.0000 3.025141 82.3183 + 100 0.0000 3.144931 85.5779 + 101 0.0000 3.169218 86.2388 + 102 0.0000 3.224937 87.7550 + 103 0.0000 3.516819 95.6975 + 104 0.0000 3.688747 100.3759 + 105 0.0000 3.884849 105.7121 + 106 0.0000 4.016902 109.3055 + 107 0.0000 4.147268 112.8529 + 108 0.0000 4.180261 113.7507 + 109 0.0000 4.328738 117.7910 + 110 0.0000 4.380790 119.2073 + 111 0.0000 4.393011 119.5399 + 112 0.0000 4.527746 123.2062 + 113 0.0000 4.577678 124.5649 + 114 0.0000 4.678594 127.3110 + 115 0.0000 4.794845 130.4744 + 116 0.0000 4.823228 131.2467 + 117 0.0000 4.867684 132.4564 + 118 0.0000 4.969553 135.2284 + 119 0.0000 5.002855 136.1346 + 120 0.0000 5.072783 138.0374 + 121 0.0000 5.105832 138.9367 + 122 0.0000 5.180017 140.9554 + 123 0.0000 5.234330 142.4334 + 124 0.0000 5.248616 142.8221 + 125 0.0000 5.274220 143.5188 + 126 0.0000 5.384383 146.5165 + 127 0.0000 5.478225 149.0701 + 128 0.0000 5.535465 150.6277 + 129 0.0000 5.695349 154.9783 + 130 0.0000 5.780544 157.2966 + 131 0.0000 5.953125 161.9928 + 132 0.0000 6.172242 167.9553 + 133 0.0000 6.407095 174.3459 + 134 0.0000 6.498170 176.8242 + 135 0.0000 6.530354 177.7000 + 136 0.0000 6.687376 181.9728 + 137 0.0000 6.722136 182.9186 + 138 0.0000 6.777669 184.4298 + 139 0.0000 6.800455 185.0498 + 140 0.0000 6.900423 187.7701 + 141 0.0000 7.097198 193.1246 + 142 0.0000 7.126058 193.9099 + 143 0.0000 7.170625 195.1226 + 144 0.0000 7.190740 195.6700 + 145 0.0000 7.247155 197.2051 + 146 0.0000 7.268947 197.7981 + 147 0.0000 7.308500 198.8744 + 148 0.0000 7.391193 201.1246 + 149 0.0000 7.463863 203.1020 + 150 0.0000 7.512776 204.4330 + 151 0.0000 7.539763 205.1674 + 152 0.0000 7.551806 205.4951 + 153 0.0000 7.670892 208.7356 + 154 0.0000 7.790033 211.9776 + 155 0.0000 7.890535 214.7124 + 156 0.0000 8.152448 221.8394 + 157 0.0000 8.349357 227.1976 + 158 0.0000 14.052165 382.3788 + 159 0.0000 15.132938 411.7882 + 160 0.0000 15.685340 426.8198 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.315171 0.000000 + 1 N : 0.344390 0.000000 + 2 O : -0.282468 0.000000 + 3 H : 0.253249 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.822533 s : 3.822533 + pz : 1.413762 p : 4.453922 + px : 1.597995 + py : 1.442165 + dz2 : 0.009008 d : 0.033692 + dxz : 0.008186 + dyz : 0.005422 + dx2y2 : 0.010138 + dxy : 0.000938 + f0 : 0.000985 f : 0.005024 + f+1 : 0.001171 + f-1 : 0.000565 + f+2 : 0.000859 + f-2 : 0.000911 + f+3 : 0.000248 + f-3 : 0.000285 + 1 N s : 3.844200 s : 3.844200 + pz : 0.744071 p : 2.635823 + px : 0.742170 + py : 1.149582 + dz2 : 0.030662 d : 0.142811 + dxz : 0.031152 + dyz : 0.019799 + dx2y2 : 0.034309 + dxy : 0.026888 + f0 : 0.006809 f : 0.032777 + f+1 : 0.001678 + f-1 : 0.005113 + f+2 : 0.003300 + f-2 : 0.005900 + f+3 : 0.003173 + f-3 : 0.006804 + 2 O s : 3.869310 s : 3.869310 + pz : 1.622838 p : 4.345535 + px : 1.331543 + py : 1.391154 + dz2 : 0.006424 d : 0.060199 + dxz : 0.004738 + dyz : 0.016914 + dx2y2 : 0.018259 + dxy : 0.013864 + f0 : 0.000837 f : 0.007424 + f+1 : 0.000475 + f-1 : 0.001100 + f+2 : 0.000389 + f-2 : 0.001127 + f+3 : 0.001384 + f-3 : 0.002112 + 3 H s : 0.638821 s : 0.638821 + pz : 0.026170 p : 0.086869 + px : 0.037655 + py : 0.023044 + dz2 : 0.000795 d : 0.021061 + dxz : 0.000412 + dyz : 0.008925 + dx2y2 : 0.004489 + dxy : 0.006440 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.591371 0.000000 + 1 N : -0.274915 0.000000 + 2 O : 0.243061 0.000000 + 3 H : -0.559517 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.113427 s : 3.113427 + pz : 1.275920 p : 3.917485 + px : 1.324878 + py : 1.316688 + dz2 : 0.063152 d : 0.289144 + dxz : 0.085112 + dyz : 0.055093 + dx2y2 : 0.038035 + dxy : 0.047753 + f0 : 0.010838 f : 0.088572 + f+1 : 0.019267 + f-1 : 0.013719 + f+2 : 0.014144 + f-2 : 0.019568 + f+3 : 0.006253 + f-3 : 0.004783 + 1 N s : 3.010333 s : 3.010333 + pz : 0.811156 p : 2.834970 + px : 0.801210 + py : 1.222604 + dz2 : 0.198812 d : 0.964641 + dxz : 0.214444 + dyz : 0.154065 + dx2y2 : 0.209649 + dxy : 0.187673 + f0 : 0.076930 f : 0.464970 + f+1 : 0.050848 + f-1 : 0.060844 + f+2 : 0.042435 + f-2 : 0.090692 + f+3 : 0.062784 + f-3 : 0.080437 + 2 O s : 3.307082 s : 3.307082 + pz : 1.350040 p : 4.012558 + px : 1.236193 + py : 1.426326 + dz2 : 0.050029 d : 0.321557 + dxz : 0.048395 + dyz : 0.043519 + dx2y2 : 0.091745 + dxy : 0.087868 + f0 : 0.009565 f : 0.115742 + f+1 : 0.008396 + f-1 : 0.018901 + f+2 : 0.006288 + f-2 : 0.020431 + f+3 : 0.027704 + f-3 : 0.024456 + 3 H s : 0.613594 s : 0.613594 + pz : 0.140742 p : 0.549405 + px : 0.157228 + py : 0.251435 + dz2 : 0.034347 d : 0.396519 + dxz : 0.037733 + dyz : 0.105885 + dx2y2 : 0.112719 + dxy : 0.105834 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3152 8.0000 -0.3152 1.8150 1.8150 -0.0000 + 1 N 6.6556 7.0000 0.3444 2.5346 2.5346 0.0000 + 2 O 8.2825 8.0000 -0.2825 1.7200 1.7200 -0.0000 + 3 H 0.7468 1.0000 0.2532 1.0093 1.0093 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8166 B( 0-O , 3-H ) : 0.9391 B( 1-N , 2-O ) : 1.6543 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 6 sec + +Total time .... 6.416 sec +Sum of individual times .... 5.800 sec ( 90.4%) + +Fock matrix formation .... 5.004 sec ( 78.0%) +Diagonalization .... 0.362 sec ( 5.6%) +Density matrix formation .... 0.030 sec ( 0.5%) +Population analysis .... 0.083 sec ( 1.3%) +Initial guess .... 0.023 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.015 sec ( 0.2%) +DIIS solution .... 0.297 sec ( 4.6%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.533 sec +Reference energy ... -204.715676053 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 10.123 sec +AO-integral generation ... 0.374 sec +Half transformation ... 0.182 sec +K-integral sorting ... 8.022 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.055 s ( 0.000 ms/b) + 377910 b 0 skpd 0.062 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.085 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.095 s ( 0.001 ms/b) +: 159120 b 0 skpd 0.055 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.089 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.067 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.054 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.097 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.059 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.826 sec +AO-integral generation ... 0.637 sec +Half transformation ... 0.085 sec +J-integral sorting ... 0.080 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.239 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.381 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090286151 +EMP2(bb)= -0.090286151 +EMP2(ab)= -0.515319467 + +Initial guess performed in 0.184 sec +E(0) ... -204.715676053 +E(MP2) ... -0.695891769 +Initial E(tot) ... -205.411567823 + ... 0.187014718 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.411567823 -0.695891769 -0.000000000 0.025073685 5.09 0.000002152 + *** Turning on DIIS *** + 1 -205.383269197 -0.667593144 0.028298625 0.009610901 4.84 0.057125992 + 2 -205.402613536 -0.686937482 -0.019344338 0.005552143 5.23 0.060396364 + 3 -205.406346844 -0.690670791 -0.003733309 0.001864985 5.36 0.074548887 + 4 -205.407915745 -0.692239692 -0.001568901 0.001437178 5.11 0.081370537 + 5 -205.408461281 -0.692785227 -0.000545535 0.000859627 5.00 0.086870376 + 6 -205.408567570 -0.692891516 -0.000106289 0.000528923 4.75 0.089569274 + 7 -205.408611932 -0.692935878 -0.000044362 0.000246172 4.61 0.090787260 + 8 -205.408622592 -0.692946539 -0.000010661 0.000117583 5.27 0.091284066 + 9 -205.408618739 -0.692942685 0.000003854 0.000049309 6.11 0.091440280 + 10 -205.408623734 -0.692947680 -0.000004995 0.000030221 5.74 0.091500914 + 11 -205.408620839 -0.692944786 0.000002895 0.000021799 5.85 0.091490432 + 12 -205.408622233 -0.692946179 -0.000001393 0.000014388 5.12 0.091503772 + 13 -205.408622067 -0.692946014 0.000000165 0.000008363 5.29 0.091500131 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.715676053 +E(CORR) ... -0.692946014 +E(TOT) ... -205.408622067 +Singles norm **1/2 ... 0.091500131 ( 0.045750065, 0.045750065) +T1 diagnostic ... 0.021566788 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.055637 + 8b-> 13b -1b-> -1b 0.041531 + 8a-> 13a -1a-> -1a 0.041531 + 10a-> 13a 10b-> 13b 0.036898 + 9a-> 13a 9b-> 13b 0.036441 + 9a-> 13a 8b-> 13b 0.030930 + 8a-> 13a 9b-> 13b 0.030930 + 11a-> 13a 11b-> 13b 0.030739 + 10a-> 13a -1a-> -1a 0.027607 + 10b-> 13b -1b-> -1b 0.027607 + 8a-> 13a 10b-> 13b 0.027048 + 10a-> 13a 8b-> 13b 0.027048 + 5a-> 13a 5b-> 13b 0.026502 + 9a-> 13a 10b-> 13b 0.026389 + 10a-> 13a 9b-> 13b 0.026389 + 8a-> 22a 8b-> 13b 0.020731 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034469768 + alpha-alpha-alpha ... -0.000894562 ( 2.6%) + alpha-alpha-beta ... -0.016340322 ( 47.4%) + alpha-beta -beta ... -0.016340322 ( 47.4%) + beta -beta -beta ... -0.000894562 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034469768 + +Final correlation energy ... -0.727415782 +E(CCSD) ... -205.408622067 +E(CCSD(T)) ... -205.443091835 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209017355 sqrt= 1.099553253 +W(HF) = 0.827117986 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.236050 0.000000 + 1 N : 0.157156 -0.000000 + 2 O : -0.160287 0.000000 + 3 H : 0.239181 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.806691 s : 3.806691 + pz : 1.382573 p : 4.356824 + px : 1.558691 + py : 1.415560 + dz2 : 0.015221 d : 0.063852 + dxz : 0.012691 + dyz : 0.012439 + dx2y2 : 0.015516 + dxy : 0.007986 + f0 : 0.001596 f : 0.008683 + f+1 : 0.001403 + f-1 : 0.001152 + f+2 : 0.001297 + f-2 : 0.001396 + f+3 : 0.000908 + f-3 : 0.000932 + 1 N s : 3.897390 s : 3.897390 + pz : 0.804995 p : 2.742105 + px : 0.822854 + py : 1.114255 + dz2 : 0.038454 d : 0.171582 + dxz : 0.038021 + dyz : 0.024634 + dx2y2 : 0.040049 + dxy : 0.030424 + f0 : 0.006363 f : 0.031767 + f+1 : 0.001684 + f-1 : 0.005276 + f+2 : 0.003236 + f-2 : 0.005759 + f+3 : 0.003306 + f-3 : 0.006143 + 2 O s : 3.856092 s : 3.856092 + pz : 1.557632 p : 4.211535 + px : 1.292906 + py : 1.360997 + dz2 : 0.011857 d : 0.082657 + dxz : 0.011292 + dyz : 0.020430 + dx2y2 : 0.023139 + dxy : 0.015938 + f0 : 0.001285 f : 0.010003 + f+1 : 0.000958 + f-1 : 0.001487 + f+2 : 0.000896 + f-2 : 0.001514 + f+3 : 0.001661 + f-3 : 0.002202 + 3 H s : 0.651985 s : 0.651985 + pz : 0.030181 p : 0.089909 + px : 0.041153 + py : 0.018575 + dz2 : 0.000633 d : 0.018925 + dxz : 0.000762 + dyz : 0.008061 + dx2y2 : 0.003642 + dxy : 0.005827 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.604206 -0.000000 + 1 N : -0.321931 -0.000000 + 2 O : 0.280709 0.000000 + 3 H : -0.562984 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.120968 s : 3.120968 + pz : 1.258207 p : 3.858330 + px : 1.301124 + py : 1.298998 + dz2 : 0.069987 d : 0.320626 + dxz : 0.091573 + dyz : 0.059990 + dx2y2 : 0.044341 + dxy : 0.054735 + f0 : 0.012922 f : 0.095870 + f+1 : 0.020774 + f-1 : 0.014142 + f+2 : 0.015176 + f-2 : 0.019985 + f+3 : 0.007106 + f-3 : 0.005765 + 1 N s : 3.015915 s : 3.015915 + pz : 0.841019 p : 2.881790 + px : 0.848854 + py : 1.191917 + dz2 : 0.201576 d : 0.970390 + dxz : 0.220844 + dyz : 0.148161 + dx2y2 : 0.206699 + dxy : 0.193111 + f0 : 0.073130 f : 0.453836 + f+1 : 0.050948 + f-1 : 0.060053 + f+2 : 0.041506 + f-2 : 0.088131 + f+3 : 0.062612 + f-3 : 0.077456 + 2 O s : 3.309233 s : 3.309233 + pz : 1.311639 p : 3.931877 + px : 1.213513 + py : 1.406725 + dz2 : 0.056514 d : 0.353775 + dxz : 0.053384 + dyz : 0.050763 + dx2y2 : 0.099398 + dxy : 0.093715 + f0 : 0.010585 f : 0.124406 + f+1 : 0.009667 + f-1 : 0.019236 + f+2 : 0.007894 + f-2 : 0.021162 + f+3 : 0.028160 + f-3 : 0.027702 + 3 H s : 0.617359 s : 0.617359 + pz : 0.142050 p : 0.559388 + px : 0.160661 + py : 0.256677 + dz2 : 0.034163 d : 0.386237 + dxz : 0.036683 + dyz : 0.102483 + dx2y2 : 0.110270 + dxy : 0.102638 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2361 8.0000 -0.2361 2.1842 1.7337 0.4504 + 1 N 6.8428 7.0000 0.1572 2.8146 2.3369 0.4777 + 2 O 8.1603 8.0000 -0.1603 2.1163 1.6167 0.4995 + 3 H 0.7608 1.0000 0.2392 1.0270 0.9529 0.0741 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7649 B( 0-O , 3-H ) : 0.8699 B( 1-N , 2-O ) : 1.5034 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 102.317 sec + +Fock Matrix Formation ... 0.533 sec ( 0.5%) +Initial Guess ... 0.184 sec ( 0.2%) +DIIS Solver ... 3.880 sec ( 3.8%) +State Vector Update ... 0.174 sec ( 0.2%) +Sigma-vector construction ... 69.319 sec ( 67.7%) + <0|H|D> ... 0.007 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.040 sec ( 0.1% of sigma) + (0-ext) ... 0.106 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.039 sec ( 0.1% of sigma) + (2-ext) ... 1.412 sec ( 2.0% of sigma) + (4-ext) ... 40.756 sec ( 58.8% of sigma) + ... 3.241 sec ( 4.7% of sigma) + ... 0.005 sec ( 0.0% of sigma) + (1-ext) ... 0.011 sec ( 0.0% of sigma) + (1-ext) ... 0.179 sec ( 0.3% of sigma) + Fock-dressing ... 4.754 sec ( 6.9% of sigma) + (ik|jl)-dressing ... 0.110 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 15.162 sec ( 21.9% of sigma) + Pair energies ... 0.021 sec ( 0.0% of sigma) +Total Time for computing (T) ... 15.044 sec ( 14.7% of ALL) + I/O of integral and amplitudes ... 1.118 sec ( 7.4% of (T)) + External N**7 contributions ... 5.623 sec ( 37.4% of (T)) + Internal N**7 contributions ... 0.455 sec ( 3.0% of (T)) + N**6 triples energy contributions ... 2.209 sec ( 14.7% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.443091835199 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.014496257 0.000153951 0.006682775 + 2 N : -0.013959387 0.001526965 -0.005307381 + 3 O : 0.008262320 -0.000405823 0.004978946 + 4 H : -0.008799190 -0.001275093 -0.006354340 + +Norm of the cartesian gradient ... 0.026321832 +RMS gradient ... 0.007598458 +MAX gradient ... 0.014496257 + +------- +TIMINGS +------- + +Total numerical gradient time ... 570.437 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 180.28 cm**-1 + 7: 648.28 cm**-1 + 8: 845.72 cm**-1 + 9: 1293.78 cm**-1 + 10: 1649.73 cm**-1 + 11: 3636.20 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 0.013328 -0.313197 0.138029 0.023141 -0.023492 -0.021955 + 1 0.019125 -0.135580 -0.108901 0.069058 0.057720 0.057458 + 2 0.107324 0.200038 -0.201120 -0.053487 0.030565 -0.008240 + 3 -0.019730 0.140893 -0.235392 0.071197 -0.271554 -0.001023 + 4 0.029753 0.156687 0.204818 -0.034869 -0.559567 0.000893 + 5 -0.104598 0.017468 0.336588 -0.046523 0.049859 0.001137 + 6 0.054803 0.191662 0.112616 -0.053205 0.283090 0.000518 + 7 -0.021965 -0.005309 -0.048104 -0.037241 0.432806 0.000034 + 8 0.011336 -0.267520 -0.109665 0.040952 -0.102907 -0.000478 + 9 -0.807213 -0.028831 -0.707266 -0.512154 -0.346867 0.354459 + 10 -0.368369 0.058898 -0.354117 -0.020478 -0.010005 -0.924921 + 11 -0.429907 0.828356 0.255621 0.845440 0.455381 0.122581 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 180.28 0.021205 107.16 0.036706 (-0.032267 -0.029512 -0.186530) + 7: 648.28 0.005778 29.20 0.002781 ( 0.045144 0.027076 -0.003195) + 8: 845.72 0.053320 269.46 0.019675 (-0.108304 -0.004153 0.089037) + 9: 1293.78 0.001755 8.87 0.000423 (-0.005202 0.017115 0.010166) + 10: 1649.73 0.029681 150.00 0.005615 (-0.055250 -0.018532 0.047101) + 11: 3636.20 0.009092 45.94 0.000780 ( 0.019638 -0.019068 -0.005569) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 180.28 E(vib) ... 0.37 +freq. 648.28 E(vib) ... 0.08 +freq. 845.72 E(vib) ... 0.04 +freq. 1293.78 E(vib) ... 0.01 +freq. 1649.73 E(vib) ... 0.00 +freq. 3636.20 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.44309184 Eh +Zero point energy ... 0.01880396 Eh 11.80 kcal/mol +Thermal vibrational correction ... 0.00080789 Eh 0.51 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42064744 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00364043 Eh 2.28 kcal/mol +Non-thermal (ZPE) correction 0.01880396 Eh 11.80 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02244440 Eh 14.08 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42064744 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.41970323 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.759452 0.426221 0.374293 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00137897 Eh 0.87 kcal/mol +Rotational entropy ... 0.00989815 Eh 6.21 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02907944 Eh 18.25 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00989815 Eh 6.21 kcal/mol| +| sn= 2 | S(rot)= 0.00924369 Eh 5.80 kcal/mol| +| sn= 3 | S(rot)= 0.00886086 Eh 5.56 kcal/mol| +| sn= 4 | S(rot)= 0.00858924 Eh 5.39 kcal/mol| +| sn= 5 | S(rot)= 0.00837855 Eh 5.26 kcal/mol| +| sn= 6 | S(rot)= 0.00820641 Eh 5.15 kcal/mol| +| sn= 7 | S(rot)= 0.00806086 Eh 5.06 kcal/mol| +| sn= 8 | S(rot)= 0.00793478 Eh 4.98 kcal/mol| +| sn= 9 | S(rot)= 0.00782357 Eh 4.91 kcal/mol| +| sn=10 | S(rot)= 0.00772409 Eh 4.85 kcal/mol| +| sn=11 | S(rot)= 0.00763410 Eh 4.79 kcal/mol| +| sn=12 | S(rot)= 0.00755195 Eh 4.74 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.41970323 Eh +Total entropy correction ... -0.02907944 Eh -18.25 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44878267 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00569084 Eh -3.57 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.443091837 Eh +Current gradient norm .... 0.026321831 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.001396003 0.132207189 0.207613262 0.471467624 0.523036496 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999692971 +Lowest eigenvalues of augmented Hessian: + -0.000119148 0.126797884 0.206318535 0.471396963 0.522743196 +Length of the computed step .... 0.024785911 +The final length of the internal step .... 0.024785911 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0101188059 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0068057625 RMS(Int)= 0.0101204813 + Iter 1: RMS(Cart)= 0.0000034349 RMS(Int)= 0.0000061399 + Iter 2: RMS(Cart)= 0.0000000121 RMS(Int)= 0.0000000190 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0022307431 0.0001000000 NO + MAX gradient 0.0033057409 0.0003000000 NO + RMS step 0.0101188059 0.0020000000 NO + MAX step 0.0225514584 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0119 Max(Angles) 0.18 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4249 -0.003306 0.0119 1.4368 + 2. B(O 2,N 1) 1.1827 0.003088 -0.0040 1.1787 + 3. B(H 3,O 0) 0.9766 0.002742 -0.0033 0.9734 + 4. A(N 1,O 0,H 3) 104.87 -0.001316 0.18 105.04 + 5. A(O 0,N 1,O 2) 112.94 -0.000376 0.01 112.95 + 6. D(O 2,N 1,O 0,H 3) 40.91 0.018827 0.00 40.91 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.505566 -0.344651 0.666298 + N 0.350395 -0.575550 -0.464356 + O 1.005907 0.363278 -0.743873 + H -0.850735 0.556923 0.541931 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.955381 -0.651296 1.259120 + 1 N 7.0000 0 14.007 0.662151 -1.087632 -0.877506 + 2 O 8.0000 0 15.999 1.900888 0.686497 -1.405716 + 3 H 1.0000 0 1.008 -1.607656 1.052431 1.024102 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.436789073570 0.00000000 0.00000000 + O 2 1 0 1.178653417911 112.95073718 0.00000000 + H 1 2 3 0.973367198344 105.04430621 40.90909089 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.715137861258 0.00000000 0.00000000 + O 2 1 0 2.227332166661 112.95073718 0.00000000 + H 1 2 3 1.839397432613 105.04430621 40.90909089 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2242 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2715 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 542 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.399991392608 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.556e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7153592524 0.000000000000 0.00034784 0.00001009 0.0017772 0.7000 + 1 -204.7153846054 -0.000025353037 0.00028676 0.00000861 0.0013914 0.7000 + ***Turning on DIIS*** + 2 -204.7154057596 -0.000021154173 0.00073682 0.00002267 0.0010824 0.0000 + 3 -204.7151340438 0.000271715741 0.00033309 0.00001117 0.0003463 0.0000 + 4 -204.7154781208 -0.000344076974 0.00014928 0.00000427 0.0001222 0.0000 + 5 -204.7155467235 -0.000068602728 0.00004647 0.00000133 0.0001041 0.0000 + 6 -204.7154658364 0.000080887179 0.00003832 0.00000091 0.0000499 0.0000 + 7 -204.7154886774 -0.000022841079 0.00001323 0.00000037 0.0000138 0.0000 + 8 -204.7154711527 0.000017524718 0.00000897 0.00000025 0.0000082 0.0000 + 9 -204.7154789943 -0.000007841546 0.00000499 0.00000015 0.0000034 0.0000 + 10 -204.7154777715 0.000001222759 0.00000231 0.00000008 0.0000018 0.0000 + 11 -204.7154745976 0.000003173878 0.00000129 0.00000005 0.0000011 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + +Total Energy : -204.71547739 Eh -5570.59134 eV + Last Energy change ... -2.7935e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.7597e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.224 sec +Reference energy ... -204.715477029 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.357 sec +AO-integral generation ... 0.144 sec +Half transformation ... 0.079 sec +K-integral sorting ... 5.358 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.025 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.036 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.350 sec +AO-integral generation ... 0.246 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.049 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.151 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.254 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090285303 +EMP2(bb)= -0.090285303 +EMP2(ab)= -0.515534658 + +Initial guess performed in 0.132 sec +E(0) ... -204.715477029 +E(MP2) ... -0.696105264 +Initial E(tot) ... -205.411582293 + ... 0.187302509 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.411582293 -0.696105264 -0.000000000 0.024785003 2.79 0.000000800 + *** Turning on DIIS *** + 1 -205.383174014 -0.667696985 0.028408279 0.009864798 2.81 0.057296269 + 2 -205.402568487 -0.687091458 -0.019394473 0.005457143 2.92 0.060493146 + 3 -205.406310143 -0.690833114 -0.003741656 0.001802307 2.91 0.074704814 + 4 -205.407883340 -0.692406311 -0.001573197 0.001522508 2.98 0.081550883 + 5 -205.408436099 -0.692959071 -0.000552759 0.000902524 2.94 0.087156592 + 6 -205.408545710 -0.693068682 -0.000109611 0.000551805 3.04 0.089965317 + 7 -205.408592278 -0.693115249 -0.000046567 0.000250931 3.06 0.091262094 + 8 -205.408603809 -0.693126780 -0.000011531 0.000120205 3.10 0.091787457 + 9 -205.408599741 -0.693122712 0.000004068 0.000049375 2.94 0.091948051 + 10 -205.408605022 -0.693127993 -0.000005281 0.000030641 2.98 0.092012366 + 11 -205.408602023 -0.693124994 0.000002999 0.000022024 3.00 0.092001422 + 12 -205.408603399 -0.693126370 -0.000001376 0.000014577 3.39 0.092015672 + 13 -205.408603230 -0.693126201 0.000000169 0.000008587 2.96 0.092011823 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.715477029 +E(CORR) ... -0.693126201 +E(TOT) ... -205.408603230 +Singles norm **1/2 ... 0.092011823 ( 0.046005912, 0.046005912) +T1 diagnostic ... 0.021687395 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.057672 + 8b-> 13b -1b-> -1b 0.040802 + 8a-> 13a -1a-> -1a 0.040802 + 9a-> 13a 9b-> 13b 0.036013 + 10a-> 13a 10b-> 13b 0.034632 + 9a-> 13a 8b-> 13b 0.031567 + 8a-> 13a 9b-> 13b 0.031567 + 11a-> 13a 11b-> 13b 0.030338 + 10b-> 13b -1b-> -1b 0.029707 + 10a-> 13a -1a-> -1a 0.029707 + 5a-> 13a 5b-> 13b 0.026905 + 10a-> 13a 8b-> 13b 0.026630 + 8a-> 13a 10b-> 13b 0.026630 + 9a-> 13a 10b-> 13b 0.025232 + 10a-> 13a 9b-> 13b 0.025232 + 8a-> 13a 8b-> 22b 0.021611 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034549621 + alpha-alpha-alpha ... -0.000894890 ( 2.6%) + alpha-alpha-beta ... -0.016379920 ( 47.4%) + alpha-beta -beta ... -0.016379920 ( 47.4%) + beta -beta -beta ... -0.000894890 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034549621 + +Final correlation energy ... -0.727675822 +E(CCSD) ... -205.408603230 +E(CCSD(T)) ... -205.443152850 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209528721 sqrt= 1.099785762 +W(HF) = 0.826768296 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 57.047 sec + +Fock Matrix Formation ... 0.224 sec ( 0.4%) +Initial Guess ... 0.132 sec ( 0.2%) +DIIS Solver ... 2.169 sec ( 3.8%) +State Vector Update ... 0.090 sec ( 0.2%) +Sigma-vector construction ... 39.549 sec ( 69.3%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (0-ext) ... 0.075 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (2-ext) ... 0.941 sec ( 2.4% of sigma) + (4-ext) ... 22.331 sec ( 56.5% of sigma) + ... 1.557 sec ( 3.9% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.107 sec ( 0.3% of sigma) + Fock-dressing ... 2.104 sec ( 5.3% of sigma) + (ik|jl)-dressing ... 0.075 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.736 sec ( 24.6% of sigma) + Pair energies ... 0.007 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.953 sec ( 12.2% of ALL) + I/O of integral and amplitudes ... 0.645 sec ( 9.3% of (T)) + External N**7 contributions ... 3.986 sec ( 57.3% of (T)) + Internal N**7 contributions ... 0.323 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.610 sec ( 23.1% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.443152850422 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.011434188 0.003481162 0.007721572 + 2 N : -0.009879651 0.003175516 -0.007911563 + 3 O : 0.006333974 -0.002888323 0.005416278 + 4 H : -0.007888511 -0.003768355 -0.005226288 + +Norm of the cartesian gradient ... 0.023543725 +RMS gradient ... 0.006796488 +MAX gradient ... 0.011434188 + +------- +TIMINGS +------- + +Total numerical gradient time ... 371.253 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.443152850 Eh +Current gradient norm .... 0.023543725 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999237 +Lowest eigenvalues of augmented Hessian: + -0.000000228 0.123429907 0.202315259 0.473309250 0.524767239 +Length of the computed step .... 0.001235572 +The final length of the internal step .... 0.001235572 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0005044201 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0002908095 RMS(Int)= 0.0005044209 + Iter 1: RMS(Cart)= 0.0000000088 RMS(Int)= 0.0000000148 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000610130 0.0000050000 NO + RMS gradient 0.0000846899 0.0001000000 YES + MAX gradient 0.0001949424 0.0003000000 YES + RMS step 0.0005044201 0.0020000000 YES + MAX step 0.0012192231 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0006 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4368 -0.000195 0.0006 1.4374 + 2. B(O 2,N 1) 1.1787 -0.000062 -0.0001 1.1786 + 3. B(H 3,O 0) 0.9734 -0.000026 0.0000 0.9734 + 4. A(N 1,O 0,H 3) 105.04 -0.000023 -0.01 105.04 + 5. A(O 0,N 1,O 2) 112.95 -0.000002 -0.00 112.95 + 6. D(O 2,N 1,O 0,H 3) 40.91 0.018092 -0.00 40.91 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.505772 -0.344626 0.666537 + N 0.350617 -0.575597 -0.464598 + O 1.006045 0.363254 -0.743991 + H -0.850889 0.556968 0.542051 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.955771 -0.651249 1.259573 + 1 N 7.0000 0 14.007 0.662570 -1.087720 -0.877963 + 2 O 8.0000 0 15.999 1.901150 0.686451 -1.405939 + 3 H 1.0000 0 1.008 -1.607947 1.052517 1.024329 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.437434258659 0.00000000 0.00000000 + O 2 1 0 1.178595863146 112.94586331 0.00000000 + H 1 2 3 0.973383013108 105.03616818 40.90909089 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.716357084382 0.00000000 0.00000000 + O 2 1 0 2.227223403919 112.94586331 0.00000000 + H 1 2 3 1.839427318186 105.03616818 40.90909089 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2242 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2715 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 542 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.387890229075 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.3878902291 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.557e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7154267890 0.000000000000 0.00001951 0.00000048 0.0000919 0.7000 + 1 -204.7154268410 -0.000000051934 0.00001608 0.00000041 0.0000708 0.7000 + ***Turning on DIIS*** + 2 -204.7154268843 -0.000000043336 0.00004188 0.00000108 0.0000541 0.0000 + 3 -204.7154412644 -0.000014380153 0.00001433 0.00000048 0.0000139 0.0000 + 4 -204.7154175965 0.000023667970 0.00000625 0.00000016 0.0000043 0.0000 + 5 -204.7154262015 -0.000008605018 0.00000182 0.00000005 0.0000016 0.0000 + 6 -204.7154331673 -0.000006965805 0.00000097 0.00000002 0.0000014 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71542654 Eh -5570.58996 eV + +Components: +Nuclear Repulsion : 69.38789023 Eh 1888.14048 eV +Electronic Energy : -274.10331677 Eh -7458.73044 eV +One Electron Energy: -418.40464931 Eh -11385.36933 eV +Two Electron Energy: 144.30133254 Eh 3926.63888 eV + +Virial components: +Potential Energy : -408.95526271 Eh -11128.23845 eV +Kinetic Energy : 204.23983618 Eh 5557.64849 eV +Virial Ratio : 2.00232859 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 6.6300e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.9440e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 8.5722e-09 Tolerance : 5.0000e-09 + Last DIIS Error ... 4.8911e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.676665 -562.6406 + 1 1.0000 -20.636708 -561.5534 + 2 1.0000 -15.803560 -430.0367 + 3 1.0000 -1.609670 -43.8014 + 4 1.0000 -1.395188 -37.9650 + 5 1.0000 -0.962159 -26.1817 + 6 1.0000 -0.773680 -21.0529 + 7 1.0000 -0.738677 -20.1004 + 8 1.0000 -0.694428 -18.8964 + 9 1.0000 -0.606713 -16.5095 + 10 1.0000 -0.534105 -14.5337 + 11 1.0000 -0.469438 -12.7740 + 12 0.0000 0.031086 0.8459 + 13 0.0000 0.070981 1.9315 + 14 0.0000 0.094157 2.5622 + 15 0.0000 0.110877 3.0171 + 16 0.0000 0.116873 3.1803 + 17 0.0000 0.151344 4.1183 + 18 0.0000 0.157247 4.2789 + 19 0.0000 0.170471 4.6388 + 20 0.0000 0.181347 4.9347 + 21 0.0000 0.193348 5.2613 + 22 0.0000 0.203407 5.5350 + 23 0.0000 0.234321 6.3762 + 24 0.0000 0.262398 7.1402 + 25 0.0000 0.293954 7.9989 + 26 0.0000 0.310557 8.4507 + 27 0.0000 0.340012 9.2522 + 28 0.0000 0.345776 9.4090 + 29 0.0000 0.379134 10.3168 + 30 0.0000 0.422137 11.4869 + 31 0.0000 0.514844 14.0096 + 32 0.0000 0.528545 14.3824 + 33 0.0000 0.534202 14.5364 + 34 0.0000 0.562608 15.3093 + 35 0.0000 0.611356 16.6358 + 36 0.0000 0.633892 17.2491 + 37 0.0000 0.650637 17.7047 + 38 0.0000 0.692752 18.8507 + 39 0.0000 0.706414 19.2225 + 40 0.0000 0.733698 19.9649 + 41 0.0000 0.744142 20.2491 + 42 0.0000 0.766509 20.8578 + 43 0.0000 0.784103 21.3365 + 44 0.0000 0.811193 22.0737 + 45 0.0000 0.834397 22.7051 + 46 0.0000 0.849325 23.1113 + 47 0.0000 0.880055 23.9475 + 48 0.0000 0.919488 25.0205 + 49 0.0000 0.941855 25.6292 + 50 0.0000 0.968472 26.3535 + 51 0.0000 0.982077 26.7237 + 52 0.0000 1.017438 27.6859 + 53 0.0000 1.026008 27.9191 + 54 0.0000 1.061626 28.8883 + 55 0.0000 1.086908 29.5763 + 56 0.0000 1.166635 31.7458 + 57 0.0000 1.198666 32.6174 + 58 0.0000 1.235285 33.6138 + 59 0.0000 1.278744 34.7964 + 60 0.0000 1.359275 36.9878 + 61 0.0000 1.411670 38.4135 + 62 0.0000 1.440529 39.1988 + 63 0.0000 1.525774 41.5184 + 64 0.0000 1.530986 41.6602 + 65 0.0000 1.546884 42.0929 + 66 0.0000 1.612867 43.8883 + 67 0.0000 1.631787 44.4032 + 68 0.0000 1.654194 45.0129 + 69 0.0000 1.732690 47.1489 + 70 0.0000 1.770823 48.1865 + 71 0.0000 1.803353 49.0717 + 72 0.0000 1.905343 51.8470 + 73 0.0000 1.961125 53.3649 + 74 0.0000 1.974851 53.7384 + 75 0.0000 2.014212 54.8095 + 76 0.0000 2.042157 55.5699 + 77 0.0000 2.078661 56.5632 + 78 0.0000 2.157933 58.7204 + 79 0.0000 2.173772 59.1513 + 80 0.0000 2.253415 61.3185 + 81 0.0000 2.306561 62.7647 + 82 0.0000 2.352310 64.0096 + 83 0.0000 2.395190 65.1764 + 84 0.0000 2.416278 65.7503 + 85 0.0000 2.449099 66.6434 + 86 0.0000 2.469701 67.2040 + 87 0.0000 2.505814 68.1867 + 88 0.0000 2.532102 68.9020 + 89 0.0000 2.557188 69.5846 + 90 0.0000 2.575640 70.0867 + 91 0.0000 2.618438 71.2513 + 92 0.0000 2.651830 72.1600 + 93 0.0000 2.693295 73.2883 + 94 0.0000 2.761603 75.1470 + 95 0.0000 2.802756 76.2669 + 96 0.0000 2.835145 77.1482 + 97 0.0000 2.942158 80.0602 + 98 0.0000 2.974867 80.9503 + 99 0.0000 3.014655 82.0329 + 100 0.0000 3.139652 85.4343 + 101 0.0000 3.170407 86.2712 + 102 0.0000 3.227963 87.8373 + 103 0.0000 3.512706 95.5856 + 104 0.0000 3.693028 100.4924 + 105 0.0000 3.880957 105.6062 + 106 0.0000 4.016832 109.3036 + 107 0.0000 4.151884 112.9785 + 108 0.0000 4.184948 113.8782 + 109 0.0000 4.326865 117.7400 + 110 0.0000 4.380982 119.2126 + 111 0.0000 4.387883 119.4004 + 112 0.0000 4.533411 123.3604 + 113 0.0000 4.582273 124.6900 + 114 0.0000 4.678540 127.3095 + 115 0.0000 4.796041 130.5069 + 116 0.0000 4.821981 131.2128 + 117 0.0000 4.867859 132.4612 + 118 0.0000 4.967631 135.1761 + 119 0.0000 4.999048 136.0310 + 120 0.0000 5.073547 138.0582 + 121 0.0000 5.107303 138.9768 + 122 0.0000 5.185652 141.1088 + 123 0.0000 5.233264 142.4043 + 124 0.0000 5.248645 142.8229 + 125 0.0000 5.278536 143.6363 + 126 0.0000 5.382860 146.4751 + 127 0.0000 5.472980 148.9273 + 128 0.0000 5.533848 150.5837 + 129 0.0000 5.699056 155.0792 + 130 0.0000 5.775901 157.1703 + 131 0.0000 5.952674 161.9805 + 132 0.0000 6.164642 167.7484 + 133 0.0000 6.402857 174.2306 + 134 0.0000 6.495176 176.7427 + 135 0.0000 6.527390 177.6193 + 136 0.0000 6.686175 181.9401 + 137 0.0000 6.721689 182.9065 + 138 0.0000 6.778347 184.4482 + 139 0.0000 6.799608 185.0267 + 140 0.0000 6.895362 187.6323 + 141 0.0000 7.096950 193.1178 + 142 0.0000 7.127109 193.9385 + 143 0.0000 7.170498 195.1192 + 144 0.0000 7.197704 195.8595 + 145 0.0000 7.246212 197.1795 + 146 0.0000 7.265349 197.7002 + 147 0.0000 7.316036 199.0795 + 148 0.0000 7.393274 201.1812 + 149 0.0000 7.462454 203.0637 + 150 0.0000 7.507965 204.3021 + 151 0.0000 7.534512 205.0245 + 152 0.0000 7.552423 205.5119 + 153 0.0000 7.664409 208.5592 + 154 0.0000 7.779866 211.7009 + 155 0.0000 7.890093 214.7003 + 156 0.0000 8.136727 221.4116 + 157 0.0000 8.349969 227.2142 + 158 0.0000 14.047188 382.2434 + 159 0.0000 15.109899 411.1613 + 160 0.0000 15.782931 429.4754 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.676665 -562.6406 + 1 1.0000 -20.636708 -561.5534 + 2 1.0000 -15.803560 -430.0367 + 3 1.0000 -1.609670 -43.8014 + 4 1.0000 -1.395188 -37.9650 + 5 1.0000 -0.962159 -26.1817 + 6 1.0000 -0.773680 -21.0529 + 7 1.0000 -0.738677 -20.1004 + 8 1.0000 -0.694428 -18.8964 + 9 1.0000 -0.606713 -16.5095 + 10 1.0000 -0.534105 -14.5337 + 11 1.0000 -0.469438 -12.7740 + 12 0.0000 0.031086 0.8459 + 13 0.0000 0.070981 1.9315 + 14 0.0000 0.094157 2.5622 + 15 0.0000 0.110877 3.0171 + 16 0.0000 0.116873 3.1803 + 17 0.0000 0.151344 4.1183 + 18 0.0000 0.157247 4.2789 + 19 0.0000 0.170471 4.6388 + 20 0.0000 0.181347 4.9347 + 21 0.0000 0.193348 5.2613 + 22 0.0000 0.203407 5.5350 + 23 0.0000 0.234321 6.3762 + 24 0.0000 0.262398 7.1402 + 25 0.0000 0.293954 7.9989 + 26 0.0000 0.310557 8.4507 + 27 0.0000 0.340012 9.2522 + 28 0.0000 0.345776 9.4090 + 29 0.0000 0.379134 10.3168 + 30 0.0000 0.422137 11.4869 + 31 0.0000 0.514844 14.0096 + 32 0.0000 0.528545 14.3824 + 33 0.0000 0.534202 14.5364 + 34 0.0000 0.562608 15.3093 + 35 0.0000 0.611356 16.6358 + 36 0.0000 0.633892 17.2491 + 37 0.0000 0.650637 17.7047 + 38 0.0000 0.692752 18.8507 + 39 0.0000 0.706414 19.2225 + 40 0.0000 0.733698 19.9649 + 41 0.0000 0.744142 20.2491 + 42 0.0000 0.766509 20.8578 + 43 0.0000 0.784103 21.3365 + 44 0.0000 0.811193 22.0737 + 45 0.0000 0.834397 22.7051 + 46 0.0000 0.849325 23.1113 + 47 0.0000 0.880055 23.9475 + 48 0.0000 0.919488 25.0205 + 49 0.0000 0.941855 25.6292 + 50 0.0000 0.968472 26.3535 + 51 0.0000 0.982077 26.7237 + 52 0.0000 1.017438 27.6859 + 53 0.0000 1.026008 27.9191 + 54 0.0000 1.061626 28.8883 + 55 0.0000 1.086908 29.5763 + 56 0.0000 1.166635 31.7458 + 57 0.0000 1.198666 32.6174 + 58 0.0000 1.235285 33.6138 + 59 0.0000 1.278744 34.7964 + 60 0.0000 1.359275 36.9878 + 61 0.0000 1.411670 38.4135 + 62 0.0000 1.440529 39.1988 + 63 0.0000 1.525774 41.5184 + 64 0.0000 1.530986 41.6602 + 65 0.0000 1.546884 42.0929 + 66 0.0000 1.612867 43.8883 + 67 0.0000 1.631787 44.4032 + 68 0.0000 1.654194 45.0129 + 69 0.0000 1.732690 47.1489 + 70 0.0000 1.770823 48.1865 + 71 0.0000 1.803353 49.0717 + 72 0.0000 1.905343 51.8470 + 73 0.0000 1.961125 53.3649 + 74 0.0000 1.974851 53.7384 + 75 0.0000 2.014212 54.8095 + 76 0.0000 2.042157 55.5699 + 77 0.0000 2.078661 56.5632 + 78 0.0000 2.157933 58.7204 + 79 0.0000 2.173772 59.1513 + 80 0.0000 2.253415 61.3185 + 81 0.0000 2.306561 62.7647 + 82 0.0000 2.352310 64.0096 + 83 0.0000 2.395190 65.1764 + 84 0.0000 2.416278 65.7503 + 85 0.0000 2.449099 66.6434 + 86 0.0000 2.469701 67.2040 + 87 0.0000 2.505814 68.1867 + 88 0.0000 2.532102 68.9020 + 89 0.0000 2.557188 69.5846 + 90 0.0000 2.575640 70.0867 + 91 0.0000 2.618438 71.2513 + 92 0.0000 2.651830 72.1600 + 93 0.0000 2.693295 73.2883 + 94 0.0000 2.761603 75.1470 + 95 0.0000 2.802756 76.2669 + 96 0.0000 2.835145 77.1482 + 97 0.0000 2.942158 80.0602 + 98 0.0000 2.974867 80.9503 + 99 0.0000 3.014655 82.0329 + 100 0.0000 3.139652 85.4343 + 101 0.0000 3.170407 86.2712 + 102 0.0000 3.227963 87.8373 + 103 0.0000 3.512706 95.5856 + 104 0.0000 3.693028 100.4924 + 105 0.0000 3.880957 105.6062 + 106 0.0000 4.016832 109.3036 + 107 0.0000 4.151884 112.9785 + 108 0.0000 4.184948 113.8782 + 109 0.0000 4.326865 117.7400 + 110 0.0000 4.380982 119.2126 + 111 0.0000 4.387883 119.4004 + 112 0.0000 4.533411 123.3604 + 113 0.0000 4.582273 124.6900 + 114 0.0000 4.678540 127.3095 + 115 0.0000 4.796041 130.5069 + 116 0.0000 4.821981 131.2128 + 117 0.0000 4.867859 132.4612 + 118 0.0000 4.967631 135.1761 + 119 0.0000 4.999048 136.0310 + 120 0.0000 5.073547 138.0582 + 121 0.0000 5.107303 138.9768 + 122 0.0000 5.185652 141.1088 + 123 0.0000 5.233264 142.4043 + 124 0.0000 5.248645 142.8229 + 125 0.0000 5.278536 143.6363 + 126 0.0000 5.382860 146.4751 + 127 0.0000 5.472980 148.9273 + 128 0.0000 5.533848 150.5837 + 129 0.0000 5.699056 155.0792 + 130 0.0000 5.775901 157.1703 + 131 0.0000 5.952674 161.9805 + 132 0.0000 6.164642 167.7484 + 133 0.0000 6.402857 174.2306 + 134 0.0000 6.495176 176.7427 + 135 0.0000 6.527390 177.6193 + 136 0.0000 6.686175 181.9401 + 137 0.0000 6.721689 182.9065 + 138 0.0000 6.778347 184.4482 + 139 0.0000 6.799608 185.0267 + 140 0.0000 6.895362 187.6323 + 141 0.0000 7.096950 193.1178 + 142 0.0000 7.127109 193.9385 + 143 0.0000 7.170498 195.1192 + 144 0.0000 7.197704 195.8595 + 145 0.0000 7.246212 197.1795 + 146 0.0000 7.265349 197.7002 + 147 0.0000 7.316036 199.0795 + 148 0.0000 7.393274 201.1812 + 149 0.0000 7.462454 203.0637 + 150 0.0000 7.507965 204.3021 + 151 0.0000 7.534512 205.0245 + 152 0.0000 7.552423 205.5119 + 153 0.0000 7.664409 208.5592 + 154 0.0000 7.779866 211.7009 + 155 0.0000 7.890093 214.7003 + 156 0.0000 8.136727 221.4116 + 157 0.0000 8.349969 227.2142 + 158 0.0000 14.047188 382.2434 + 159 0.0000 15.109899 411.1613 + 160 0.0000 15.782931 429.4754 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.320769 0.000000 + 1 N : 0.348720 0.000000 + 2 O : -0.276987 0.000000 + 3 H : 0.249036 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.824655 s : 3.824655 + pz : 1.417970 p : 4.458111 + px : 1.599116 + py : 1.441024 + dz2 : 0.008755 d : 0.033101 + dxz : 0.008206 + dyz : 0.005263 + dx2y2 : 0.009938 + dxy : 0.000939 + f0 : 0.000952 f : 0.004903 + f+1 : 0.001166 + f-1 : 0.000547 + f+2 : 0.000842 + f-2 : 0.000882 + f+3 : 0.000243 + f-3 : 0.000271 + 1 N s : 3.844060 s : 3.844060 + pz : 0.742907 p : 2.632557 + px : 0.743031 + py : 1.146619 + dz2 : 0.030039 d : 0.142138 + dxz : 0.031522 + dyz : 0.019708 + dx2y2 : 0.034206 + dxy : 0.026662 + f0 : 0.006648 f : 0.032525 + f+1 : 0.001678 + f-1 : 0.005072 + f+2 : 0.003278 + f-2 : 0.005913 + f+3 : 0.003178 + f-3 : 0.006759 + 2 O s : 3.868490 s : 3.868490 + pz : 1.617362 p : 4.339783 + px : 1.331027 + py : 1.391394 + dz2 : 0.006488 d : 0.061221 + dxz : 0.004902 + dyz : 0.017167 + dx2y2 : 0.018661 + dxy : 0.014003 + f0 : 0.000848 f : 0.007493 + f+1 : 0.000466 + f-1 : 0.001105 + f+2 : 0.000391 + f-2 : 0.001153 + f+3 : 0.001385 + f-3 : 0.002145 + 3 H s : 0.641994 s : 0.641994 + pz : 0.026846 p : 0.087700 + px : 0.038085 + py : 0.022769 + dz2 : 0.000815 d : 0.021270 + dxz : 0.000403 + dyz : 0.009008 + dx2y2 : 0.004601 + dxy : 0.006443 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.592210 0.000000 + 1 N : -0.267359 0.000000 + 2 O : 0.244527 0.000000 + 3 H : -0.569378 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.116168 s : 3.116168 + pz : 1.275783 p : 3.922066 + px : 1.325842 + py : 1.320442 + dz2 : 0.061667 d : 0.283535 + dxz : 0.084399 + dyz : 0.053337 + dx2y2 : 0.037375 + dxy : 0.046757 + f0 : 0.010393 f : 0.086021 + f+1 : 0.018919 + f-1 : 0.013198 + f+2 : 0.013795 + f-2 : 0.018909 + f+3 : 0.006148 + f-3 : 0.004659 + 1 N s : 3.014732 s : 3.014732 + pz : 0.807117 p : 2.833746 + px : 0.802273 + py : 1.224356 + dz2 : 0.195901 d : 0.958121 + dxz : 0.214010 + dyz : 0.151967 + dx2y2 : 0.209536 + dxy : 0.186707 + f0 : 0.075467 f : 0.460761 + f+1 : 0.050289 + f-1 : 0.060197 + f+2 : 0.041886 + f-2 : 0.089973 + f+3 : 0.062586 + f-3 : 0.080364 + 2 O s : 3.306081 s : 3.306081 + pz : 1.345316 p : 4.009743 + px : 1.236277 + py : 1.428150 + dz2 : 0.050231 d : 0.323529 + dxz : 0.048625 + dyz : 0.043688 + dx2y2 : 0.092398 + dxy : 0.088587 + f0 : 0.009588 f : 0.116120 + f+1 : 0.008409 + f-1 : 0.018908 + f+2 : 0.006328 + f-2 : 0.020406 + f+3 : 0.027919 + f-3 : 0.024563 + 3 H s : 0.616955 s : 0.616955 + pz : 0.142604 p : 0.555053 + px : 0.159212 + py : 0.253236 + dz2 : 0.034233 d : 0.397370 + dxz : 0.037467 + dyz : 0.106127 + dx2y2 : 0.113219 + dxy : 0.106323 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3208 8.0000 -0.3208 1.8191 1.8191 0.0000 + 1 N 6.6513 7.0000 0.3487 2.5390 2.5390 0.0000 + 2 O 8.2770 8.0000 -0.2770 1.7282 1.7282 0.0000 + 3 H 0.7510 1.0000 0.2490 1.0122 1.0122 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8152 B( 0-O , 3-H ) : 0.9434 B( 1-N , 2-O ) : 1.6614 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.362 sec +Sum of individual times .... 1.103 sec ( 80.9%) + +Fock matrix formation .... 0.871 sec ( 63.9%) +Diagonalization .... 0.087 sec ( 6.4%) +Density matrix formation .... 0.007 sec ( 0.5%) +Population analysis .... 0.062 sec ( 4.6%) +Initial guess .... 0.010 sec ( 0.7%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.006 sec ( 0.4%) +DIIS solution .... 0.066 sec ( 4.8%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.211 sec +Reference energy ... -204.715427029 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.384 sec +AO-integral generation ... 0.146 sec +Half transformation ... 0.082 sec +K-integral sorting ... 5.383 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.024 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.038 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.038 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.036 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.356 sec +AO-integral generation ... 0.252 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.049 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.156 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.252 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090290337 +EMP2(bb)= -0.090290337 +EMP2(ab)= -0.515573994 + +Initial guess performed in 0.132 sec +E(0) ... -204.715427029 +E(MP2) ... -0.696154668 +Initial E(tot) ... -205.411581697 + ... 0.187350860 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.411581697 -0.696154668 -0.000000000 0.024777934 2.90 0.000000697 + *** Turning on DIIS *** + 1 -205.383151330 -0.667724301 0.028430367 0.009878059 2.90 0.057318192 + 2 -205.402554077 -0.687127048 -0.019402747 0.005454612 3.03 0.060510184 + 3 -205.406297268 -0.690870239 -0.003743191 0.001800660 2.91 0.074728944 + 4 -205.407871389 -0.692444360 -0.001574121 0.001526549 3.06 0.081578504 + 5 -205.408424834 -0.692997805 -0.000553445 0.000904749 2.96 0.087191403 + 6 -205.408534644 -0.693107615 -0.000109810 0.000553164 3.13 0.090006144 + 7 -205.408581344 -0.693154315 -0.000046700 0.000251392 3.06 0.091307342 + 8 -205.408592929 -0.693165900 -0.000011585 0.000120473 3.09 0.091834501 + 9 -205.408588850 -0.693161821 0.000004079 0.000049346 2.96 0.091995521 + 10 -205.408594150 -0.693167121 -0.000005300 0.000030636 2.99 0.092060065 + 11 -205.408591143 -0.693164114 0.000003007 0.000022019 2.98 0.092049085 + 12 -205.408592520 -0.693165491 -0.000001377 0.000014581 3.05 0.092063380 + 13 -205.408592352 -0.693165322 0.000000169 0.000008602 3.11 0.092059519 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.715427029 +E(CORR) ... -0.693165322 +E(TOT) ... -205.408592352 +Singles norm **1/2 ... 0.092059519 ( 0.046029759, 0.046029759) +T1 diagnostic ... 0.021698637 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.057764 + 8a-> 13a -1a-> -1a 0.040785 + 8b-> 13b -1b-> -1b 0.040785 + 9a-> 13a 9b-> 13b 0.036013 + 10a-> 13a 10b-> 13b 0.034550 + 9a-> 13a 8b-> 13b 0.031606 + 8a-> 13a 9b-> 13b 0.031606 + 11a-> 13a 11b-> 13b 0.030317 + 10a-> 13a -1a-> -1a 0.029803 + 10b-> 13b -1b-> -1b 0.029803 + 5a-> 13a 5b-> 13b 0.026933 + 8a-> 13a 10b-> 13b 0.026620 + 10a-> 13a 8b-> 13b 0.026620 + 9a-> 13a 10b-> 13b 0.025193 + 10a-> 13a 9b-> 13b 0.025193 + 8a-> 22a 8b-> 13b 0.021639 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034560624 + alpha-alpha-alpha ... -0.000895019 ( 2.6%) + alpha-alpha-beta ... -0.016385293 ( 47.4%) + alpha-beta -beta ... -0.016385293 ( 47.4%) + beta -beta -beta ... -0.000895019 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034560624 + +Final correlation energy ... -0.727725946 +E(CCSD) ... -205.408592352 +E(CCSD(T)) ... -205.443152975 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209593774 sqrt= 1.099815336 +W(HF) = 0.826723832 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.242754 0.000000 + 1 N : 0.161612 -0.000000 + 2 O : -0.154749 0.000000 + 3 H : 0.235892 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.809417 s : 3.809417 + pz : 1.386397 p : 4.361428 + px : 1.560289 + py : 1.414742 + dz2 : 0.014997 d : 0.063333 + dxz : 0.012764 + dyz : 0.012279 + dx2y2 : 0.015320 + dxy : 0.007972 + f0 : 0.001570 f : 0.008577 + f+1 : 0.001397 + f-1 : 0.001137 + f+2 : 0.001279 + f-2 : 0.001373 + f+3 : 0.000903 + f-3 : 0.000919 + 1 N s : 3.896756 s : 3.896756 + pz : 0.804777 p : 2.739236 + px : 0.823174 + py : 1.111285 + dz2 : 0.037896 d : 0.170886 + dxz : 0.038292 + dyz : 0.024555 + dx2y2 : 0.039956 + dxy : 0.030187 + f0 : 0.006219 f : 0.031511 + f+1 : 0.001691 + f-1 : 0.005230 + f+2 : 0.003213 + f-2 : 0.005751 + f+3 : 0.003309 + f-3 : 0.006096 + 2 O s : 3.855524 s : 3.855524 + pz : 1.551891 p : 4.205710 + px : 1.292920 + py : 1.360898 + dz2 : 0.011902 d : 0.083478 + dxz : 0.011431 + dyz : 0.020609 + dx2y2 : 0.023496 + dxy : 0.016040 + f0 : 0.001290 f : 0.010038 + f+1 : 0.000946 + f-1 : 0.001489 + f+2 : 0.000895 + f-2 : 0.001533 + f+3 : 0.001662 + f-3 : 0.002224 + 3 H s : 0.654324 s : 0.654324 + pz : 0.030908 p : 0.090780 + px : 0.041561 + py : 0.018311 + dz2 : 0.000640 d : 0.019004 + dxz : 0.000747 + dyz : 0.008106 + dx2y2 : 0.003720 + dxy : 0.005792 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.604997 -0.000000 + 1 N : -0.314737 0.000000 + 2 O : 0.282039 0.000000 + 3 H : -0.572299 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.123553 s : 3.123553 + pz : 1.258047 p : 3.863104 + px : 1.302410 + py : 1.302647 + dz2 : 0.068394 d : 0.315060 + dxz : 0.090977 + dyz : 0.058299 + dx2y2 : 0.043682 + dxy : 0.053708 + f0 : 0.012370 f : 0.093286 + f+1 : 0.020454 + f-1 : 0.013646 + f+2 : 0.014845 + f-2 : 0.019341 + f+3 : 0.007005 + f-3 : 0.005625 + 1 N s : 3.020247 s : 3.020247 + pz : 0.837677 p : 2.880752 + px : 0.849536 + py : 1.193539 + dz2 : 0.198844 d : 0.963930 + dxz : 0.220077 + dyz : 0.146192 + dx2y2 : 0.206625 + dxy : 0.192192 + f0 : 0.071748 f : 0.449808 + f+1 : 0.050410 + f-1 : 0.059405 + f+2 : 0.041015 + f-2 : 0.087399 + f+3 : 0.062403 + f-3 : 0.077428 + 2 O s : 3.308203 s : 3.308203 + pz : 1.306921 p : 3.929420 + px : 1.214079 + py : 1.408419 + dz2 : 0.056696 d : 0.355538 + dxz : 0.053552 + dyz : 0.050900 + dx2y2 : 0.099960 + dxy : 0.094429 + f0 : 0.010619 f : 0.124801 + f+1 : 0.009671 + f-1 : 0.019246 + f+2 : 0.007920 + f-2 : 0.021166 + f+3 : 0.028361 + f-3 : 0.027818 + 3 H s : 0.620318 s : 0.620318 + pz : 0.143869 p : 0.565111 + px : 0.162694 + py : 0.258549 + dz2 : 0.034068 d : 0.386869 + dxz : 0.036434 + dyz : 0.102626 + dx2y2 : 0.110694 + dxy : 0.103048 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2428 8.0000 -0.2428 2.1896 1.7365 0.4531 + 1 N 6.8384 7.0000 0.1616 2.8188 2.3401 0.4786 + 2 O 8.1547 8.0000 -0.1547 2.1237 1.6253 0.4985 + 3 H 0.7641 1.0000 0.2359 1.0289 0.9547 0.0742 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7622 B( 0-O , 2-O ) : 0.1005 B( 0-O , 3-H ) : 0.8738 +B( 1-N , 2-O ) : 1.5109 + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 57.523 sec + +Fock Matrix Formation ... 0.211 sec ( 0.4%) +Initial Guess ... 0.132 sec ( 0.2%) +DIIS Solver ... 2.109 sec ( 3.7%) +State Vector Update ... 0.097 sec ( 0.2%) +Sigma-vector construction ... 39.923 sec ( 69.4%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.025 sec ( 0.1% of sigma) + (0-ext) ... 0.073 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (2-ext) ... 0.951 sec ( 2.4% of sigma) + (4-ext) ... 22.578 sec ( 56.6% of sigma) + ... 1.470 sec ( 3.7% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.109 sec ( 0.3% of sigma) + Fock-dressing ... 2.120 sec ( 5.3% of sigma) + (ik|jl)-dressing ... 0.079 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.853 sec ( 24.7% of sigma) + Pair energies ... 0.006 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.988 sec ( 12.1% of ALL) + I/O of integral and amplitudes ... 0.790 sec ( 11.3% of (T)) + External N**7 contributions ... 4.003 sec ( 57.3% of (T)) + Internal N**7 contributions ... 0.324 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.730 sec ( 24.8% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.443152975056 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.028.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.028.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.484652, -0.289527 -0.289427) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.68077 -0.21136 -0.68207 +Nuclear contribution : -1.03856 0.66876 0.65390 + ----------------------------------------- +Total Dipole Moment : -0.35780 0.45739 -0.02817 + ----------------------------------------- +Magnitude (a.u.) : 0.58139 +Magnitude (Debye) : 1.47779 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.757498 0.422688 0.371494 +Rotational constants in MHz : 82667.697045 12671.877989 11137.102057 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.111573 0.425119 0.380586 +x,y,z [Debye]: 0.283597 1.080566 0.967372 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.484652, -0.289527 -0.289427) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.77062 -0.13352 -0.68907 +Nuclear contribution : -1.03856 0.66876 0.65390 + ----------------------------------------- +Total Dipole Moment : -0.26794 0.53524 -0.03517 + ----------------------------------------- +Magnitude (a.u.) : 0.59959 +Magnitude (Debye) : 1.52404 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.757498 0.422688 0.371494 +Rotational constants in MHz : 82667.697045 12671.877989 11137.102057 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.023314 0.493693 0.339460 +x,y,z [Debye]: 0.059260 1.254869 0.862838 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 29 * + * * + * Dihedral ( 2, 1, 0, 3) : 49.09090909 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0340121168 RMS(Int)= 0.0001707432 + Iter 1: RMS(Cart)= 0.0000406677 RMS(Int)= 0.0000000180 + Iter 2: RMS(Cart)= 0.0000000043 RMS(Int)= 0.0000000000 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4386 0.000000 + 2. B(O 2,N 1) 1.1800 0.000000 + 3. B(H 3,O 0) 0.9754 0.000000 + 4. A(N 1,O 0,H 3) 104.8560 0.000000 + 5. A(O 0,N 1,O 2) 112.7901 0.000000 + 6. D(O 2,N 1,O 0,H 3) 49.0909 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.480375 -0.332625 0.683078 + N 0.329942 -0.562929 -0.483076 + O 1.031505 0.350451 -0.739831 + H -0.881071 0.545104 0.539829 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.907777 -0.628570 1.290830 + 1 N 7.0000 0 14.007 0.623499 -1.063782 -0.912880 + 2 O 8.0000 0 15.999 1.949262 0.662256 -1.398078 + 3 H 1.0000 0 1.008 -1.664982 1.030096 1.020128 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.437434258659 0.00000000 0.00000000 + O 2 1 0 1.178595863146 112.94586331 0.00000000 + H 1 2 3 0.973383013108 105.03616818 40.90909089 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.716357084382 0.00000000 0.00000000 + O 2 1 0 2.227223403919 112.94586331 0.00000000 + H 1 2 3 1.839427318186 105.03616818 40.90909089 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2241 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2713 + la=0 lb=0: 555 shell pairs + la=1 lb=0: 541 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.296585763929 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.2965857639 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.589e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7088844753 0.000000000000 0.00160209 0.00005064 0.0146248 0.7000 + 1 -204.7096430428 -0.000758567436 0.00146181 0.00004718 0.0121763 0.7000 + ***Turning on DIIS*** + 2 -204.7103031487 -0.000660105971 0.00394414 0.00013100 0.0099605 0.0000 + 3 -204.7135471419 -0.003243993181 0.00188230 0.00006182 0.0042746 0.0000 + 4 -204.7116871449 0.001859997038 0.00090723 0.00003306 0.0017425 0.0000 + 5 -204.7135595883 -0.001872443424 0.00087118 0.00003955 0.0008979 0.0000 + 6 -204.7129336836 0.000625904688 0.00051150 0.00002595 0.0007618 0.0000 + 7 -204.7123668889 0.000566794708 0.00041733 0.00001628 0.0003761 0.0000 + 8 -204.7133687770 -0.001001888087 0.00024345 0.00001025 0.0002205 0.0000 + 9 -204.7128679623 0.000500814735 0.00013658 0.00000401 0.0000868 0.0000 + 10 -204.7128833070 -0.000015344750 0.00004681 0.00000145 0.0000455 0.0000 + 11 -204.7130676346 -0.000184327618 0.00002888 0.00000073 0.0000240 0.0000 + 12 -204.7129602622 0.000107372446 0.00000769 0.00000022 0.0000071 0.0000 + 13 -204.7129840871 -0.000023824955 0.00000253 0.00000008 0.0000027 0.0000 + 14 -204.7129752742 0.000008812963 0.00000096 0.00000004 0.0000013 0.0000 + 15 -204.7129733110 0.000001963194 0.00000061 0.00000003 0.0000014 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 16 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71297676 Eh -5570.52330 eV + +Components: +Nuclear Repulsion : 69.29658576 Eh 1885.65596 eV +Electronic Energy : -274.00956253 Eh -7456.17926 eV +One Electron Energy: -418.23990652 Eh -11380.88645 eV +Two Electron Energy: 144.23034399 Eh 3924.70719 eV + +Virial components: +Potential Energy : -408.94677559 Eh -11128.00750 eV +Kinetic Energy : 204.23379883 Eh 5557.48420 eV +Virial Ratio : 2.00234622 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -3.4528e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.9192e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.3747e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.1168e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.677687 -562.6685 + 1 1.0000 -20.634857 -561.5030 + 2 1.0000 -15.802653 -430.0121 + 3 1.0000 -1.607913 -43.7535 + 4 1.0000 -1.393683 -37.9240 + 5 1.0000 -0.961011 -26.1504 + 6 1.0000 -0.772719 -21.0268 + 7 1.0000 -0.736862 -20.0510 + 8 1.0000 -0.696272 -18.9465 + 9 1.0000 -0.602932 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2.5601 + 15 0.0000 0.109928 2.9913 + 16 0.0000 0.114996 3.1292 + 17 0.0000 0.153104 4.1662 + 18 0.0000 0.156597 4.2612 + 19 0.0000 0.171741 4.6733 + 20 0.0000 0.180198 4.9034 + 21 0.0000 0.192485 5.2378 + 22 0.0000 0.203207 5.5296 + 23 0.0000 0.235033 6.3956 + 24 0.0000 0.265992 7.2380 + 25 0.0000 0.293229 7.9792 + 26 0.0000 0.311921 8.4878 + 27 0.0000 0.339828 9.2472 + 28 0.0000 0.344072 9.3627 + 29 0.0000 0.370967 10.0945 + 30 0.0000 0.420785 11.4502 + 31 0.0000 0.514348 13.9961 + 32 0.0000 0.531205 14.4548 + 33 0.0000 0.535119 14.5613 + 34 0.0000 0.562315 15.3014 + 35 0.0000 0.607815 16.5395 + 36 0.0000 0.633793 17.2464 + 37 0.0000 0.646555 17.5937 + 38 0.0000 0.696207 18.9447 + 39 0.0000 0.711677 19.3657 + 40 0.0000 0.733735 19.9660 + 41 0.0000 0.740433 20.1482 + 42 0.0000 0.768117 20.9015 + 43 0.0000 0.783405 21.3175 + 44 0.0000 0.813862 22.1463 + 45 0.0000 0.829817 22.5805 + 46 0.0000 0.851431 23.1686 + 47 0.0000 0.881416 23.9845 + 48 0.0000 0.915872 24.9221 + 49 0.0000 0.942076 25.6352 + 50 0.0000 0.972548 26.4644 + 51 0.0000 0.978112 26.6158 + 52 0.0000 1.007736 27.4219 + 53 0.0000 1.017633 27.6912 + 54 0.0000 1.056292 28.7432 + 55 0.0000 1.087825 29.6012 + 56 0.0000 1.162628 31.6367 + 57 0.0000 1.203933 32.7607 + 58 0.0000 1.231952 33.5231 + 59 0.0000 1.280692 34.8494 + 60 0.0000 1.348094 36.6835 + 61 0.0000 1.411627 38.4123 + 62 0.0000 1.446002 39.3477 + 63 0.0000 1.517161 41.2840 + 64 0.0000 1.543939 42.0127 + 65 0.0000 1.549389 42.1610 + 66 0.0000 1.616366 43.9836 + 67 0.0000 1.634099 44.4661 + 68 0.0000 1.653887 45.0046 + 69 0.0000 1.732547 47.1450 + 70 0.0000 1.762948 47.9723 + 71 0.0000 1.797098 48.9015 + 72 0.0000 1.911920 52.0260 + 73 0.0000 1.961606 53.3780 + 74 0.0000 1.972787 53.6823 + 75 0.0000 2.011636 54.7394 + 76 0.0000 2.048289 55.7368 + 77 0.0000 2.079794 56.5941 + 78 0.0000 2.156750 58.6882 + 79 0.0000 2.173597 59.1466 + 80 0.0000 2.255054 61.3631 + 81 0.0000 2.307970 62.8031 + 82 0.0000 2.345539 63.8254 + 83 0.0000 2.388876 65.0046 + 84 0.0000 2.419900 65.8488 + 85 0.0000 2.453368 66.7595 + 86 0.0000 2.469584 67.2008 + 87 0.0000 2.499471 68.0141 + 88 0.0000 2.522652 68.6449 + 89 0.0000 2.555394 69.5358 + 90 0.0000 2.576126 70.0999 + 91 0.0000 2.615075 71.1598 + 92 0.0000 2.658959 72.3539 + 93 0.0000 2.691288 73.2337 + 94 0.0000 2.770585 75.3915 + 95 0.0000 2.809874 76.4606 + 96 0.0000 2.827288 76.9344 + 97 0.0000 2.938696 79.9660 + 98 0.0000 2.974779 80.9479 + 99 0.0000 3.009050 81.8804 + 100 0.0000 3.138209 85.3950 + 101 0.0000 3.170633 86.2773 + 102 0.0000 3.224569 87.7450 + 103 0.0000 3.510719 95.5315 + 104 0.0000 3.687617 100.3452 + 105 0.0000 3.876874 105.4951 + 106 0.0000 4.019989 109.3895 + 107 0.0000 4.151687 112.9731 + 108 0.0000 4.187050 113.9354 + 109 0.0000 4.337660 118.0337 + 110 0.0000 4.369375 118.8968 + 111 0.0000 4.388627 119.4206 + 112 0.0000 4.538294 123.4933 + 113 0.0000 4.597069 125.0926 + 114 0.0000 4.675154 127.2174 + 115 0.0000 4.776083 129.9638 + 116 0.0000 4.808808 130.8543 + 117 0.0000 4.868467 132.4777 + 118 0.0000 4.965086 135.1069 + 119 0.0000 4.996496 135.9616 + 120 0.0000 5.068979 137.9339 + 121 0.0000 5.105365 138.9241 + 122 0.0000 5.177651 140.8910 + 123 0.0000 5.231229 142.3490 + 124 0.0000 5.250123 142.8631 + 125 0.0000 5.273761 143.5063 + 126 0.0000 5.385626 146.5503 + 127 0.0000 5.480531 149.1328 + 128 0.0000 5.529840 150.4746 + 129 0.0000 5.698553 155.0655 + 130 0.0000 5.772854 157.0874 + 131 0.0000 5.962719 162.2538 + 132 0.0000 6.167160 167.8170 + 133 0.0000 6.407453 174.3557 + 134 0.0000 6.493063 176.6852 + 135 0.0000 6.524676 177.5455 + 136 0.0000 6.686090 181.9378 + 137 0.0000 6.716161 182.7560 + 138 0.0000 6.779425 184.4775 + 139 0.0000 6.804369 185.1563 + 140 0.0000 6.882797 187.2904 + 141 0.0000 7.091726 192.9757 + 142 0.0000 7.122171 193.8041 + 143 0.0000 7.165461 194.9821 + 144 0.0000 7.200050 195.9233 + 145 0.0000 7.247961 197.2270 + 146 0.0000 7.269763 197.8203 + 147 0.0000 7.312287 198.9775 + 148 0.0000 7.391523 201.1336 + 149 0.0000 7.466701 203.1793 + 150 0.0000 7.503157 204.1713 + 151 0.0000 7.533269 204.9907 + 152 0.0000 7.559975 205.7174 + 153 0.0000 7.678351 208.9386 + 154 0.0000 7.745495 210.7656 + 155 0.0000 7.899168 214.9473 + 156 0.0000 8.099804 220.4069 + 157 0.0000 8.363851 227.5920 + 158 0.0000 14.023295 381.5933 + 159 0.0000 15.094665 410.7467 + 160 0.0000 15.767965 429.0681 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.328886 0.000000 + 1 N : 0.346608 0.000000 + 2 O : -0.270669 0.000000 + 3 H : 0.252946 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.830549 s : 3.830549 + pz : 1.388179 p : 4.461282 + px : 1.606814 + py : 1.466290 + dz2 : 0.008925 d : 0.032254 + dxz : 0.008302 + dyz : 0.005779 + dx2y2 : 0.008060 + dxy : 0.001187 + f0 : 0.001066 f : 0.004801 + f+1 : 0.001113 + f-1 : 0.000619 + f+2 : 0.000738 + f-2 : 0.000747 + f+3 : 0.000319 + f-3 : 0.000200 + 1 N s : 3.837829 s : 3.837829 + pz : 0.759614 p : 2.640872 + px : 0.753418 + py : 1.127840 + dz2 : 0.029886 d : 0.142208 + dxz : 0.032592 + dyz : 0.019596 + dx2y2 : 0.034746 + dxy : 0.025389 + f0 : 0.007210 f : 0.032483 + f+1 : 0.001773 + f-1 : 0.005130 + f+2 : 0.003219 + f-2 : 0.005917 + f+3 : 0.003031 + f-3 : 0.006203 + 2 O s : 3.872645 s : 3.872645 + pz : 1.645968 p : 4.330119 + px : 1.296214 + py : 1.387937 + dz2 : 0.005802 d : 0.060482 + dxz : 0.005426 + dyz : 0.015939 + dx2y2 : 0.020339 + dxy : 0.012976 + f0 : 0.000924 f : 0.007422 + f+1 : 0.000504 + f-1 : 0.000966 + f+2 : 0.000271 + f-2 : 0.001182 + f+3 : 0.001471 + f-3 : 0.002104 + 3 H s : 0.638317 s : 0.638317 + pz : 0.025447 p : 0.087779 + px : 0.038135 + py : 0.024197 + dz2 : 0.001028 d : 0.020958 + dxz : 0.000905 + dyz : 0.008125 + dx2y2 : 0.005778 + dxy : 0.005122 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.587476 0.000000 + 1 N : -0.268561 0.000000 + 2 O : 0.243635 0.000000 + 3 H : -0.562550 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.117218 s : 3.117218 + pz : 1.265593 p : 3.926707 + px : 1.331306 + py : 1.329808 + dz2 : 0.067289 d : 0.282876 + dxz : 0.082561 + dyz : 0.055669 + dx2y2 : 0.032147 + dxy : 0.045210 + f0 : 0.011715 f : 0.085722 + f+1 : 0.018987 + f-1 : 0.014668 + f+2 : 0.013418 + f-2 : 0.017487 + f+3 : 0.006275 + f-3 : 0.003171 + 1 N s : 3.015685 s : 3.015685 + pz : 0.822346 p : 2.836512 + px : 0.815772 + py : 1.198393 + dz2 : 0.199528 d : 0.956315 + dxz : 0.219183 + dyz : 0.151431 + dx2y2 : 0.197647 + dxy : 0.188526 + f0 : 0.081897 f : 0.460049 + f+1 : 0.051467 + f-1 : 0.060150 + f+2 : 0.038172 + f-2 : 0.090591 + f+3 : 0.062950 + f-3 : 0.074823 + 2 O s : 3.309665 s : 3.309665 + pz : 1.365146 p : 4.007683 + px : 1.228980 + py : 1.413557 + dz2 : 0.050340 d : 0.323025 + dxz : 0.051548 + dyz : 0.041596 + dx2y2 : 0.084394 + dxy : 0.095148 + f0 : 0.010062 f : 0.115992 + f+1 : 0.009445 + f-1 : 0.017989 + f+2 : 0.005338 + f-2 : 0.020907 + f+3 : 0.029158 + f-3 : 0.023093 + 3 H s : 0.616006 s : 0.616006 + pz : 0.142044 p : 0.553782 + px : 0.164355 + py : 0.247383 + dz2 : 0.033420 d : 0.392763 + dxz : 0.042004 + dyz : 0.100460 + dx2y2 : 0.114399 + dxy : 0.102479 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3289 8.0000 -0.3289 1.8154 1.8154 -0.0000 + 1 N 6.6534 7.0000 0.3466 2.5463 2.5463 0.0000 + 2 O 8.2707 8.0000 -0.2707 1.7397 1.7397 -0.0000 + 3 H 0.7471 1.0000 0.2529 1.0072 1.0072 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8123 B( 0-O , 3-H ) : 0.9436 B( 1-N , 2-O ) : 1.6754 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.583 sec +Sum of individual times .... 2.312 sec ( 89.5%) + +Fock matrix formation .... 1.880 sec ( 72.8%) +Diagonalization .... 0.185 sec ( 7.2%) +Density matrix formation .... 0.014 sec ( 0.5%) +Population analysis .... 0.063 sec ( 2.4%) +Initial guess .... 0.010 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.006 sec ( 0.2%) +DIIS solution .... 0.160 sec ( 6.2%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.205 sec +Reference energy ... -204.712975375 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.360 sec +AO-integral generation ... 0.144 sec +Half transformation ... 0.080 sec +K-integral sorting ... 5.368 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.024 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.038 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.037 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.031 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.023 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.040 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.024 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.358 sec +AO-integral generation ... 0.254 sec +Half transformation ... 0.043 sec +J-integral sorting ... 0.048 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.157 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.246 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090173271 +EMP2(bb)= -0.090173271 +EMP2(ab)= -0.515560240 + +Initial guess performed in 0.132 sec +E(0) ... -204.712975375 +E(MP2) ... -0.695906782 +Initial E(tot) ... -205.408882158 + ... 0.187328500 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.408882158 -0.695906782 -0.000000000 0.023386269 3.01 0.000002461 + *** Turning on DIIS *** + 1 -205.380764340 -0.667788965 0.028117817 0.009339304 3.04 0.056667475 + 2 -205.400108263 -0.687132887 -0.019343922 0.005100158 3.06 0.059884462 + 3 -205.403862404 -0.690887028 -0.003754141 0.001704689 3.05 0.073824190 + 4 -205.405422932 -0.692447557 -0.001560529 0.001429466 3.09 0.080476947 + 5 -205.405960790 -0.692985414 -0.000537858 0.000870907 3.13 0.085843470 + 6 -205.406065902 -0.693090526 -0.000105112 0.000534548 3.11 0.088540856 + 7 -205.406110727 -0.693135352 -0.000044825 0.000257359 3.16 0.089806017 + 8 -205.406121826 -0.693146450 -0.000011099 0.000119274 3.14 0.090350352 + 9 -205.406118213 -0.693142837 0.000003613 0.000062176 2.99 0.090530762 + 10 -205.406123371 -0.693147995 -0.000005158 0.000037012 3.08 0.090601489 + 11 -205.406120207 -0.693144832 0.000003164 0.000026138 3.18 0.090592741 + 12 -205.406122015 -0.693146640 -0.000001808 0.000016492 3.06 0.090609609 + 13 -205.406121773 -0.693146398 0.000000242 0.000009351 3.12 0.090605266 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.712975375 +E(CORR) ... -0.693146398 +E(TOT) ... -205.406121773 +Singles norm **1/2 ... 0.090605266 ( 0.045302633, 0.045302633) +T1 diagnostic ... 0.021355866 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.054352 + 9a-> 13a 9b-> 13b 0.044485 + 8b-> 13b -1b-> -1b 0.038126 + 8a-> 13a -1a-> -1a 0.038126 + 9a-> 13a 8b-> 13b 0.035292 + 8a-> 13a 9b-> 13b 0.035292 + 11a-> 13a 11b-> 13b 0.030913 + 10a-> 13a 10b-> 13b 0.028271 + 10a-> 13a -1a-> -1a 0.027953 + 10b-> 13b -1b-> -1b 0.027953 + 5a-> 13a 5b-> 13b 0.027198 + 9a-> 13a 10b-> 13b 0.026478 + 10a-> 13a 9b-> 13b 0.026478 + 8a-> 13a 10b-> 13b 0.023200 + 10a-> 13a 8b-> 13b 0.023200 + 8a-> 13a 8b-> 22b 0.020026 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034422841 + alpha-alpha-alpha ... -0.000887009 ( 2.6%) + alpha-alpha-beta ... -0.016324412 ( 47.4%) + alpha-beta -beta ... -0.016324412 ( 47.4%) + beta -beta -beta ... -0.000887009 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034422841 + +Final correlation energy ... -0.727569239 +E(CCSD) ... -205.406121773 +E(CCSD(T)) ... -205.440544615 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209415465 sqrt= 1.099734270 +W(HF) = 0.826845720 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.254759 0.000000 + 1 N : 0.162678 -0.000000 + 2 O : -0.147839 -0.000000 + 3 H : 0.239919 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.813563 s : 3.813563 + pz : 1.360117 p : 4.370157 + px : 1.570755 + py : 1.439285 + dz2 : 0.014902 d : 0.062563 + dxz : 0.012934 + dyz : 0.012752 + dx2y2 : 0.013912 + dxy : 0.008062 + f0 : 0.001655 f : 0.008476 + f+1 : 0.001335 + f-1 : 0.001190 + f+2 : 0.001204 + f-2 : 0.001262 + f+3 : 0.000976 + f-3 : 0.000853 + 1 N s : 3.891856 s : 3.891856 + pz : 0.814523 p : 2.742632 + px : 0.828694 + py : 1.099415 + dz2 : 0.037773 d : 0.171386 + dxz : 0.039751 + dyz : 0.024917 + dx2y2 : 0.039627 + dxy : 0.029318 + f0 : 0.006742 f : 0.031449 + f+1 : 0.001741 + f-1 : 0.005290 + f+2 : 0.003268 + f-2 : 0.005735 + f+3 : 0.003189 + f-3 : 0.005484 + 2 O s : 3.859135 s : 3.859135 + pz : 1.577833 p : 4.196177 + px : 1.261234 + py : 1.357111 + dz2 : 0.011246 d : 0.082576 + dxz : 0.011950 + dyz : 0.019766 + dx2y2 : 0.024400 + dxy : 0.015214 + f0 : 0.001364 f : 0.009950 + f+1 : 0.000977 + f-1 : 0.001374 + f+2 : 0.000808 + f-2 : 0.001547 + f+3 : 0.001724 + f-3 : 0.002156 + 3 H s : 0.649868 s : 0.649868 + pz : 0.029449 p : 0.091621 + px : 0.041490 + py : 0.020683 + dz2 : 0.000824 d : 0.018591 + dxz : 0.001138 + dyz : 0.007293 + dx2y2 : 0.004817 + dxy : 0.004518 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.598727 0.000000 + 1 N : -0.314607 -0.000000 + 2 O : 0.282335 -0.000000 + 3 H : -0.566454 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.124110 s : 3.124110 + pz : 1.250230 p : 3.869998 + px : 1.308684 + py : 1.311085 + dz2 : 0.073704 d : 0.314226 + dxz : 0.089130 + dyz : 0.060639 + dx2y2 : 0.038318 + dxy : 0.052434 + f0 : 0.013734 f : 0.092939 + f+1 : 0.020510 + f-1 : 0.015011 + f+2 : 0.014355 + f-2 : 0.018119 + f+3 : 0.007136 + f-3 : 0.004073 + 1 N s : 3.021254 s : 3.021254 + pz : 0.848110 p : 2.881264 + px : 0.860181 + py : 1.172973 + dz2 : 0.203278 d : 0.962746 + dxz : 0.224713 + dyz : 0.145515 + dx2y2 : 0.194333 + dxy : 0.194907 + f0 : 0.077983 f : 0.449344 + f+1 : 0.051969 + f-1 : 0.059432 + f+2 : 0.037285 + f-2 : 0.087843 + f+3 : 0.062408 + f-3 : 0.072425 + 2 O s : 3.311929 s : 3.311929 + pz : 1.324354 p : 3.926859 + px : 1.208355 + py : 1.394150 + dz2 : 0.056611 d : 0.354346 + dxz : 0.056361 + dyz : 0.048306 + dx2y2 : 0.092541 + dxy : 0.100527 + f0 : 0.011047 f : 0.124531 + f+1 : 0.010640 + f-1 : 0.018204 + f+2 : 0.006724 + f-2 : 0.021711 + f+3 : 0.029658 + f-3 : 0.026548 + 3 H s : 0.618989 s : 0.618989 + pz : 0.143375 p : 0.564922 + px : 0.168411 + py : 0.253136 + dz2 : 0.033355 d : 0.382543 + dxz : 0.040645 + dyz : 0.097369 + dx2y2 : 0.111344 + dxy : 0.099831 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2548 8.0000 -0.2548 2.1801 1.7282 0.4519 + 1 N 6.8373 7.0000 0.1627 2.8227 2.3412 0.4815 + 2 O 8.1478 8.0000 -0.1478 2.1319 1.6322 0.4997 + 3 H 0.7601 1.0000 0.2399 1.0248 0.9506 0.0742 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7548 B( 0-O , 3-H ) : 0.8761 B( 1-N , 2-O ) : 1.5234 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 58.723 sec + +Fock Matrix Formation ... 0.205 sec ( 0.3%) +Initial Guess ... 0.132 sec ( 0.2%) +DIIS Solver ... 2.062 sec ( 3.5%) +State Vector Update ... 0.096 sec ( 0.2%) +Sigma-vector construction ... 41.043 sec ( 69.9%) + <0|H|D> ... 0.005 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.028 sec ( 0.1% of sigma) + (0-ext) ... 0.075 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (2-ext) ... 0.968 sec ( 2.4% of sigma) + (4-ext) ... 24.006 sec ( 58.5% of sigma) + ... 1.323 sec ( 3.2% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.108 sec ( 0.3% of sigma) + Fock-dressing ... 2.125 sec ( 5.2% of sigma) + (ik|jl)-dressing ... 0.083 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.733 sec ( 23.7% of sigma) + Pair energies ... 0.006 sec ( 0.0% of sigma) +Total Time for computing (T) ... 7.150 sec ( 12.2% of ALL) + I/O of integral and amplitudes ... 0.909 sec ( 12.7% of (T)) + External N**7 contributions ... 3.987 sec ( 55.8% of (T)) + Internal N**7 contributions ... 0.333 sec ( 4.7% of (T)) + N**6 triples energy contributions ... 1.831 sec ( 25.6% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.440544614586 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.014136749 0.000578136 0.005366478 + 2 N : -0.013726701 0.002124299 -0.004097976 + 3 O : 0.008391432 -0.000855553 0.004255780 + 4 H : -0.008801480 -0.001846882 -0.005524283 + +Norm of the cartesian gradient ... 0.025285645 +RMS gradient ... 0.007299337 +MAX gradient ... 0.014136749 + +------- +TIMINGS +------- + +Total numerical gradient time ... 374.980 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: -268.16 cm**-1 ***imaginary mode*** + 7: 629.77 cm**-1 + 8: 826.95 cm**-1 + 9: 1263.41 cm**-1 + 10: 1654.32 cm**-1 + 11: 3657.98 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 0.025973 0.353811 -0.103297 0.018614 -0.026440 -0.025775 + 1 0.025897 0.136079 0.113704 0.066173 0.051804 0.055925 + 2 0.093765 -0.256423 0.202492 -0.052369 0.040289 -0.009108 + 3 -0.026630 -0.174236 0.206487 0.066120 -0.326323 -0.000768 + 4 0.030256 -0.155600 -0.211599 -0.042594 -0.574342 0.000719 + 5 -0.097743 0.016166 -0.358019 -0.045712 0.041777 0.000805 + 6 0.047288 -0.206383 -0.119424 -0.046392 0.329965 0.000537 + 7 -0.025424 0.004753 0.048306 -0.027609 0.451597 0.000049 + 8 0.017315 0.290931 0.131525 0.037785 -0.101554 -0.000468 + 9 -0.792755 0.081184 0.665713 -0.477899 -0.283030 0.411271 + 10 -0.427957 -0.073100 0.368921 -0.020215 -0.009040 -0.898417 + 11 -0.404838 -0.772350 -0.326556 0.866671 0.391887 0.140803 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 7: 629.77 0.007779 39.31 0.003855 (-0.053098 -0.026072 0.018858) + 8: 826.95 0.051293 259.21 0.019356 ( 0.104163 0.001711 -0.092213) + 9: 1263.41 0.001991 10.06 0.000492 (-0.008294 0.015845 0.013112) + 10: 1654.32 0.030220 152.72 0.005700 (-0.055772 -0.018267 0.047500) + 11: 3657.98 0.009925 50.16 0.000847 ( 0.021253 -0.018983 -0.005889) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 7 +The total number of vibrations considered is 5 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 629.77 E(vib) ... 0.09 +freq. 826.95 E(vib) ... 0.04 +freq. 1263.41 E(vib) ... 0.01 +freq. 1654.32 E(vib) ... 0.00 +freq. 3657.98 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.44054462 Eh +Zero point energy ... 0.01829922 Eh 11.48 kcal/mol +Thermal vibrational correction ... 0.00023085 Eh 0.14 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.41918201 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00306339 Eh 1.92 kcal/mol +Non-thermal (ZPE) correction 0.01829922 Eh 11.48 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02136261 Eh 13.41 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.41918201 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.41823780 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.752639 0.420504 0.371576 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00029749 Eh 0.19 kcal/mol +Rotational entropy ... 0.00990913 Eh 6.22 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02800894 Eh 17.58 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00990913 Eh 6.22 kcal/mol| +| sn= 2 | S(rot)= 0.00925468 Eh 5.81 kcal/mol| +| sn= 3 | S(rot)= 0.00887184 Eh 5.57 kcal/mol| +| sn= 4 | S(rot)= 0.00860022 Eh 5.40 kcal/mol| +| sn= 5 | S(rot)= 0.00838953 Eh 5.26 kcal/mol| +| sn= 6 | S(rot)= 0.00821739 Eh 5.16 kcal/mol| +| sn= 7 | S(rot)= 0.00807184 Eh 5.07 kcal/mol| +| sn= 8 | S(rot)= 0.00794576 Eh 4.99 kcal/mol| +| sn= 9 | S(rot)= 0.00783456 Eh 4.92 kcal/mol| +| sn=10 | S(rot)= 0.00773508 Eh 4.85 kcal/mol| +| sn=11 | S(rot)= 0.00764509 Eh 4.80 kcal/mol| +| sn=12 | S(rot)= 0.00756293 Eh 4.75 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.41823780 Eh +Total entropy correction ... -0.02800894 Eh -17.58 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44624674 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00570212 Eh -3.58 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.440544617 Eh +Current gradient norm .... 0.025285646 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + -0.009251039 0.123803480 0.198872952 0.475544457 0.515156010 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999628171 +Lowest eigenvalues of augmented Hessian: + -0.000129604 0.118243079 0.197955119 0.475421629 0.514771212 +Length of the computed step .... 0.027277714 +The final length of the internal step .... 0.027277714 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0111360802 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0064272867 RMS(Int)= 0.0111375699 + Iter 1: RMS(Cart)= 0.0000070399 RMS(Int)= 0.0000105627 + Iter 2: RMS(Cart)= 0.0000000181 RMS(Int)= 0.0000000303 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0022875232 0.0001000000 NO + MAX gradient 0.0034012532 0.0003000000 NO + RMS step 0.0111360802 0.0020000000 NO + MAX step 0.0252728468 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0134 Max(Angles) 0.08 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4386 -0.003336 0.0134 1.4520 + 2. B(O 2,N 1) 1.1800 0.003401 -0.0043 1.1757 + 3. B(H 3,O 0) 0.9754 0.002765 -0.0032 0.9722 + 4. A(N 1,O 0,H 3) 104.86 -0.001000 0.03 104.88 + 5. A(O 0,N 1,O 2) 112.79 0.000232 -0.08 112.71 + 6. D(O 2,N 1,O 0,H 3) 49.09 0.018121 0.00 49.09 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.484708 -0.330080 0.687024 + N 0.335422 -0.562717 -0.488345 + O 1.033806 0.348363 -0.742116 + H -0.884519 0.544434 0.543438 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.915965 -0.623760 1.298287 + 1 N 7.0000 0 14.007 0.633856 -1.063382 -0.922838 + 2 O 8.0000 0 15.999 1.953610 0.658310 -1.402397 + 3 H 1.0000 0 1.008 -1.671499 1.028832 1.026948 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.451972644741 0.00000000 0.00000000 + O 2 1 0 1.175672857364 112.71200058 0.00000000 + H 1 2 3 0.972235035765 104.88287914 49.09090930 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.743830652506 0.00000000 0.00000000 + O 2 1 0 2.221699723503 112.71200058 0.00000000 + H 1 2 3 1.837257955399 104.88287914 49.09090930 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2237 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2709 + la=0 lb=0: 554 shell pairs + la=1 lb=0: 538 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.146354146294 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.604e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7125471033 0.000000000000 0.00038424 0.00001071 0.0019183 0.7000 + 1 -204.7125764704 -0.000029367134 0.00031607 0.00000911 0.0015104 0.7000 + ***Turning on DIIS*** + 2 -204.7126009139 -0.000024443458 0.00081013 0.00002394 0.0011802 0.0000 + 3 -204.7122544389 0.000346474992 0.00032811 0.00001164 0.0003934 0.0000 + 4 -204.7127258426 -0.000471403664 0.00014471 0.00000428 0.0001350 0.0000 + 5 -204.7127844491 -0.000058606578 0.00004876 0.00000135 0.0000979 0.0000 + 6 -204.7126438608 0.000140588319 0.00003645 0.00000088 0.0000564 0.0000 + 7 -204.7126989133 -0.000055052499 0.00001128 0.00000033 0.0000124 0.0000 + 8 -204.7126728359 0.000026077445 0.00000696 0.00000019 0.0000068 0.0000 + 9 -204.7126854562 -0.000012620335 0.00000403 0.00000012 0.0000033 0.0000 + 10 -204.7126821067 0.000003349481 0.00000216 0.00000007 0.0000015 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + +Total Energy : -204.71267865 Eh -5570.51519 eV + Last Energy change ... 3.4614e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.2085e-06 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.206 sec +Reference energy ... -204.712682253 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.354 sec +AO-integral generation ... 0.143 sec +Half transformation ... 0.079 sec +K-integral sorting ... 5.357 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.025 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.036 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.347 sec +AO-integral generation ... 0.242 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.162 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.251 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090188435 +EMP2(bb)= -0.090188435 +EMP2(ab)= -0.515860830 + +Initial guess performed in 0.133 sec +E(0) ... -204.712682253 +E(MP2) ... -0.696237700 +Initial E(tot) ... -205.408919952 + ... 0.187711364 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.408919952 -0.696237700 -0.000000000 0.023133480 2.74 0.000002099 + *** Turning on DIIS *** + 1 -205.380635968 -0.667953715 0.028283985 0.009635536 2.87 0.056877174 + 2 -205.400045284 -0.687363031 -0.019409316 0.005008348 2.81 0.060010764 + 3 -205.403809550 -0.691127297 -0.003764266 0.001793862 2.88 0.074011474 + 4 -205.405375384 -0.692693131 -0.001565834 0.001505833 2.82 0.080686343 + 5 -205.405919863 -0.693237610 -0.000544479 0.000910595 2.84 0.086147921 + 6 -205.406027839 -0.693345586 -0.000107976 0.000556892 2.80 0.088948066 + 7 -205.406074829 -0.693392576 -0.000046990 0.000262807 2.84 0.090293144 + 8 -205.406086782 -0.693404529 -0.000011953 0.000122696 2.89 0.090867155 + 9 -205.406082949 -0.693400696 0.000003833 0.000061972 2.81 0.091051551 + 10 -205.406088421 -0.693406168 -0.000005472 0.000037240 2.79 0.091126892 + 11 -205.406085152 -0.693402900 0.000003268 0.000026307 2.77 0.091116968 + 12 -205.406086911 -0.693404658 -0.000001759 0.000016684 2.79 0.091135010 + 13 -205.406086711 -0.693404458 0.000000201 0.000009628 2.83 0.091130320 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.712682253 +E(CORR) ... -0.693404458 +E(TOT) ... -205.406086711 +Singles norm **1/2 ... 0.091130320 ( 0.045565160, 0.045565160) +T1 diagnostic ... 0.021479622 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.056656 + 9a-> 13a 9b-> 13b 0.043511 + 8b-> 13b -1b-> -1b 0.037411 + 8a-> 13a -1a-> -1a 0.037411 + 8a-> 13a 9b-> 13b 0.035923 + 9a-> 13a 8b-> 13b 0.035923 + 11a-> 13a 11b-> 13b 0.030345 + 10b-> 13b -1b-> -1b 0.029858 + 10a-> 13a -1a-> -1a 0.029858 + 5a-> 13a 5b-> 13b 0.027646 + 10a-> 13a 10b-> 13b 0.026173 + 10a-> 13a 9b-> 13b 0.024881 + 9a-> 13a 10b-> 13b 0.024881 + 8a-> 13a 10b-> 13b 0.022650 + 10a-> 13a 8b-> 13b 0.022650 + 11a-> 25a 11b-> 25b 0.022534 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034524492 + alpha-alpha-alpha ... -0.000887457 ( 2.6%) + alpha-alpha-beta ... -0.016374789 ( 47.4%) + alpha-beta -beta ... -0.016374789 ( 47.4%) + beta -beta -beta ... -0.000887457 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034524492 + +Final correlation energy ... -0.727928950 +E(CCSD) ... -205.406086711 +E(CCSD(T)) ... -205.440611203 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209998762 sqrt= 1.099999437 +W(HF) = 0.826447127 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 54.488 sec + +Fock Matrix Formation ... 0.206 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 1.630 sec ( 3.0%) +State Vector Update ... 0.084 sec ( 0.2%) +Sigma-vector construction ... 37.769 sec ( 69.3%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.024 sec ( 0.1% of sigma) + (0-ext) ... 0.068 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.025 sec ( 0.1% of sigma) + (2-ext) ... 0.928 sec ( 2.5% of sigma) + (4-ext) ... 20.994 sec ( 55.6% of sigma) + ... 1.310 sec ( 3.5% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.106 sec ( 0.3% of sigma) + Fock-dressing ... 2.118 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.073 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.555 sec ( 25.3% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.762 sec ( 12.4% of ALL) + I/O of integral and amplitudes ... 0.725 sec ( 10.7% of (T)) + External N**7 contributions ... 3.916 sec ( 57.9% of (T)) + Internal N**7 contributions ... 0.310 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.620 sec ( 24.0% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.440611202800 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.010909111 0.003876973 0.006601468 + 2 N : -0.009353777 0.003692165 -0.007027972 + 3 O : 0.006024676 -0.003346524 0.004903114 + 4 H : -0.007580009 -0.004222614 -0.004476610 + +Norm of the cartesian gradient ... 0.022248598 +RMS gradient ... 0.006422617 +MAX gradient ... 0.010909111 + +------- +TIMINGS +------- + +Total numerical gradient time ... 356.257 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.440611203 Eh +Current gradient norm .... 0.022248598 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999998922 +Lowest eigenvalues of augmented Hessian: + -0.000000298 0.114493046 0.194055709 0.477282558 0.516259412 +Length of the computed step .... 0.001468260 +The final length of the internal step .... 0.001468260 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0005994145 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0003424654 RMS(Int)= 0.0005994161 + Iter 1: RMS(Cart)= 0.0000000137 RMS(Int)= 0.0000000233 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000665862 0.0000050000 NO + RMS gradient 0.0000939090 0.0001000000 YES + MAX gradient 0.0002158068 0.0003000000 YES + RMS step 0.0005994145 0.0020000000 YES + MAX step 0.0014477895 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0008 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4520 -0.000216 0.0008 1.4527 + 2. B(O 2,N 1) 1.1757 -0.000072 -0.0001 1.1756 + 3. B(H 3,O 0) 0.9722 -0.000020 0.0000 0.9722 + 4. A(N 1,O 0,H 3) 104.88 -0.000025 -0.01 104.87 + 5. A(O 0,N 1,O 2) 112.71 -0.000006 -0.01 112.71 + 6. D(O 2,N 1,O 0,H 3) 49.09 0.017335 -0.00 49.09 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.484948 -0.330049 0.687319 + N 0.335675 -0.562769 -0.488636 + O 1.033968 0.348336 -0.742255 + H -0.884694 0.544482 0.543573 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.916419 -0.623703 1.298844 + 1 N 7.0000 0 14.007 0.634334 -1.063478 -0.923389 + 2 O 8.0000 0 15.999 1.953916 0.658259 -1.402659 + 3 H 1.0000 0 1.008 -1.671829 1.028922 1.027203 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.452738781927 0.00000000 0.00000000 + O 2 1 0 1.175604895331 112.70653084 0.00000000 + H 1 2 3 0.972247279578 104.87238466 49.09090930 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.745278441969 0.00000000 0.00000000 + O 2 1 0 2.221571293872 112.70653084 0.00000000 + H 1 2 3 1.837281092853 104.87238466 49.09090930 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2237 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2709 + la=0 lb=0: 554 shell pairs + la=1 lb=0: 538 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.132282200132 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.1322822001 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.606e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7126222720 0.000000000000 0.00002254 0.00000056 0.0001068 0.7000 + 1 -204.7126223419 -0.000000069914 0.00001857 0.00000047 0.0000829 0.7000 + ***Turning on DIIS*** + 2 -204.7126224004 -0.000000058427 0.00004833 0.00000125 0.0000638 0.0000 + 3 -204.7126359110 -0.000013510606 0.00001661 0.00000055 0.0000167 0.0000 + 4 -204.7126131458 0.000022765132 0.00000698 0.00000018 0.0000052 0.0000 + 5 -204.7126218358 -0.000008689983 0.00000234 0.00000006 0.0000019 0.0000 + 6 -204.7126281141 -0.000006278260 0.00000111 0.00000002 0.0000017 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71262233 Eh -5570.51365 eV + +Components: +Nuclear Repulsion : 69.13228220 Eh 1881.18504 eV +Electronic Energy : -273.84490453 Eh -7451.69869 eV +One Electron Energy: -417.91051284 Eh -11371.92319 eV +Two Electron Energy: 144.06560830 Eh 3920.22450 eV + +Virial components: +Potential Energy : -408.94905474 Eh -11128.06952 eV +Kinetic Energy : 204.23643241 Eh 5557.55587 eV +Virial Ratio : 2.00233156 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 5.7817e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.5329e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 9.5596e-09 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.8739e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.680664 -562.7495 + 1 1.0000 -20.631638 -561.4154 + 2 1.0000 -15.804052 -430.0501 + 3 1.0000 -1.611132 -43.8411 + 4 1.0000 -1.389815 -37.8188 + 5 1.0000 -0.960584 -26.1388 + 6 1.0000 -0.772264 -21.0144 + 7 1.0000 -0.737408 -20.0659 + 8 1.0000 -0.695883 -18.9359 + 9 1.0000 -0.605165 -16.4674 + 10 1.0000 -0.533784 -14.5250 + 11 1.0000 -0.467257 -12.7147 + 12 0.0000 0.031004 0.8437 + 13 0.0000 0.069216 1.8835 + 14 0.0000 0.093667 2.5488 + 15 0.0000 0.109701 2.9851 + 16 0.0000 0.115325 3.1382 + 17 0.0000 0.153187 4.1684 + 18 0.0000 0.157155 4.2764 + 19 0.0000 0.171308 4.6615 + 20 0.0000 0.180391 4.9087 + 21 0.0000 0.192366 5.2345 + 22 0.0000 0.202924 5.5218 + 23 0.0000 0.234603 6.3839 + 24 0.0000 0.266342 7.2475 + 25 0.0000 0.290171 7.8960 + 26 0.0000 0.310247 8.4422 + 27 0.0000 0.337789 9.1917 + 28 0.0000 0.343666 9.3516 + 29 0.0000 0.370085 10.0705 + 30 0.0000 0.421925 11.4812 + 31 0.0000 0.513977 13.9860 + 32 0.0000 0.531171 14.4539 + 33 0.0000 0.534856 14.5542 + 34 0.0000 0.561764 15.2864 + 35 0.0000 0.607741 16.5375 + 36 0.0000 0.634299 17.2601 + 37 0.0000 0.647707 17.6250 + 38 0.0000 0.696148 18.9431 + 39 0.0000 0.710742 19.3403 + 40 0.0000 0.734584 19.9890 + 41 0.0000 0.741243 20.1703 + 42 0.0000 0.767868 20.8947 + 43 0.0000 0.782801 21.3011 + 44 0.0000 0.814131 22.1536 + 45 0.0000 0.828767 22.5519 + 46 0.0000 0.850729 23.1495 + 47 0.0000 0.881570 23.9887 + 48 0.0000 0.915846 24.9214 + 49 0.0000 0.942497 25.6466 + 50 0.0000 0.973206 26.4823 + 51 0.0000 0.979111 26.6430 + 52 0.0000 1.008294 27.4371 + 53 0.0000 1.019212 27.7342 + 54 0.0000 1.055504 28.7217 + 55 0.0000 1.087549 29.5937 + 56 0.0000 1.161117 31.5956 + 57 0.0000 1.203871 32.7590 + 58 0.0000 1.231022 33.4978 + 59 0.0000 1.280063 34.8323 + 60 0.0000 1.349671 36.7264 + 61 0.0000 1.412291 38.4304 + 62 0.0000 1.449035 39.4303 + 63 0.0000 1.518073 41.3089 + 64 0.0000 1.540775 41.9266 + 65 0.0000 1.551312 42.2133 + 66 0.0000 1.612869 43.8884 + 67 0.0000 1.632929 44.4343 + 68 0.0000 1.654101 45.0104 + 69 0.0000 1.729933 47.0739 + 70 0.0000 1.761576 47.9349 + 71 0.0000 1.794783 48.8385 + 72 0.0000 1.913476 52.0683 + 73 0.0000 1.958616 53.2967 + 74 0.0000 1.969839 53.6020 + 75 0.0000 2.007247 54.6200 + 76 0.0000 2.047891 55.7259 + 77 0.0000 2.076161 56.4952 + 78 0.0000 2.157795 58.7166 + 79 0.0000 2.172910 59.1279 + 80 0.0000 2.252321 61.2888 + 81 0.0000 2.307547 62.7915 + 82 0.0000 2.343231 63.7626 + 83 0.0000 2.389515 65.0220 + 84 0.0000 2.419754 65.8448 + 85 0.0000 2.452235 66.7287 + 86 0.0000 2.471744 67.2596 + 87 0.0000 2.495923 67.9175 + 88 0.0000 2.521939 68.6254 + 89 0.0000 2.554907 69.5225 + 90 0.0000 2.577577 70.1394 + 91 0.0000 2.612585 71.0920 + 92 0.0000 2.655592 72.2623 + 93 0.0000 2.692676 73.2714 + 94 0.0000 2.767767 75.3148 + 95 0.0000 2.808055 76.4111 + 96 0.0000 2.824746 76.8652 + 97 0.0000 2.930453 79.7417 + 98 0.0000 2.971239 80.8515 + 99 0.0000 2.997782 81.5738 + 100 0.0000 3.130708 85.1909 + 101 0.0000 3.170507 86.2739 + 102 0.0000 3.228734 87.8583 + 103 0.0000 3.505934 95.4013 + 104 0.0000 3.691456 100.4496 + 105 0.0000 3.872609 105.3790 + 106 0.0000 4.020685 109.4084 + 107 0.0000 4.155824 113.0857 + 108 0.0000 4.192113 114.0732 + 109 0.0000 4.336941 118.0142 + 110 0.0000 4.365167 118.7822 + 111 0.0000 4.387707 119.3956 + 112 0.0000 4.542259 123.6011 + 113 0.0000 4.600730 125.1922 + 114 0.0000 4.674592 127.2021 + 115 0.0000 4.773564 129.8953 + 116 0.0000 4.812125 130.9446 + 117 0.0000 4.869062 132.4939 + 118 0.0000 4.961461 135.0082 + 119 0.0000 4.992419 135.8506 + 120 0.0000 5.068795 137.9289 + 121 0.0000 5.107084 138.9708 + 122 0.0000 5.183518 141.0507 + 123 0.0000 5.228529 142.2755 + 124 0.0000 5.249861 142.8560 + 125 0.0000 5.279606 143.6654 + 126 0.0000 5.384842 146.5290 + 127 0.0000 5.473633 148.9451 + 128 0.0000 5.526247 150.3768 + 129 0.0000 5.702354 155.1689 + 130 0.0000 5.769148 156.9865 + 131 0.0000 5.958671 162.1437 + 132 0.0000 6.161807 167.6713 + 133 0.0000 6.402557 174.2224 + 134 0.0000 6.490073 176.6039 + 135 0.0000 6.521971 177.4718 + 136 0.0000 6.686048 181.9366 + 137 0.0000 6.716241 182.7582 + 138 0.0000 6.780103 184.4960 + 139 0.0000 6.804385 185.1567 + 140 0.0000 6.878319 187.1686 + 141 0.0000 7.089913 192.9263 + 142 0.0000 7.122292 193.8074 + 143 0.0000 7.162861 194.9114 + 144 0.0000 7.206775 196.1063 + 145 0.0000 7.247168 197.2055 + 146 0.0000 7.267802 197.7669 + 147 0.0000 7.320455 199.1997 + 148 0.0000 7.392476 201.1595 + 149 0.0000 7.465119 203.1362 + 150 0.0000 7.494781 203.9433 + 151 0.0000 7.533164 204.9878 + 152 0.0000 7.560725 205.7378 + 153 0.0000 7.671561 208.7538 + 154 0.0000 7.731566 210.3866 + 155 0.0000 7.901240 215.0037 + 156 0.0000 8.080374 219.8781 + 157 0.0000 8.363663 227.5868 + 158 0.0000 14.024743 381.6327 + 159 0.0000 15.065062 409.9412 + 160 0.0000 15.873625 431.9433 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.680664 -562.7495 + 1 1.0000 -20.631638 -561.4154 + 2 1.0000 -15.804052 -430.0501 + 3 1.0000 -1.611132 -43.8411 + 4 1.0000 -1.389815 -37.8188 + 5 1.0000 -0.960584 -26.1388 + 6 1.0000 -0.772264 -21.0144 + 7 1.0000 -0.737408 -20.0659 + 8 1.0000 -0.695883 -18.9359 + 9 1.0000 -0.605165 -16.4674 + 10 1.0000 -0.533784 -14.5250 + 11 1.0000 -0.467257 -12.7147 + 12 0.0000 0.031004 0.8437 + 13 0.0000 0.069216 1.8835 + 14 0.0000 0.093667 2.5488 + 15 0.0000 0.109701 2.9851 + 16 0.0000 0.115325 3.1382 + 17 0.0000 0.153187 4.1684 + 18 0.0000 0.157155 4.2764 + 19 0.0000 0.171308 4.6615 + 20 0.0000 0.180391 4.9087 + 21 0.0000 0.192366 5.2345 + 22 0.0000 0.202924 5.5218 + 23 0.0000 0.234603 6.3839 + 24 0.0000 0.266342 7.2475 + 25 0.0000 0.290171 7.8960 + 26 0.0000 0.310247 8.4422 + 27 0.0000 0.337789 9.1917 + 28 0.0000 0.343666 9.3516 + 29 0.0000 0.370085 10.0705 + 30 0.0000 0.421925 11.4812 + 31 0.0000 0.513977 13.9860 + 32 0.0000 0.531171 14.4539 + 33 0.0000 0.534856 14.5542 + 34 0.0000 0.561764 15.2864 + 35 0.0000 0.607741 16.5375 + 36 0.0000 0.634299 17.2601 + 37 0.0000 0.647707 17.6250 + 38 0.0000 0.696148 18.9431 + 39 0.0000 0.710742 19.3403 + 40 0.0000 0.734584 19.9890 + 41 0.0000 0.741243 20.1703 + 42 0.0000 0.767868 20.8947 + 43 0.0000 0.782801 21.3011 + 44 0.0000 0.814131 22.1536 + 45 0.0000 0.828767 22.5519 + 46 0.0000 0.850729 23.1495 + 47 0.0000 0.881570 23.9887 + 48 0.0000 0.915846 24.9214 + 49 0.0000 0.942497 25.6466 + 50 0.0000 0.973206 26.4823 + 51 0.0000 0.979111 26.6430 + 52 0.0000 1.008294 27.4371 + 53 0.0000 1.019212 27.7342 + 54 0.0000 1.055504 28.7217 + 55 0.0000 1.087549 29.5937 + 56 0.0000 1.161117 31.5956 + 57 0.0000 1.203871 32.7590 + 58 0.0000 1.231022 33.4978 + 59 0.0000 1.280063 34.8323 + 60 0.0000 1.349671 36.7264 + 61 0.0000 1.412291 38.4304 + 62 0.0000 1.449035 39.4303 + 63 0.0000 1.518073 41.3089 + 64 0.0000 1.540775 41.9266 + 65 0.0000 1.551312 42.2133 + 66 0.0000 1.612869 43.8884 + 67 0.0000 1.632929 44.4343 + 68 0.0000 1.654101 45.0104 + 69 0.0000 1.729933 47.0739 + 70 0.0000 1.761576 47.9349 + 71 0.0000 1.794783 48.8385 + 72 0.0000 1.913476 52.0683 + 73 0.0000 1.958616 53.2967 + 74 0.0000 1.969839 53.6020 + 75 0.0000 2.007247 54.6200 + 76 0.0000 2.047891 55.7259 + 77 0.0000 2.076161 56.4952 + 78 0.0000 2.157795 58.7166 + 79 0.0000 2.172910 59.1279 + 80 0.0000 2.252321 61.2888 + 81 0.0000 2.307547 62.7915 + 82 0.0000 2.343231 63.7626 + 83 0.0000 2.389515 65.0220 + 84 0.0000 2.419754 65.8448 + 85 0.0000 2.452235 66.7287 + 86 0.0000 2.471744 67.2596 + 87 0.0000 2.495923 67.9175 + 88 0.0000 2.521939 68.6254 + 89 0.0000 2.554907 69.5225 + 90 0.0000 2.577577 70.1394 + 91 0.0000 2.612585 71.0920 + 92 0.0000 2.655592 72.2623 + 93 0.0000 2.692676 73.2714 + 94 0.0000 2.767767 75.3148 + 95 0.0000 2.808055 76.4111 + 96 0.0000 2.824746 76.8652 + 97 0.0000 2.930453 79.7417 + 98 0.0000 2.971239 80.8515 + 99 0.0000 2.997782 81.5738 + 100 0.0000 3.130708 85.1909 + 101 0.0000 3.170507 86.2739 + 102 0.0000 3.228734 87.8583 + 103 0.0000 3.505934 95.4013 + 104 0.0000 3.691456 100.4496 + 105 0.0000 3.872609 105.3790 + 106 0.0000 4.020685 109.4084 + 107 0.0000 4.155824 113.0857 + 108 0.0000 4.192113 114.0732 + 109 0.0000 4.336941 118.0142 + 110 0.0000 4.365167 118.7822 + 111 0.0000 4.387707 119.3956 + 112 0.0000 4.542259 123.6011 + 113 0.0000 4.600730 125.1922 + 114 0.0000 4.674592 127.2021 + 115 0.0000 4.773564 129.8953 + 116 0.0000 4.812125 130.9446 + 117 0.0000 4.869062 132.4939 + 118 0.0000 4.961461 135.0082 + 119 0.0000 4.992419 135.8506 + 120 0.0000 5.068795 137.9289 + 121 0.0000 5.107084 138.9708 + 122 0.0000 5.183518 141.0507 + 123 0.0000 5.228529 142.2755 + 124 0.0000 5.249861 142.8560 + 125 0.0000 5.279606 143.6654 + 126 0.0000 5.384842 146.5290 + 127 0.0000 5.473633 148.9451 + 128 0.0000 5.526247 150.3768 + 129 0.0000 5.702354 155.1689 + 130 0.0000 5.769148 156.9865 + 131 0.0000 5.958671 162.1437 + 132 0.0000 6.161807 167.6713 + 133 0.0000 6.402557 174.2224 + 134 0.0000 6.490073 176.6039 + 135 0.0000 6.521971 177.4718 + 136 0.0000 6.686048 181.9366 + 137 0.0000 6.716241 182.7582 + 138 0.0000 6.780103 184.4960 + 139 0.0000 6.804385 185.1567 + 140 0.0000 6.878319 187.1686 + 141 0.0000 7.089913 192.9263 + 142 0.0000 7.122292 193.8074 + 143 0.0000 7.162861 194.9114 + 144 0.0000 7.206775 196.1063 + 145 0.0000 7.247168 197.2055 + 146 0.0000 7.267802 197.7669 + 147 0.0000 7.320455 199.1997 + 148 0.0000 7.392476 201.1595 + 149 0.0000 7.465119 203.1362 + 150 0.0000 7.494781 203.9433 + 151 0.0000 7.533164 204.9878 + 152 0.0000 7.560725 205.7378 + 153 0.0000 7.671561 208.7538 + 154 0.0000 7.731566 210.3866 + 155 0.0000 7.901240 215.0037 + 156 0.0000 8.080374 219.8781 + 157 0.0000 8.363663 227.5868 + 158 0.0000 14.024743 381.6327 + 159 0.0000 15.065062 409.9412 + 160 0.0000 15.873625 431.9433 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.335398 0.000000 + 1 N : 0.351097 0.000000 + 2 O : -0.264751 0.000000 + 3 H : 0.249053 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.833270 s : 3.833270 + pz : 1.392342 p : 4.465831 + px : 1.608379 + py : 1.465110 + dz2 : 0.008680 d : 0.031621 + dxz : 0.008318 + dyz : 0.005573 + dx2y2 : 0.007898 + dxy : 0.001152 + f0 : 0.001028 f : 0.004676 + f+1 : 0.001109 + f-1 : 0.000596 + f+2 : 0.000724 + f-2 : 0.000716 + f+3 : 0.000311 + f-3 : 0.000192 + 1 N s : 3.837894 s : 3.837894 + pz : 0.758434 p : 2.637235 + px : 0.754500 + py : 1.124301 + dz2 : 0.029252 d : 0.141568 + dxz : 0.032975 + dyz : 0.019515 + dx2y2 : 0.034670 + dxy : 0.025156 + f0 : 0.007038 f : 0.032205 + f+1 : 0.001783 + f-1 : 0.005073 + f+2 : 0.003187 + f-2 : 0.005926 + f+3 : 0.003034 + f-3 : 0.006165 + 2 O s : 3.871614 s : 3.871614 + pz : 1.640840 p : 4.324162 + px : 1.296552 + py : 1.386770 + dz2 : 0.005835 d : 0.061485 + dxz : 0.005562 + dyz : 0.016206 + dx2y2 : 0.020758 + dxy : 0.013125 + f0 : 0.000939 f : 0.007490 + f+1 : 0.000494 + f-1 : 0.000968 + f+2 : 0.000270 + f-2 : 0.001208 + f+3 : 0.001474 + f-3 : 0.002137 + 3 H s : 0.641408 s : 0.641408 + pz : 0.026032 p : 0.088461 + px : 0.038440 + py : 0.023988 + dz2 : 0.001061 d : 0.021079 + dxz : 0.000888 + dyz : 0.008159 + dx2y2 : 0.005861 + dxy : 0.005109 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.588014 0.000000 + 1 N : -0.259720 0.000000 + 2 O : 0.245408 0.000000 + 3 H : -0.573701 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.120632 s : 3.120632 + pz : 1.265207 p : 3.931685 + px : 1.332974 + py : 1.333505 + dz2 : 0.065584 d : 0.276683 + dxz : 0.081732 + dyz : 0.053729 + dx2y2 : 0.031486 + dxy : 0.044152 + f0 : 0.011206 f : 0.082986 + f+1 : 0.018638 + f-1 : 0.014045 + f+2 : 0.013032 + f-2 : 0.016839 + f+3 : 0.006149 + f-3 : 0.003078 + 1 N s : 3.020615 s : 3.020615 + pz : 0.817600 p : 2.834836 + px : 0.817192 + py : 1.200044 + dz2 : 0.196240 d : 0.948780 + dxz : 0.218320 + dyz : 0.149233 + dx2y2 : 0.197372 + dxy : 0.187614 + f0 : 0.080367 f : 0.455490 + f+1 : 0.050805 + f-1 : 0.059335 + f+2 : 0.037501 + f-2 : 0.089879 + f+3 : 0.062760 + f-3 : 0.074845 + 2 O s : 3.308306 s : 3.308306 + pz : 1.360361 p : 4.004645 + px : 1.229661 + py : 1.414623 + dz2 : 0.050552 d : 0.325231 + dxz : 0.051787 + dyz : 0.041829 + dx2y2 : 0.085160 + dxy : 0.095903 + f0 : 0.010111 f : 0.116410 + f+1 : 0.009427 + f-1 : 0.018005 + f+2 : 0.005319 + f-2 : 0.020897 + f+3 : 0.029371 + f-3 : 0.023278 + 3 H s : 0.619429 s : 0.619429 + pz : 0.144238 p : 0.560041 + px : 0.166466 + py : 0.249338 + dz2 : 0.033420 d : 0.394231 + dxz : 0.041925 + dyz : 0.100868 + dx2y2 : 0.114992 + dxy : 0.103026 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3354 8.0000 -0.3354 1.8194 1.8194 0.0000 + 1 N 6.6489 7.0000 0.3511 2.5515 2.5515 0.0000 + 2 O 8.2648 8.0000 -0.2648 1.7484 1.7484 0.0000 + 3 H 0.7509 1.0000 0.2491 1.0096 1.0096 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8112 B( 0-O , 3-H ) : 0.9475 B( 1-N , 2-O ) : 1.6829 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.326 sec +Sum of individual times .... 1.071 sec ( 80.8%) + +Fock matrix formation .... 0.830 sec ( 62.5%) +Diagonalization .... 0.095 sec ( 7.2%) +Density matrix formation .... 0.007 sec ( 0.5%) +Population analysis .... 0.064 sec ( 4.8%) +Initial guess .... 0.009 sec ( 0.7%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.4%) +DIIS solution .... 0.066 sec ( 5.0%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.206 sec +Reference energy ... -204.712622595 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.375 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.375 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.025 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.034 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.036 s ( 0.000 ms/b) + 159120 b 0 skpd 0.017 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.030 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.347 sec +AO-integral generation ... 0.243 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.049 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.149 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.252 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090194731 +EMP2(bb)= -0.090194731 +EMP2(ab)= -0.515908280 + +Initial guess performed in 0.133 sec +E(0) ... -204.712622595 +E(MP2) ... -0.696297742 +Initial E(tot) ... -205.408920337 + ... 0.187769658 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.408920337 -0.696297742 -0.000000000 0.023127881 2.75 0.000000690 + *** Turning on DIIS *** + 1 -205.380608980 -0.667986385 0.028311357 0.009651821 2.72 0.056903539 + 2 -205.400028248 -0.687405653 -0.019419268 0.005005821 2.80 0.060031153 + 3 -205.403794286 -0.691171691 -0.003766038 0.001798198 2.87 0.074039649 + 4 -205.405361203 -0.692738608 -0.001566917 0.001509727 2.85 0.080718143 + 5 -205.405906409 -0.693283813 -0.000545205 0.000912822 2.87 0.086186871 + 6 -205.406014573 -0.693391977 -0.000108164 0.000558322 2.85 0.088993000 + 7 -205.406061701 -0.693439106 -0.000047129 0.000263356 2.91 0.090342783 + 8 -205.406073711 -0.693451116 -0.000012010 0.000123039 2.92 0.090918763 + 9 -205.406069866 -0.693447270 0.000003846 0.000061930 2.84 0.091103611 + 10 -205.406075361 -0.693452765 -0.000005495 0.000037229 2.79 0.091179236 + 11 -205.406072083 -0.693449488 0.000003278 0.000026302 2.82 0.091169242 + 12 -205.406073842 -0.693451246 -0.000001759 0.000016694 2.98 0.091187339 + 13 -205.406073643 -0.693451047 0.000000199 0.000009650 2.90 0.091182628 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.712622595 +E(CORR) ... -0.693451047 +E(TOT) ... -205.406073643 +Singles norm **1/2 ... 0.091182628 ( 0.045591314, 0.045591314) +T1 diagnostic ... 0.021491951 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.056767 + 9a-> 13a 9b-> 13b 0.043488 + 8b-> 13b -1b-> -1b 0.037393 + 8a-> 13a -1a-> -1a 0.037393 + 9a-> 13a 8b-> 13b 0.035965 + 8a-> 13a 9b-> 13b 0.035965 + 11a-> 13a 11b-> 13b 0.030316 + 10b-> 13b -1b-> -1b 0.029952 + 10a-> 13a -1a-> -1a 0.029952 + 5a-> 13a 5b-> 13b 0.027678 + 10a-> 13a 10b-> 13b 0.026092 + 10a-> 13a 9b-> 13b 0.024822 + 9a-> 13a 10b-> 13b 0.024822 + 11a-> 25a 11b-> 25b 0.022927 + 8a-> 13a 10b-> 13b 0.022632 + 10a-> 13a 8b-> 13b 0.022632 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034537721 + alpha-alpha-alpha ... -0.000887601 ( 2.6%) + alpha-alpha-beta ... -0.016381259 ( 47.4%) + alpha-beta -beta ... -0.016381259 ( 47.4%) + beta -beta -beta ... -0.000887601 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034537721 + +Final correlation energy ... -0.727988768 +E(CCSD) ... -205.406073643 +E(CCSD(T)) ... -205.440611363 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210073902 sqrt= 1.100033591 +W(HF) = 0.826395808 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.262368 -0.000000 + 1 N : 0.167275 0.000000 + 2 O : -0.141689 -0.000000 + 3 H : 0.236781 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.816928 s : 3.816928 + pz : 1.363816 p : 4.375056 + px : 1.572823 + py : 1.438417 + dz2 : 0.014695 d : 0.062015 + dxz : 0.013006 + dyz : 0.012546 + dx2y2 : 0.013750 + dxy : 0.008018 + f0 : 0.001625 f : 0.008368 + f+1 : 0.001329 + f-1 : 0.001172 + f+2 : 0.001189 + f-2 : 0.001238 + f+3 : 0.000969 + f-3 : 0.000846 + 1 N s : 3.891289 s : 3.891289 + pz : 0.814627 p : 2.739636 + px : 0.829218 + py : 1.095791 + dz2 : 0.037184 d : 0.170630 + dxz : 0.039987 + dyz : 0.024849 + dx2y2 : 0.039554 + dxy : 0.029056 + f0 : 0.006587 f : 0.031170 + f+1 : 0.001758 + f-1 : 0.005230 + f+2 : 0.003238 + f-2 : 0.005723 + f+3 : 0.003189 + f-3 : 0.005445 + 2 O s : 3.858378 s : 3.858378 + pz : 1.572073 p : 4.189930 + px : 1.262074 + py : 1.355784 + dz2 : 0.011264 d : 0.083396 + dxz : 0.012071 + dyz : 0.019974 + dx2y2 : 0.024764 + dxy : 0.015323 + f0 : 0.001373 f : 0.009985 + f+1 : 0.000964 + f-1 : 0.001373 + f+2 : 0.000805 + f-2 : 0.001566 + f+3 : 0.001726 + f-3 : 0.002177 + 3 H s : 0.652224 s : 0.652224 + pz : 0.030084 p : 0.092400 + px : 0.041813 + py : 0.020502 + dz2 : 0.000843 d : 0.018595 + dxz : 0.001117 + dyz : 0.007293 + dx2y2 : 0.004869 + dxy : 0.004473 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.599193 0.000000 + 1 N : -0.306199 -0.000000 + 2 O : 0.284045 -0.000000 + 3 H : -0.577040 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.127335 s : 3.127335 + pz : 1.249834 p : 3.875196 + px : 1.310680 + py : 1.314681 + dz2 : 0.071924 d : 0.308103 + dxz : 0.088415 + dyz : 0.058769 + dx2y2 : 0.037674 + dxy : 0.051321 + f0 : 0.013111 f : 0.090173 + f+1 : 0.020200 + f-1 : 0.014416 + f+2 : 0.013992 + f-2 : 0.017475 + f+3 : 0.007013 + f-3 : 0.003966 + 1 N s : 3.026064 s : 3.026064 + pz : 0.844351 p : 2.880020 + px : 0.861233 + py : 1.174435 + dz2 : 0.200145 d : 0.955129 + dxz : 0.223423 + dyz : 0.143417 + dx2y2 : 0.194127 + dxy : 0.194016 + f0 : 0.076529 f : 0.444986 + f+1 : 0.051354 + f-1 : 0.058620 + f+2 : 0.036682 + f-2 : 0.087097 + f+3 : 0.062220 + f-3 : 0.072484 + 2 O s : 3.310546 s : 3.310546 + pz : 1.319356 p : 3.924080 + px : 1.209522 + py : 1.395202 + dz2 : 0.056800 d : 0.356345 + dxz : 0.056537 + dyz : 0.048510 + dx2y2 : 0.093219 + dxy : 0.101279 + f0 : 0.011115 f : 0.124984 + f+1 : 0.010612 + f-1 : 0.018222 + f+2 : 0.006693 + f-2 : 0.021737 + f+3 : 0.029860 + f-3 : 0.026746 + 3 H s : 0.622021 s : 0.622021 + pz : 0.145486 p : 0.571271 + px : 0.170612 + py : 0.255173 + dz2 : 0.033360 d : 0.383748 + dxz : 0.040567 + dyz : 0.097676 + dx2y2 : 0.111852 + dxy : 0.100293 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2624 8.0000 -0.2624 2.1855 1.7304 0.4551 + 1 N 6.8327 7.0000 0.1673 2.8274 2.3448 0.4826 + 2 O 8.1417 8.0000 -0.1417 2.1403 1.6418 0.4985 + 3 H 0.7632 1.0000 0.2368 1.0263 0.9520 0.0743 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7517 B( 0-O , 3-H ) : 0.8796 B( 1-N , 2-O ) : 1.5317 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 55.046 sec + +Fock Matrix Formation ... 0.206 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 1.808 sec ( 3.3%) +State Vector Update ... 0.084 sec ( 0.2%) +Sigma-vector construction ... 37.964 sec ( 69.0%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.024 sec ( 0.1% of sigma) + (0-ext) ... 0.068 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.025 sec ( 0.1% of sigma) + (2-ext) ... 0.925 sec ( 2.4% of sigma) + (4-ext) ... 21.247 sec ( 56.0% of sigma) + ... 1.320 sec ( 3.5% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.109 sec ( 0.3% of sigma) + Fock-dressing ... 2.118 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.074 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.493 sec ( 25.0% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.849 sec ( 12.4% of ALL) + I/O of integral and amplitudes ... 0.654 sec ( 9.6% of (T)) + External N**7 contributions ... 3.885 sec ( 56.7% of (T)) + Internal N**7 contributions ... 0.308 sec ( 4.5% of (T)) + N**6 triples energy contributions ... 1.546 sec ( 22.6% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.440611363079 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.029.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.029.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.506218, -0.283031 -0.288418) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.71511 -0.19687 -0.73528 +Nuclear contribution : -1.08075 0.65376 0.65501 + ----------------------------------------- +Total Dipole Moment : -0.36564 0.45689 -0.08027 + ----------------------------------------- +Magnitude (a.u.) : 0.59066 +Magnitude (Debye) : 1.50135 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.745223 0.417016 0.368682 +Rotational constants in MHz : 82299.716865 12501.822645 11052.798146 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.089138 0.375738 0.446945 +x,y,z [Debye]: 0.226572 0.955049 1.136043 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.506218, -0.283031 -0.288418) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.82015 -0.12139 -0.74553 +Nuclear contribution : -1.08075 0.65376 0.65501 + ----------------------------------------- +Total Dipole Moment : -0.26060 0.53237 -0.09052 + ----------------------------------------- +Magnitude (a.u.) : 0.59960 +Magnitude (Debye) : 1.52407 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.745223 0.417016 0.368682 +Rotational constants in MHz : 82299.716865 12501.822645 11052.798146 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.010039 0.445662 0.401011 +x,y,z [Debye]: -0.025517 1.132784 1.019288 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 30 * + * * + * Dihedral ( 2, 1, 0, 3) : 57.27272727 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0350419601 RMS(Int)= 0.0001909704 + Iter 1: RMS(Cart)= 0.0000468627 RMS(Int)= 0.0000000521 + Iter 2: RMS(Cart)= 0.0000000128 RMS(Int)= 0.0000000000 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4538 0.000000 + 2. B(O 2,N 1) 1.1771 0.000000 + 3. B(H 3,O 0) 0.9744 0.000000 + 4. A(N 1,O 0,H 3) 104.7041 0.000000 + 5. A(O 0,N 1,O 2) 112.5597 0.000000 + 6. D(O 2,N 1,O 0,H 3) 57.2727 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.460043 -0.315919 0.701689 + N 0.315749 -0.547590 -0.505758 + O 1.060799 0.333141 -0.739754 + H -0.916504 0.530367 0.543823 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.869355 -0.597000 1.326000 + 1 N 7.0000 0 14.007 0.596679 -1.034794 -0.955744 + 2 O 8.0000 0 15.999 2.004620 0.629546 -1.397933 + 3 H 1.0000 0 1.008 -1.731942 1.002248 1.027677 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.452738781927 0.00000000 0.00000000 + O 2 1 0 1.175604895331 112.70653084 0.00000000 + H 1 2 3 0.972247279578 104.87238466 49.09090930 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.745278441969 0.00000000 0.00000000 + O 2 1 0 2.221571293872 112.70653084 0.00000000 + H 1 2 3 1.837281092853 104.87238466 49.09090930 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2235 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2706 + la=0 lb=0: 553 shell pairs + la=1 lb=0: 537 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.037595992617 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.0375959926 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.643e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7062341831 0.000000000000 0.00153952 0.00004983 0.0155325 0.7000 + 1 -204.7070106769 -0.000776493871 0.00141754 0.00004635 0.0129176 0.7000 + ***Turning on DIIS*** + 2 -204.7076850812 -0.000674404236 0.00389832 0.00012873 0.0105547 0.0000 + 3 -204.7108599462 -0.003174865022 0.00183222 0.00006116 0.0044415 0.0000 + 4 -204.7091559973 0.001703948905 0.00088553 0.00003302 0.0017914 0.0000 + 5 -204.7109678150 -0.001811817749 0.00100773 0.00003988 0.0009302 0.0000 + 6 -204.7103921343 0.000575680707 0.00058834 0.00002598 0.0007989 0.0000 + 7 -204.7097941854 0.000597948952 0.00041405 0.00001629 0.0003769 0.0000 + 8 -204.7107929050 -0.000998719668 0.00024942 0.00001037 0.0002260 0.0000 + 9 -204.7102899284 0.000502976631 0.00014484 0.00000425 0.0000900 0.0000 + 10 -204.7103121641 -0.000022235691 0.00005166 0.00000160 0.0000471 0.0000 + 11 -204.7104977586 -0.000185594473 0.00003111 0.00000079 0.0000252 0.0000 + 12 -204.7103881744 0.000109584220 0.00000783 0.00000023 0.0000069 0.0000 + 13 -204.7104117194 -0.000023545090 0.00000244 0.00000008 0.0000027 0.0000 + 14 -204.7104035239 0.000008195573 0.00000092 0.00000004 0.0000017 0.0000 + 15 -204.7104004418 0.000003082053 0.00000073 0.00000003 0.0000017 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 16 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71040454 Eh -5570.45330 eV + +Components: +Nuclear Repulsion : 69.03759599 Eh 1878.60849 eV +Electronic Energy : -273.74800053 Eh -7449.06180 eV +One Electron Energy: -417.73944860 Eh -11367.26830 eV +Two Electron Energy: 143.99144806 Eh 3918.20650 eV + +Virial components: +Potential Energy : -408.93963571 Eh -11127.81321 eV +Kinetic Energy : 204.22923117 Eh 5557.35991 eV +Virial Ratio : 2.00235605 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -4.0989e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.6944e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.5488e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.2548e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.681602 -562.7750 + 1 1.0000 -20.629967 -561.3699 + 2 1.0000 -15.803119 -430.0247 + 3 1.0000 -1.609248 -43.7899 + 4 1.0000 -1.388371 -37.7795 + 5 1.0000 -0.959508 -26.1095 + 6 1.0000 -0.771310 -20.9884 + 7 1.0000 -0.735515 -20.0144 + 8 1.0000 -0.697380 -18.9767 + 9 1.0000 -0.601765 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196.0554 + 145 0.0000 7.249353 197.2649 + 146 0.0000 7.272462 197.8938 + 147 0.0000 7.316427 199.0901 + 148 0.0000 7.390966 201.1184 + 149 0.0000 7.466152 203.1643 + 150 0.0000 7.483502 203.6364 + 151 0.0000 7.537689 205.1109 + 152 0.0000 7.573310 206.0802 + 153 0.0000 7.682311 209.0463 + 154 0.0000 7.706369 209.7010 + 155 0.0000 7.904338 215.0880 + 156 0.0000 8.049547 219.0393 + 157 0.0000 8.376268 227.9298 + 158 0.0000 14.012113 381.2890 + 159 0.0000 15.038349 409.2143 + 160 0.0000 15.846895 431.2159 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.681602 -562.7750 + 1 1.0000 -20.629967 -561.3699 + 2 1.0000 -15.803119 -430.0247 + 3 1.0000 -1.609248 -43.7899 + 4 1.0000 -1.388371 -37.7795 + 5 1.0000 -0.959508 -26.1095 + 6 1.0000 -0.771310 -20.9884 + 7 1.0000 -0.735515 -20.0144 + 8 1.0000 -0.697380 -18.9767 + 9 1.0000 -0.601765 -16.3749 + 10 1.0000 -0.534156 -14.5351 + 11 1.0000 -0.466335 -12.6896 + 12 0.0000 0.030578 0.8321 + 13 0.0000 0.067801 1.8450 + 14 0.0000 0.093574 2.5463 + 15 0.0000 0.108619 2.9557 + 16 0.0000 0.113973 3.1014 + 17 0.0000 0.154378 4.2008 + 18 0.0000 0.156455 4.2574 + 19 0.0000 0.172863 4.7038 + 20 0.0000 0.179336 4.8800 + 21 0.0000 0.191561 5.2126 + 22 0.0000 0.202763 5.5174 + 23 0.0000 0.235288 6.4025 + 24 0.0000 0.269623 7.3368 + 25 0.0000 0.290399 7.9022 + 26 0.0000 0.311057 8.4643 + 27 0.0000 0.337273 9.1777 + 28 0.0000 0.341705 9.2983 + 29 0.0000 0.363059 9.8793 + 30 0.0000 0.421138 11.4597 + 31 0.0000 0.512669 13.9504 + 32 0.0000 0.532527 14.4908 + 33 0.0000 0.537170 14.6171 + 34 0.0000 0.561863 15.2891 + 35 0.0000 0.604831 16.4583 + 36 0.0000 0.633697 17.2438 + 37 0.0000 0.644440 17.5361 + 38 0.0000 0.700334 19.0571 + 39 0.0000 0.716061 19.4850 + 40 0.0000 0.734014 19.9735 + 41 0.0000 0.740059 20.1380 + 42 0.0000 0.768258 20.9053 + 43 0.0000 0.783163 21.3109 + 44 0.0000 0.814161 22.1544 + 45 0.0000 0.824479 22.4352 + 46 0.0000 0.853124 23.2147 + 47 0.0000 0.882265 24.0076 + 48 0.0000 0.908279 24.7155 + 49 0.0000 0.945979 25.7414 + 50 0.0000 0.974427 26.5155 + 51 0.0000 0.979188 26.6450 + 52 0.0000 0.993280 27.0285 + 53 0.0000 1.017629 27.6911 + 54 0.0000 1.051120 28.6024 + 55 0.0000 1.088712 29.6254 + 56 0.0000 1.158922 31.5359 + 57 0.0000 1.209784 32.9199 + 58 0.0000 1.228826 33.4381 + 59 0.0000 1.282192 34.8902 + 60 0.0000 1.336180 36.3593 + 61 0.0000 1.410496 38.3815 + 62 0.0000 1.455845 39.6156 + 63 0.0000 1.510660 41.1071 + 64 0.0000 1.540280 41.9131 + 65 0.0000 1.568022 42.6681 + 66 0.0000 1.608103 43.7587 + 67 0.0000 1.636259 44.5249 + 68 0.0000 1.653963 45.0066 + 69 0.0000 1.732950 47.1560 + 70 0.0000 1.753609 47.7181 + 71 0.0000 1.790449 48.7206 + 72 0.0000 1.920824 52.2683 + 73 0.0000 1.948647 53.0254 + 74 0.0000 1.970932 53.6318 + 75 0.0000 2.008389 54.6511 + 76 0.0000 2.047734 55.7217 + 77 0.0000 2.082193 56.6594 + 78 0.0000 2.154245 58.6200 + 79 0.0000 2.177422 59.2507 + 80 0.0000 2.258465 61.4559 + 81 0.0000 2.310222 62.8643 + 82 0.0000 2.335305 63.5469 + 83 0.0000 2.380865 64.7866 + 84 0.0000 2.423430 65.9449 + 85 0.0000 2.455501 66.8176 + 86 0.0000 2.465150 67.0801 + 87 0.0000 2.496732 67.9395 + 88 0.0000 2.511487 68.3410 + 89 0.0000 2.553517 69.4847 + 90 0.0000 2.580631 70.2225 + 91 0.0000 2.609190 70.9997 + 92 0.0000 2.667422 72.5842 + 93 0.0000 2.683459 73.0206 + 94 0.0000 2.767451 75.3062 + 95 0.0000 2.819410 76.7201 + 96 0.0000 2.822426 76.8021 + 97 0.0000 2.930550 79.7443 + 98 0.0000 2.971649 80.8627 + 99 0.0000 2.994413 81.4821 + 100 0.0000 3.127414 85.1013 + 101 0.0000 3.170758 86.2807 + 102 0.0000 3.222859 87.6985 + 103 0.0000 3.503207 95.3271 + 104 0.0000 3.691731 100.4571 + 105 0.0000 3.862993 105.1174 + 106 0.0000 4.024241 109.5052 + 107 0.0000 4.156708 113.1098 + 108 0.0000 4.195106 114.1546 + 109 0.0000 4.319204 117.5315 + 110 0.0000 4.365530 118.7921 + 111 0.0000 4.394670 119.5851 + 112 0.0000 4.543983 123.6481 + 113 0.0000 4.612468 125.5116 + 114 0.0000 4.673050 127.1601 + 115 0.0000 4.752320 129.3172 + 116 0.0000 4.811182 130.9189 + 117 0.0000 4.873172 132.6058 + 118 0.0000 4.954274 134.8127 + 119 0.0000 4.987087 135.7055 + 120 0.0000 5.063769 137.7921 + 121 0.0000 5.106040 138.9424 + 122 0.0000 5.176691 140.8649 + 123 0.0000 5.222972 142.1243 + 124 0.0000 5.246752 142.7714 + 125 0.0000 5.278547 143.6366 + 126 0.0000 5.389784 146.6635 + 127 0.0000 5.488938 149.3616 + 128 0.0000 5.523262 150.2956 + 129 0.0000 5.698877 155.0743 + 130 0.0000 5.762077 156.7941 + 131 0.0000 5.966907 162.3678 + 132 0.0000 6.163718 167.7233 + 133 0.0000 6.410572 174.4405 + 134 0.0000 6.488692 176.5663 + 135 0.0000 6.520086 177.4206 + 136 0.0000 6.685259 181.9152 + 137 0.0000 6.711189 182.6208 + 138 0.0000 6.779843 184.4889 + 139 0.0000 6.809823 185.3047 + 140 0.0000 6.866183 186.8383 + 141 0.0000 7.086173 192.8246 + 142 0.0000 7.117494 193.6769 + 143 0.0000 7.154301 194.6784 + 144 0.0000 7.204903 196.0554 + 145 0.0000 7.249353 197.2649 + 146 0.0000 7.272462 197.8938 + 147 0.0000 7.316427 199.0901 + 148 0.0000 7.390966 201.1184 + 149 0.0000 7.466152 203.1643 + 150 0.0000 7.483502 203.6364 + 151 0.0000 7.537689 205.1109 + 152 0.0000 7.573310 206.0802 + 153 0.0000 7.682311 209.0463 + 154 0.0000 7.706369 209.7010 + 155 0.0000 7.904338 215.0880 + 156 0.0000 8.049547 219.0393 + 157 0.0000 8.376268 227.9298 + 158 0.0000 14.012113 381.2890 + 159 0.0000 15.038349 409.2143 + 160 0.0000 15.846895 431.2159 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.342301 0.000000 + 1 N : 0.348109 0.000000 + 2 O : -0.258256 0.000000 + 3 H : 0.252448 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.838688 s : 3.838688 + pz : 1.365621 p : 4.468239 + px : 1.608750 + py : 1.493868 + dz2 : 0.009023 d : 0.030780 + dxz : 0.008337 + dyz : 0.005858 + dx2y2 : 0.006108 + dxy : 0.001455 + f0 : 0.001142 f : 0.004593 + f+1 : 0.001055 + f-1 : 0.000662 + f+2 : 0.000609 + f-2 : 0.000594 + f+3 : 0.000374 + f-3 : 0.000157 + 1 N s : 3.832307 s : 3.832307 + pz : 0.776164 p : 2.645930 + px : 0.767699 + py : 1.102068 + dz2 : 0.029056 d : 0.141508 + dxz : 0.034145 + dyz : 0.019512 + dx2y2 : 0.035182 + dxy : 0.023614 + f0 : 0.007492 f : 0.032145 + f+1 : 0.001983 + f-1 : 0.005160 + f+2 : 0.003068 + f-2 : 0.005909 + f+3 : 0.003034 + f-3 : 0.005500 + 2 O s : 3.875086 s : 3.875086 + pz : 1.667299 p : 4.314977 + px : 1.267089 + py : 1.380589 + dz2 : 0.005298 d : 0.060776 + dxz : 0.006131 + dyz : 0.014800 + dx2y2 : 0.022393 + dxy : 0.012154 + f0 : 0.001000 f : 0.007418 + f+1 : 0.000527 + f-1 : 0.000852 + f+2 : 0.000167 + f-2 : 0.001236 + f+3 : 0.001599 + f-3 : 0.002038 + 3 H s : 0.638504 s : 0.638504 + pz : 0.024596 p : 0.088285 + px : 0.038173 + py : 0.025516 + dz2 : 0.001232 d : 0.020763 + dxz : 0.001432 + dyz : 0.007252 + dx2y2 : 0.007055 + dxy : 0.003791 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.583336 0.000000 + 1 N : -0.260941 0.000000 + 2 O : 0.244628 0.000000 + 3 H : -0.567023 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.121679 s : 3.121679 + pz : 1.255514 p : 3.936158 + px : 1.336318 + py : 1.344326 + dz2 : 0.071324 d : 0.276080 + dxz : 0.079703 + dyz : 0.055482 + dx2y2 : 0.026658 + dxy : 0.042913 + f0 : 0.012750 f : 0.082747 + f+1 : 0.018547 + f-1 : 0.015236 + f+2 : 0.012581 + f-2 : 0.015387 + f+3 : 0.006139 + f-3 : 0.002108 + 1 N s : 3.021464 s : 3.021464 + pz : 0.832906 p : 2.837771 + px : 0.835759 + py : 1.169106 + dz2 : 0.199623 d : 0.947052 + dxz : 0.224556 + dyz : 0.148074 + dx2y2 : 0.185227 + dxy : 0.189572 + f0 : 0.086068 f : 0.454654 + f+1 : 0.052310 + f-1 : 0.059259 + f+2 : 0.034290 + f-2 : 0.089936 + f+3 : 0.063448 + f-3 : 0.069344 + 2 O s : 3.311868 s : 3.311868 + pz : 1.379608 p : 4.002568 + px : 1.227565 + py : 1.395396 + dz2 : 0.050538 d : 0.324642 + dxz : 0.055337 + dyz : 0.039576 + dx2y2 : 0.077157 + dxy : 0.102034 + f0 : 0.010620 f : 0.116293 + f+1 : 0.010544 + f-1 : 0.016911 + f+2 : 0.004712 + f-2 : 0.021270 + f+3 : 0.030063 + f-3 : 0.022174 + 3 H s : 0.618510 s : 0.618510 + pz : 0.143379 p : 0.558369 + px : 0.172197 + py : 0.242793 + dz2 : 0.032691 d : 0.390144 + dxz : 0.047380 + dyz : 0.094435 + dx2y2 : 0.116351 + dxy : 0.099285 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3423 8.0000 -0.3423 1.8147 1.8147 -0.0000 + 1 N 6.6519 7.0000 0.3481 2.5587 2.5587 -0.0000 + 2 O 8.2583 8.0000 -0.2583 1.7590 1.7590 0.0000 + 3 H 0.7476 1.0000 0.2524 1.0046 1.0046 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8084 B( 0-O , 3-H ) : 0.9472 B( 1-N , 2-O ) : 1.6964 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.498 sec +Sum of individual times .... 2.234 sec ( 89.4%) + +Fock matrix formation .... 1.812 sec ( 72.5%) +Diagonalization .... 0.185 sec ( 7.4%) +Density matrix formation .... 0.014 sec ( 0.5%) +Population analysis .... 0.055 sec ( 2.2%) +Initial guess .... 0.009 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.2%) +DIIS solution .... 0.159 sec ( 6.4%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.203 sec +Reference energy ... -204.710403243 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.337 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.343 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.024 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.346 sec +AO-integral generation ... 0.243 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.049 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.165 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.251 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090080510 +EMP2(bb)= -0.090080510 +EMP2(ab)= -0.515900409 + +Initial guess performed in 0.131 sec +E(0) ... -204.710403243 +E(MP2) ... -0.696061429 +Initial E(tot) ... -205.406464672 + ... 0.187754072 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.406464672 -0.696061429 -0.000000000 0.021887020 2.73 0.000002668 + *** Turning on DIIS *** + 1 -205.378454536 -0.668051293 0.028010137 0.009181034 2.69 0.056223146 + 2 -205.397817039 -0.687413796 -0.019362503 0.004681371 2.80 0.059350634 + 3 -205.401592001 -0.691188758 -0.003774962 0.001611432 2.81 0.073022621 + 4 -205.403143791 -0.692740548 -0.001551790 0.001336376 2.79 0.079450905 + 5 -205.403669036 -0.693265793 -0.000525245 0.000830321 2.89 0.084578581 + 6 -205.403769299 -0.693366056 -0.000100263 0.000512246 2.82 0.087166088 + 7 -205.403812535 -0.693409292 -0.000043236 0.000259791 2.88 0.088406995 + 8 -205.403823452 -0.693420209 -0.000010917 0.000130462 2.89 0.088969746 + 9 -205.403820202 -0.693416959 0.000003250 0.000075765 2.80 0.089172824 + 10 -205.403825434 -0.693422191 -0.000005232 0.000043312 2.78 0.089252417 + 11 -205.403822040 -0.693418797 0.000003394 0.000029284 2.78 0.089249754 + 12 -205.403824382 -0.693421139 -0.000002342 0.000017736 2.79 0.089268526 + 13 -205.403823976 -0.693420733 0.000000406 0.000009891 2.84 0.089264708 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.710403243 +E(CORR) ... -0.693420733 +E(TOT) ... -205.403823976 +Singles norm **1/2 ... 0.089264708 ( 0.044632354, 0.044632354) +T1 diagnostic ... 0.021039893 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.053745 + 9a-> 13a 9b-> 13b 0.051985 + 9a-> 13a 8b-> 13b 0.039187 + 8a-> 13a 9b-> 13b 0.039187 + 8a-> 13a -1a-> -1a 0.034961 + 8b-> 13b -1b-> -1b 0.034961 + 11a-> 13a 11b-> 13b 0.030767 + 5a-> 13a 5b-> 13b 0.027966 + 10a-> 13a -1a-> -1a 0.026578 + 10b-> 13b -1b-> -1b 0.026578 + 10a-> 13a 9b-> 13b 0.023917 + 9a-> 13a 10b-> 13b 0.023917 + 11a-> 25a 11b-> 25b 0.020343 + 9a-> 13a 9b-> 22b 0.020112 + 9a-> 22a 9b-> 13b 0.020112 + 11a-> 25a -1a-> -1a 0.019979 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034392363 + alpha-alpha-alpha ... -0.000879139 ( 2.6%) + alpha-alpha-beta ... -0.016317042 ( 47.4%) + alpha-beta -beta ... -0.016317042 ( 47.4%) + beta -beta -beta ... -0.000879139 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034392363 + +Final correlation energy ... -0.727813096 +E(CCSD) ... -205.403823976 +E(CCSD(T)) ... -205.438216339 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209703326 sqrt= 1.099865140 +W(HF) = 0.826648963 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.273408 -0.000000 + 1 N : 0.167855 0.000000 + 2 O : -0.134551 -0.000000 + 3 H : 0.240104 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.820514 s : 3.820514 + pz : 1.340051 p : 4.383402 + px : 1.576772 + py : 1.466579 + dz2 : 0.014733 d : 0.061209 + dxz : 0.013097 + dyz : 0.012805 + dx2y2 : 0.012401 + dxy : 0.008173 + f0 : 0.001698 f : 0.008283 + f+1 : 0.001279 + f-1 : 0.001220 + f+2 : 0.001103 + f-2 : 0.001139 + f+3 : 0.001028 + f-3 : 0.000814 + 1 N s : 3.886924 s : 3.886924 + pz : 0.826417 p : 2.743223 + px : 0.835585 + py : 1.081221 + dz2 : 0.036975 d : 0.170911 + dxz : 0.041573 + dyz : 0.025302 + dx2y2 : 0.039139 + dxy : 0.027922 + f0 : 0.007019 f : 0.031086 + f+1 : 0.001910 + f-1 : 0.005307 + f+2 : 0.003238 + f-2 : 0.005684 + f+3 : 0.003155 + f-3 : 0.004774 + 2 O s : 3.861409 s : 3.861409 + pz : 1.595806 p : 4.180724 + px : 1.235489 + py : 1.349428 + dz2 : 0.010744 d : 0.082521 + dxz : 0.012649 + dyz : 0.018948 + dx2y2 : 0.025574 + dxy : 0.014606 + f0 : 0.001435 f : 0.009897 + f+1 : 0.000994 + f-1 : 0.001276 + f+2 : 0.000731 + f-2 : 0.001581 + f+3 : 0.001808 + f-3 : 0.002071 + 3 H s : 0.648626 s : 0.648626 + pz : 0.028588 p : 0.093062 + px : 0.041348 + py : 0.023125 + dz2 : 0.001000 d : 0.018209 + dxz : 0.001546 + dyz : 0.006460 + dx2y2 : 0.006001 + dxy : 0.003202 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.592766 -0.000000 + 1 N : -0.305985 -0.000000 + 2 O : 0.284644 0.000000 + 3 H : -0.571424 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.127862 s : 3.127862 + pz : 1.242233 p : 3.882221 + px : 1.315439 + py : 1.324550 + dz2 : 0.077395 d : 0.307271 + dxz : 0.086345 + dyz : 0.060550 + dx2y2 : 0.032720 + dxy : 0.050260 + f0 : 0.014642 f : 0.089880 + f+1 : 0.020134 + f-1 : 0.015542 + f+2 : 0.013427 + f-2 : 0.016190 + f+3 : 0.007004 + f-3 : 0.002940 + 1 N s : 3.026981 s : 3.026981 + pz : 0.855647 p : 2.880621 + px : 0.875602 + py : 1.149372 + dz2 : 0.204240 d : 0.953996 + dxz : 0.229100 + dyz : 0.142503 + dx2y2 : 0.181598 + dxy : 0.196554 + f0 : 0.082176 f : 0.444388 + f+1 : 0.053053 + f-1 : 0.058575 + f+2 : 0.033530 + f-2 : 0.086939 + f+3 : 0.062538 + f-3 : 0.067577 + 2 O s : 3.314277 s : 3.314277 + pz : 1.336095 p : 3.921334 + px : 1.208873 + py : 1.376366 + dz2 : 0.056648 d : 0.355022 + dxz : 0.059919 + dyz : 0.045807 + dx2y2 : 0.085587 + dxy : 0.107061 + f0 : 0.011567 f : 0.124723 + f+1 : 0.011647 + f-1 : 0.017077 + f+2 : 0.005883 + f-2 : 0.022147 + f+3 : 0.030810 + f-3 : 0.025593 + 3 H s : 0.620728 s : 0.620728 + pz : 0.144684 p : 0.570700 + px : 0.176910 + py : 0.249106 + dz2 : 0.032769 d : 0.379996 + dxz : 0.045717 + dyz : 0.091599 + dx2y2 : 0.112713 + dxy : 0.097198 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2734 8.0000 -0.2734 2.1736 1.7198 0.4538 + 1 N 6.8321 7.0000 0.1679 2.8313 2.3458 0.4855 + 2 O 8.1346 8.0000 -0.1346 2.1479 1.6482 0.4997 + 3 H 0.7599 1.0000 0.2401 1.0226 0.9483 0.0743 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7437 B( 0-O , 3-H ) : 0.8813 B( 1-N , 2-O ) : 1.5442 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 54.458 sec + +Fock Matrix Formation ... 0.203 sec ( 0.4%) +Initial Guess ... 0.131 sec ( 0.2%) +DIIS Solver ... 1.768 sec ( 3.2%) +State Vector Update ... 0.083 sec ( 0.2%) +Sigma-vector construction ... 37.451 sec ( 68.8%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.024 sec ( 0.1% of sigma) + (0-ext) ... 0.070 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (2-ext) ... 0.936 sec ( 2.5% of sigma) + (4-ext) ... 20.849 sec ( 55.7% of sigma) + ... 1.317 sec ( 3.5% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.108 sec ( 0.3% of sigma) + Fock-dressing ... 2.091 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.073 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.325 sec ( 24.9% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.902 sec ( 12.7% of ALL) + I/O of integral and amplitudes ... 0.810 sec ( 11.7% of (T)) + External N**7 contributions ... 3.902 sec ( 56.5% of (T)) + Internal N**7 contributions ... 0.311 sec ( 4.5% of (T)) + N**6 triples energy contributions ... 1.705 sec ( 24.7% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.438216339104 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.012480547 0.000700559 0.003762031 + 2 N : -0.012366683 0.002220721 -0.002583377 + 3 O : 0.007923773 -0.000935524 0.003158031 + 4 H : -0.008037637 -0.001985756 -0.004336684 + +Norm of the cartesian gradient ... 0.022269626 +RMS gradient ... 0.006428687 +MAX gradient ... 0.012480547 + +------- +TIMINGS +------- + +Total numerical gradient time ... 358.616 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: -413.16 cm**-1 ***imaginary mode*** + 7: 585.94 cm**-1 + 8: 800.88 cm**-1 + 9: 1227.43 cm**-1 + 10: 1650.45 cm**-1 + 11: 3679.30 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 0.030321 0.402807 -0.045637 0.013306 -0.020207 -0.029433 + 1 0.028299 0.127106 0.126796 0.062295 0.045871 0.054326 + 2 0.084593 -0.328770 0.186593 -0.049775 0.039523 -0.009812 + 3 -0.030794 -0.220234 0.162794 0.061832 -0.381385 -0.000754 + 4 0.036009 -0.126189 -0.228766 -0.046359 -0.571585 -0.000108 + 5 -0.088279 0.077809 -0.377963 -0.045808 0.039107 0.000223 + 6 0.045641 -0.210172 -0.134782 -0.039152 0.369461 0.000590 + 7 -0.029012 -0.006816 0.050822 -0.020389 0.455098 0.000416 + 8 0.015740 0.304386 0.171340 0.034227 -0.094673 -0.000239 + 9 -0.777765 0.002821 0.601465 -0.448984 -0.243720 0.468279 + 10 -0.489070 -0.155741 0.359734 -0.020940 -0.008730 -0.867367 + 11 -0.365794 -0.694181 -0.429017 0.883317 0.331930 0.156441 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 7: 585.94 0.013049 65.94 0.006950 (-0.069727 -0.025241 0.038089) + 8: 800.88 0.045040 227.62 0.017550 ( 0.094496 -0.002685 -0.092808) + 9: 1227.43 0.002274 11.49 0.000578 (-0.010785 0.015029 0.015361) + 10: 1650.45 0.032273 163.10 0.006102 (-0.057889 -0.017797 0.049338) + 11: 3679.30 0.010561 53.37 0.000896 ( 0.022448 -0.018786 -0.006241) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 7 +The total number of vibrations considered is 5 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 585.94 E(vib) ... 0.11 +freq. 800.88 E(vib) ... 0.05 +freq. 1227.43 E(vib) ... 0.01 +freq. 1650.45 E(vib) ... 0.00 +freq. 3679.30 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.43821634 Eh +Zero point energy ... 0.01809776 Eh 11.36 kcal/mol +Thermal vibrational correction ... 0.00026366 Eh 0.17 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.41702238 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00309621 Eh 1.94 kcal/mol +Non-thermal (ZPE) correction 0.01809776 Eh 11.36 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02119396 Eh 13.30 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.41702238 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.41607817 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.743921 0.414678 0.368691 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00034443 Eh 0.22 kcal/mol +Rotational entropy ... 0.00992090 Eh 6.23 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02806764 Eh 17.61 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00992090 Eh 6.23 kcal/mol| +| sn= 2 | S(rot)= 0.00926644 Eh 5.81 kcal/mol| +| sn= 3 | S(rot)= 0.00888361 Eh 5.57 kcal/mol| +| sn= 4 | S(rot)= 0.00861198 Eh 5.40 kcal/mol| +| sn= 5 | S(rot)= 0.00840130 Eh 5.27 kcal/mol| +| sn= 6 | S(rot)= 0.00822915 Eh 5.16 kcal/mol| +| sn= 7 | S(rot)= 0.00808361 Eh 5.07 kcal/mol| +| sn= 8 | S(rot)= 0.00795753 Eh 4.99 kcal/mol| +| sn= 9 | S(rot)= 0.00784632 Eh 4.92 kcal/mol| +| sn=10 | S(rot)= 0.00774684 Eh 4.86 kcal/mol| +| sn=11 | S(rot)= 0.00765685 Eh 4.80 kcal/mol| +| sn=12 | S(rot)= 0.00757469 Eh 4.75 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.41607817 Eh +Total entropy correction ... -0.02806764 Eh -17.61 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44414581 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00592947 Eh -3.72 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.438216341 Eh +Current gradient norm .... 0.022269626 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + -0.020037104 0.107483999 0.188245267 0.480223550 0.504117631 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999545254 +Lowest eigenvalues of augmented Hessian: + -0.000132575 0.100924366 0.187764401 0.480007652 0.503797677 +Length of the computed step .... 0.030168073 +The final length of the internal step .... 0.030168073 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0123160642 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0062708903 RMS(Int)= 0.0123162491 + Iter 1: RMS(Cart)= 0.0000115861 RMS(Int)= 0.0000161132 + Iter 2: RMS(Cart)= 0.0000000460 RMS(Int)= 0.0000000776 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0022911561 0.0001000000 NO + MAX gradient 0.0036879493 0.0003000000 NO + RMS step 0.0123160642 0.0020000000 NO + MAX step 0.0281276894 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0149 Max(Angles) 0.18 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4538 -0.003053 0.0149 1.4687 + 2. B(O 2,N 1) 1.1771 0.003688 -0.0044 1.1727 + 3. B(H 3,O 0) 0.9744 0.002743 -0.0031 0.9714 + 4. A(N 1,O 0,H 3) 104.70 -0.000619 -0.18 104.53 + 5. A(O 0,N 1,O 2) 112.56 0.000817 -0.15 112.41 + 6. D(O 2,N 1,O 0,H 3) 57.27 0.015901 0.00 57.27 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.464650 -0.313813 0.706936 + N 0.320987 -0.547600 -0.511699 + O 1.062209 0.331638 -0.741327 + H -0.918546 0.529776 0.546090 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.878060 -0.593021 1.335915 + 1 N 7.0000 0 14.007 0.606577 -1.034815 -0.966971 + 2 O 8.0000 0 15.999 2.007285 0.626704 -1.400905 + 3 H 1.0000 0 1.008 -1.735800 1.001131 1.031961 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.468656404258 0.00000000 0.00000000 + O 2 1 0 1.172688809459 112.41082080 0.00000000 + H 1 2 3 0.971357583677 104.52554099 57.27272713 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.775358388877 0.00000000 0.00000000 + O 2 1 0 2.216060690192 112.41082080 0.00000000 + H 1 2 3 1.835599811256 104.52554099 57.27272713 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2235 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2706 + la=0 lb=0: 553 shell pairs + la=1 lb=0: 537 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.873570581879 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.659e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7097985164 0.000000000000 0.00042179 0.00001132 0.0020117 0.7000 + 1 -204.7098326360 -0.000034119679 0.00034641 0.00000961 0.0015964 0.7000 + ***Turning on DIIS*** + 2 -204.7098609989 -0.000028362822 0.00088608 0.00002521 0.0012622 0.0000 + 3 -204.7094467524 0.000414246427 0.00031756 0.00001212 0.0004286 0.0000 + 4 -204.7100412431 -0.000594490708 0.00014120 0.00000427 0.0001412 0.0000 + 5 -204.7100669222 -0.000025679047 0.00005298 0.00000139 0.0000853 0.0000 + 6 -204.7098735428 0.000193379336 0.00003364 0.00000082 0.0000618 0.0000 + 7 -204.7099760007 -0.000102457837 0.00000864 0.00000028 0.0000103 0.0000 + 8 -204.7099477383 0.000028262403 0.00000339 0.00000011 0.0000044 0.0000 + 9 -204.7099500929 -0.000002354585 0.00000133 0.00000004 0.0000017 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 10 CYCLES * + ***************************************************** + +Total Energy : -204.70995989 Eh -5570.44120 eV + Last Energy change ... -9.7973e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.2263e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.227 sec +Reference energy ... -204.709954494 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.410 sec +AO-integral generation ... 0.148 sec +Half transformation ... 0.083 sec +K-integral sorting ... 5.412 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.022 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.030 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.030 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.040 s ( 0.000 ms/b) + 159120 b 0 skpd 0.017 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.363 sec +AO-integral generation ... 0.245 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.150 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.256 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090120635 +EMP2(bb)= -0.090120635 +EMP2(ab)= -0.516332375 + +Initial guess performed in 0.134 sec +E(0) ... -204.709954494 +E(MP2) ... -0.696573645 +Initial E(tot) ... -205.406528138 + ... 0.188287942 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.406528138 -0.696573645 -0.000000000 0.021684432 2.75 0.000001475 + *** Turning on DIIS *** + 1 -205.378263307 -0.668308814 0.028264831 0.009517698 3.06 0.056492634 + 2 -205.397715997 -0.687761503 -0.019452690 0.004596950 2.84 0.059523487 + 3 -205.401504056 -0.691549562 -0.003788059 0.001681332 2.78 0.073261295 + 4 -205.403063276 -0.693108782 -0.001559220 0.001398794 2.82 0.079710961 + 5 -205.403594807 -0.693640313 -0.000531531 0.000864100 2.86 0.084920069 + 6 -205.403697298 -0.693742804 -0.000102491 0.000532902 2.84 0.087596478 + 7 -205.403742513 -0.693788019 -0.000045215 0.000266119 2.89 0.088912939 + 8 -205.403754218 -0.693799724 -0.000011705 0.000128840 2.90 0.089505267 + 9 -205.403750748 -0.693796255 0.000003469 0.000075318 2.82 0.089711808 + 10 -205.403756297 -0.693801804 -0.000005549 0.000043231 2.79 0.089796791 + 11 -205.403752772 -0.693798278 0.000003526 0.000029416 2.79 0.089791844 + 12 -205.403755102 -0.693800609 -0.000002331 0.000017818 2.85 0.089812539 + 13 -205.403754763 -0.693800270 0.000000339 0.000010285 2.86 0.089807561 + 14 -205.403755160 -0.693800666 -0.000000396 0.000004583 2.83 0.089814768 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.709954494 +E(CORR) ... -0.693800666 +E(TOT) ... -205.403755160 +Singles norm **1/2 ... 0.089814768 ( 0.044907384, 0.044907384) +T1 diagnostic ... 0.021169544 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.056278 + 9a-> 13a 9b-> 13b 0.050222 + 8a-> 13a 9b-> 13b 0.039720 + 9a-> 13a 8b-> 13b 0.039720 + 8a-> 13a -1a-> -1a 0.034288 + 8b-> 13b -1b-> -1b 0.034288 + 11a-> 13a 11b-> 13b 0.030048 + 5a-> 13a 5b-> 13b 0.028454 + 10b-> 13b -1b-> -1b 0.028143 + 10a-> 13a -1a-> -1a 0.028143 + 11a-> 25a 11b-> 25b 0.027257 + 11a-> 25a -1a-> -1a 0.023192 + 11b-> 25b -1b-> -1b 0.023192 + 9a-> 13a 10b-> 13b 0.022109 + 10a-> 13a 9b-> 13b 0.022109 + 8a-> 13a 8b-> 22b 0.020625 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034527427 + alpha-alpha-alpha ... -0.000879834 ( 2.5%) + alpha-alpha-beta ... -0.016383880 ( 47.5%) + alpha-beta -beta ... -0.016383880 ( 47.5%) + beta -beta -beta ... -0.000879834 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034527427 + +Final correlation energy ... -0.728328093 +E(CCSD) ... -205.403755160 +E(CCSD(T)) ... -205.438282587 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210407968 sqrt= 1.100185424 +W(HF) = 0.826167727 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 57.804 sec + +Fock Matrix Formation ... 0.227 sec ( 0.4%) +Initial Guess ... 0.134 sec ( 0.2%) +DIIS Solver ... 1.895 sec ( 3.3%) +State Vector Update ... 0.090 sec ( 0.2%) +Sigma-vector construction ... 40.680 sec ( 70.4%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (0-ext) ... 0.072 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (2-ext) ... 1.000 sec ( 2.5% of sigma) + (4-ext) ... 22.721 sec ( 55.9% of sigma) + ... 1.461 sec ( 3.6% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.115 sec ( 0.3% of sigma) + Fock-dressing ... 2.234 sec ( 5.5% of sigma) + (ik|jl)-dressing ... 0.079 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.139 sec ( 24.9% of sigma) + Pair energies ... 0.006 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.791 sec ( 11.7% of ALL) + I/O of integral and amplitudes ... 0.639 sec ( 9.4% of (T)) + External N**7 contributions ... 3.886 sec ( 57.2% of (T)) + Internal N**7 contributions ... 0.311 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.583 sec ( 23.3% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.438282586838 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.009166046 0.003765240 0.005336606 + 2 N : -0.007998158 0.003630957 -0.005744176 + 3 O : 0.005374528 -0.003225750 0.003893519 + 4 H : -0.006542417 -0.004170446 -0.003485949 + +Norm of the cartesian gradient ... 0.019068847 +RMS gradient ... 0.005504702 +MAX gradient ... 0.009166046 + +------- +TIMINGS +------- + +Total numerical gradient time ... 367.303 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.438282587 Eh +Current gradient norm .... 0.019068847 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999554 +Lowest eigenvalues of augmented Hessian: + -0.000000208 0.104066605 0.184876172 0.476641066 0.506452749 +Length of the computed step .... 0.000943980 +The final length of the internal step .... 0.000943980 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0003853782 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0002555009 RMS(Int)= 0.0003853777 + Iter 1: RMS(Cart)= 0.0000000831 RMS(Int)= 0.0000001386 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000662460 0.0000050000 NO + RMS gradient 0.0001267133 0.0001000000 NO + MAX gradient 0.0002164478 0.0003000000 YES + RMS step 0.0003853782 0.0020000000 YES + MAX step 0.0007689978 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0002 Max(Angles) 0.04 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4687 0.000068 -0.0002 1.4684 + 2. B(O 2,N 1) 1.1727 0.000216 -0.0001 1.1726 + 3. B(H 3,O 0) 0.9714 0.000012 -0.0000 0.9713 + 4. A(N 1,O 0,H 3) 104.53 -0.000113 0.04 104.57 + 5. A(O 0,N 1,O 2) 112.41 0.000179 -0.01 112.40 + 6. D(O 2,N 1,O 0,H 3) 57.27 0.015112 -0.00 57.27 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.464492 -0.313673 0.706659 + N 0.321070 -0.547694 -0.511704 + O 1.062124 0.331560 -0.741237 + H -0.918701 0.529806 0.546281 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.877763 -0.592756 1.335392 + 1 N 7.0000 0 14.007 0.606734 -1.034991 -0.966980 + 2 O 8.0000 0 15.999 2.007124 0.626558 -1.400734 + 3 H 1.0000 0 1.008 -1.736093 1.001189 1.032322 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.468428412669 0.00000000 0.00000000 + O 2 1 0 1.172576088405 112.39608056 0.00000000 + H 1 2 3 0.971330828622 104.56960132 57.27272713 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.774927547214 0.00000000 0.00000000 + O 2 1 0 2.215847678270 112.39608056 0.00000000 + H 1 2 3 1.835549251531 104.56960132 57.27272713 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2235 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2706 + la=0 lb=0: 553 shell pairs + la=1 lb=0: 537 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.882153262695 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.8821532627 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.659e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7100007749 0.000000000000 0.00000809 0.00000031 0.0000648 0.7000 + 1 -204.7100007971 -0.000000022256 0.00000669 0.00000027 0.0000516 0.7000 + ***Turning on DIIS*** + 2 -204.7100008155 -0.000000018427 0.00001739 0.00000073 0.0000402 0.0000 + 3 -204.7099880117 0.000012803888 0.00001018 0.00000034 0.0000100 0.0000 + 4 -204.7100012099 -0.000013198289 0.00000294 0.00000014 0.0000043 0.0000 + 5 -204.7100125214 -0.000011311443 0.00000239 0.00000011 0.0000032 0.0000 + 6 -204.7099954307 0.000017090715 0.00000290 0.00000012 0.0000019 0.0000 + 7 -204.7100021881 -0.000006757430 0.00000212 0.00000008 0.0000014 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71000112 Eh -5570.44233 eV + +Components: +Nuclear Repulsion : 68.88215326 Eh 1874.37868 eV +Electronic Energy : -273.59215439 Eh -7444.82101 eV +One Electron Energy: -417.42606541 Eh -11358.74071 eV +Two Electron Energy: 143.83391103 Eh 3913.91970 eV + +Virial components: +Potential Energy : -408.94320974 Eh -11127.91047 eV +Kinetic Energy : 204.23320862 Eh 5557.46814 eV +Virial Ratio : 2.00233455 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.0639e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.0825e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.6994e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.3131e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.684600 -562.8566 + 1 1.0000 -20.626749 -561.2824 + 2 1.0000 -15.804637 -430.0660 + 3 1.0000 -1.613061 -43.8936 + 4 1.0000 -1.384220 -37.6665 + 5 1.0000 -0.959194 -26.1010 + 6 1.0000 -0.770718 -20.9723 + 7 1.0000 -0.736422 -20.0391 + 8 1.0000 -0.697223 -18.9724 + 9 1.0000 -0.604304 -16.4439 + 10 1.0000 -0.533006 -14.5038 + 11 1.0000 -0.464986 -12.6529 + 12 0.0000 0.030982 0.8431 + 13 0.0000 0.067766 1.8440 + 14 0.0000 0.093135 2.5343 + 15 0.0000 0.108319 2.9475 + 16 0.0000 0.114282 3.1098 + 17 0.0000 0.154419 4.2020 + 18 0.0000 0.157122 4.2755 + 19 0.0000 0.172359 4.6901 + 20 0.0000 0.179493 4.8843 + 21 0.0000 0.191448 5.2096 + 22 0.0000 0.202447 5.5089 + 23 0.0000 0.234787 6.3889 + 24 0.0000 0.269685 7.3385 + 25 0.0000 0.286893 7.8068 + 26 0.0000 0.309521 8.4225 + 27 0.0000 0.335459 9.1283 + 28 0.0000 0.341476 9.2920 + 29 0.0000 0.362378 9.8608 + 30 0.0000 0.422473 11.4961 + 31 0.0000 0.512362 13.9421 + 32 0.0000 0.532304 14.4847 + 33 0.0000 0.537008 14.6127 + 34 0.0000 0.561141 15.2694 + 35 0.0000 0.604661 16.4537 + 36 0.0000 0.634101 17.2548 + 37 0.0000 0.645763 17.5721 + 38 0.0000 0.700105 19.0508 + 39 0.0000 0.715068 19.4580 + 40 0.0000 0.734023 19.9738 + 41 0.0000 0.742070 20.1928 + 42 0.0000 0.767720 20.8907 + 43 0.0000 0.783019 21.3070 + 44 0.0000 0.814327 22.1590 + 45 0.0000 0.823943 22.4206 + 46 0.0000 0.852454 23.1964 + 47 0.0000 0.882392 24.0111 + 48 0.0000 0.908222 24.7140 + 49 0.0000 0.946536 25.7565 + 50 0.0000 0.974692 26.5227 + 51 0.0000 0.980568 26.6826 + 52 0.0000 0.993866 27.0445 + 53 0.0000 1.019445 27.7405 + 54 0.0000 1.050658 28.5899 + 55 0.0000 1.088863 29.6295 + 56 0.0000 1.157571 31.4991 + 57 0.0000 1.209672 32.9168 + 58 0.0000 1.227885 33.4125 + 59 0.0000 1.281416 34.8691 + 60 0.0000 1.337363 36.3915 + 61 0.0000 1.412038 38.4235 + 62 0.0000 1.458881 39.6982 + 63 0.0000 1.511602 41.1328 + 64 0.0000 1.536256 41.8036 + 65 0.0000 1.569627 42.7117 + 66 0.0000 1.605195 43.6796 + 67 0.0000 1.634536 44.4780 + 68 0.0000 1.654047 45.0089 + 69 0.0000 1.730660 47.0936 + 70 0.0000 1.752276 47.6819 + 71 0.0000 1.787620 48.6436 + 72 0.0000 1.921830 52.2957 + 73 0.0000 1.944825 52.9214 + 74 0.0000 1.968930 53.5773 + 75 0.0000 2.004370 54.5417 + 76 0.0000 2.047528 55.7161 + 77 0.0000 2.078823 56.5677 + 78 0.0000 2.153946 58.6119 + 79 0.0000 2.177261 59.2463 + 80 0.0000 2.255971 61.3881 + 81 0.0000 2.309506 62.8449 + 82 0.0000 2.333831 63.5068 + 83 0.0000 2.380830 64.7857 + 84 0.0000 2.423380 65.9435 + 85 0.0000 2.453999 66.7767 + 86 0.0000 2.466769 67.1242 + 87 0.0000 2.492523 67.8250 + 88 0.0000 2.512873 68.3788 + 89 0.0000 2.553471 69.4835 + 90 0.0000 2.582396 70.2706 + 91 0.0000 2.606736 70.9329 + 92 0.0000 2.665330 72.5273 + 93 0.0000 2.683611 73.0248 + 94 0.0000 2.762954 75.1838 + 95 0.0000 2.814278 76.5804 + 96 0.0000 2.821222 76.7694 + 97 0.0000 2.924255 79.5730 + 98 0.0000 2.968788 80.7848 + 99 0.0000 2.983169 81.1761 + 100 0.0000 3.117891 84.8421 + 101 0.0000 3.169857 86.2562 + 102 0.0000 3.227683 87.8297 + 103 0.0000 3.498421 95.1969 + 104 0.0000 3.694939 100.5444 + 105 0.0000 3.858838 105.0043 + 106 0.0000 4.025744 109.5461 + 107 0.0000 4.160208 113.2050 + 108 0.0000 4.200567 114.3032 + 109 0.0000 4.319792 117.5475 + 110 0.0000 4.362941 118.7217 + 111 0.0000 4.392536 119.5270 + 112 0.0000 4.546429 123.7146 + 113 0.0000 4.614831 125.5759 + 114 0.0000 4.671952 127.1303 + 115 0.0000 4.749564 129.2422 + 116 0.0000 4.815841 131.0457 + 117 0.0000 4.873979 132.6277 + 118 0.0000 4.950059 134.6980 + 119 0.0000 4.983206 135.5999 + 120 0.0000 5.062700 137.7631 + 121 0.0000 5.107677 138.9869 + 122 0.0000 5.182429 141.0211 + 123 0.0000 5.218998 142.0162 + 124 0.0000 5.247714 142.7976 + 125 0.0000 5.284462 143.7975 + 126 0.0000 5.389673 146.6605 + 127 0.0000 5.480795 149.1400 + 128 0.0000 5.517961 150.1514 + 129 0.0000 5.703031 155.1874 + 130 0.0000 5.759866 156.7339 + 131 0.0000 5.959250 162.1594 + 132 0.0000 6.161331 167.6583 + 133 0.0000 6.405294 174.2969 + 134 0.0000 6.485920 176.4909 + 135 0.0000 6.517609 177.3532 + 136 0.0000 6.686246 181.9420 + 137 0.0000 6.712227 182.6490 + 138 0.0000 6.780580 184.5090 + 139 0.0000 6.810149 185.3136 + 140 0.0000 6.862921 186.7496 + 141 0.0000 7.082850 192.7342 + 142 0.0000 7.116964 193.6624 + 143 0.0000 7.149185 194.5392 + 144 0.0000 7.211452 196.2336 + 145 0.0000 7.249623 197.2723 + 146 0.0000 7.272194 197.8865 + 147 0.0000 7.324921 199.3212 + 148 0.0000 7.390875 201.1159 + 149 0.0000 7.464537 203.1204 + 150 0.0000 7.478378 203.4970 + 151 0.0000 7.538359 205.1292 + 152 0.0000 7.573116 206.0750 + 153 0.0000 7.677156 208.9060 + 154 0.0000 7.690663 209.2736 + 155 0.0000 7.908165 215.1921 + 156 0.0000 8.028159 218.4573 + 157 0.0000 8.375564 227.9107 + 158 0.0000 14.021027 381.5316 + 159 0.0000 15.008904 408.4130 + 160 0.0000 15.957911 434.2368 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.684600 -562.8566 + 1 1.0000 -20.626749 -561.2824 + 2 1.0000 -15.804637 -430.0660 + 3 1.0000 -1.613061 -43.8936 + 4 1.0000 -1.384220 -37.6665 + 5 1.0000 -0.959194 -26.1010 + 6 1.0000 -0.770718 -20.9723 + 7 1.0000 -0.736422 -20.0391 + 8 1.0000 -0.697223 -18.9724 + 9 1.0000 -0.604304 -16.4439 + 10 1.0000 -0.533006 -14.5038 + 11 1.0000 -0.464986 -12.6529 + 12 0.0000 0.030982 0.8431 + 13 0.0000 0.067766 1.8440 + 14 0.0000 0.093135 2.5343 + 15 0.0000 0.108319 2.9475 + 16 0.0000 0.114282 3.1098 + 17 0.0000 0.154419 4.2020 + 18 0.0000 0.157122 4.2755 + 19 0.0000 0.172359 4.6901 + 20 0.0000 0.179493 4.8843 + 21 0.0000 0.191448 5.2096 + 22 0.0000 0.202447 5.5089 + 23 0.0000 0.234787 6.3889 + 24 0.0000 0.269685 7.3385 + 25 0.0000 0.286893 7.8068 + 26 0.0000 0.309521 8.4225 + 27 0.0000 0.335459 9.1283 + 28 0.0000 0.341476 9.2920 + 29 0.0000 0.362378 9.8608 + 30 0.0000 0.422473 11.4961 + 31 0.0000 0.512362 13.9421 + 32 0.0000 0.532304 14.4847 + 33 0.0000 0.537008 14.6127 + 34 0.0000 0.561141 15.2694 + 35 0.0000 0.604661 16.4537 + 36 0.0000 0.634101 17.2548 + 37 0.0000 0.645763 17.5721 + 38 0.0000 0.700105 19.0508 + 39 0.0000 0.715068 19.4580 + 40 0.0000 0.734023 19.9738 + 41 0.0000 0.742070 20.1928 + 42 0.0000 0.767720 20.8907 + 43 0.0000 0.783019 21.3070 + 44 0.0000 0.814327 22.1590 + 45 0.0000 0.823943 22.4206 + 46 0.0000 0.852454 23.1964 + 47 0.0000 0.882392 24.0111 + 48 0.0000 0.908222 24.7140 + 49 0.0000 0.946536 25.7565 + 50 0.0000 0.974692 26.5227 + 51 0.0000 0.980568 26.6826 + 52 0.0000 0.993866 27.0445 + 53 0.0000 1.019445 27.7405 + 54 0.0000 1.050658 28.5899 + 55 0.0000 1.088863 29.6295 + 56 0.0000 1.157571 31.4991 + 57 0.0000 1.209672 32.9168 + 58 0.0000 1.227885 33.4125 + 59 0.0000 1.281416 34.8691 + 60 0.0000 1.337363 36.3915 + 61 0.0000 1.412038 38.4235 + 62 0.0000 1.458881 39.6982 + 63 0.0000 1.511602 41.1328 + 64 0.0000 1.536256 41.8036 + 65 0.0000 1.569627 42.7117 + 66 0.0000 1.605195 43.6796 + 67 0.0000 1.634536 44.4780 + 68 0.0000 1.654047 45.0089 + 69 0.0000 1.730660 47.0936 + 70 0.0000 1.752276 47.6819 + 71 0.0000 1.787620 48.6436 + 72 0.0000 1.921830 52.2957 + 73 0.0000 1.944825 52.9214 + 74 0.0000 1.968930 53.5773 + 75 0.0000 2.004370 54.5417 + 76 0.0000 2.047528 55.7161 + 77 0.0000 2.078823 56.5677 + 78 0.0000 2.153946 58.6119 + 79 0.0000 2.177261 59.2463 + 80 0.0000 2.255971 61.3881 + 81 0.0000 2.309506 62.8449 + 82 0.0000 2.333831 63.5068 + 83 0.0000 2.380830 64.7857 + 84 0.0000 2.423380 65.9435 + 85 0.0000 2.453999 66.7767 + 86 0.0000 2.466769 67.1242 + 87 0.0000 2.492523 67.8250 + 88 0.0000 2.512873 68.3788 + 89 0.0000 2.553471 69.4835 + 90 0.0000 2.582396 70.2706 + 91 0.0000 2.606736 70.9329 + 92 0.0000 2.665330 72.5273 + 93 0.0000 2.683611 73.0248 + 94 0.0000 2.762954 75.1838 + 95 0.0000 2.814278 76.5804 + 96 0.0000 2.821222 76.7694 + 97 0.0000 2.924255 79.5730 + 98 0.0000 2.968788 80.7848 + 99 0.0000 2.983169 81.1761 + 100 0.0000 3.117891 84.8421 + 101 0.0000 3.169857 86.2562 + 102 0.0000 3.227683 87.8297 + 103 0.0000 3.498421 95.1969 + 104 0.0000 3.694939 100.5444 + 105 0.0000 3.858838 105.0043 + 106 0.0000 4.025744 109.5461 + 107 0.0000 4.160208 113.2050 + 108 0.0000 4.200567 114.3032 + 109 0.0000 4.319792 117.5475 + 110 0.0000 4.362941 118.7217 + 111 0.0000 4.392536 119.5270 + 112 0.0000 4.546429 123.7146 + 113 0.0000 4.614831 125.5759 + 114 0.0000 4.671952 127.1303 + 115 0.0000 4.749564 129.2422 + 116 0.0000 4.815841 131.0457 + 117 0.0000 4.873979 132.6277 + 118 0.0000 4.950059 134.6980 + 119 0.0000 4.983206 135.5999 + 120 0.0000 5.062700 137.7631 + 121 0.0000 5.107677 138.9869 + 122 0.0000 5.182429 141.0211 + 123 0.0000 5.218998 142.0162 + 124 0.0000 5.247714 142.7976 + 125 0.0000 5.284462 143.7975 + 126 0.0000 5.389673 146.6605 + 127 0.0000 5.480795 149.1400 + 128 0.0000 5.517961 150.1514 + 129 0.0000 5.703031 155.1874 + 130 0.0000 5.759866 156.7339 + 131 0.0000 5.959250 162.1594 + 132 0.0000 6.161331 167.6583 + 133 0.0000 6.405294 174.2969 + 134 0.0000 6.485920 176.4909 + 135 0.0000 6.517609 177.3532 + 136 0.0000 6.686246 181.9420 + 137 0.0000 6.712227 182.6490 + 138 0.0000 6.780580 184.5090 + 139 0.0000 6.810149 185.3136 + 140 0.0000 6.862921 186.7496 + 141 0.0000 7.082850 192.7342 + 142 0.0000 7.116964 193.6624 + 143 0.0000 7.149185 194.5392 + 144 0.0000 7.211452 196.2336 + 145 0.0000 7.249623 197.2723 + 146 0.0000 7.272194 197.8865 + 147 0.0000 7.324921 199.3212 + 148 0.0000 7.390875 201.1159 + 149 0.0000 7.464537 203.1204 + 150 0.0000 7.478378 203.4970 + 151 0.0000 7.538359 205.1292 + 152 0.0000 7.573116 206.0750 + 153 0.0000 7.677156 208.9060 + 154 0.0000 7.690663 209.2736 + 155 0.0000 7.908165 215.1921 + 156 0.0000 8.028159 218.4573 + 157 0.0000 8.375564 227.9107 + 158 0.0000 14.021027 381.5316 + 159 0.0000 15.008904 408.4130 + 160 0.0000 15.957911 434.2368 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.349069 0.000000 + 1 N : 0.352372 0.000000 + 2 O : -0.252211 0.000000 + 3 H : 0.248907 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.841701 s : 3.841701 + pz : 1.369391 p : 4.472735 + px : 1.610690 + py : 1.492653 + dz2 : 0.008795 d : 0.030160 + dxz : 0.008340 + dyz : 0.005636 + dx2y2 : 0.005987 + dxy : 0.001403 + f0 : 0.001101 f : 0.004473 + f+1 : 0.001052 + f-1 : 0.000637 + f+2 : 0.000598 + f-2 : 0.000566 + f+3 : 0.000365 + f-3 : 0.000154 + 1 N s : 3.832629 s : 3.832629 + pz : 0.775032 p : 2.642184 + px : 0.768908 + py : 1.098245 + dz2 : 0.028474 d : 0.140950 + dxz : 0.034518 + dyz : 0.019433 + dx2y2 : 0.035144 + dxy : 0.023381 + f0 : 0.007326 f : 0.031864 + f+1 : 0.002001 + f-1 : 0.005091 + f+2 : 0.003024 + f-2 : 0.005915 + f+3 : 0.003029 + f-3 : 0.005477 + 2 O s : 3.873913 s : 3.873913 + pz : 1.662807 p : 4.309119 + px : 1.268007 + py : 1.378305 + dz2 : 0.005307 d : 0.061700 + dxz : 0.006237 + dyz : 0.015052 + dx2y2 : 0.022798 + dxy : 0.012306 + f0 : 0.001018 f : 0.007480 + f+1 : 0.000516 + f-1 : 0.000851 + f+2 : 0.000162 + f-2 : 0.001261 + f+3 : 0.001605 + f-3 : 0.002067 + 3 H s : 0.641460 s : 0.641460 + pz : 0.025071 p : 0.088817 + px : 0.038366 + py : 0.025380 + dz2 : 0.001277 d : 0.020815 + dxz : 0.001408 + dyz : 0.007249 + dx2y2 : 0.007103 + dxy : 0.003778 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.583713 0.000000 + 1 N : -0.251547 0.000000 + 2 O : 0.246614 0.000000 + 3 H : -0.578780 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.125399 s : 3.125399 + pz : 1.254853 p : 3.941068 + px : 1.338527 + py : 1.347688 + dz2 : 0.069516 d : 0.269785 + dxz : 0.078810 + dyz : 0.053528 + dx2y2 : 0.026043 + dxy : 0.041889 + f0 : 0.012218 f : 0.080034 + f+1 : 0.018215 + f-1 : 0.014566 + f+2 : 0.012182 + f-2 : 0.014809 + f+3 : 0.006009 + f-3 : 0.002036 + 1 N s : 3.026466 s : 3.026466 + pz : 0.827818 p : 2.835777 + px : 0.837458 + py : 1.170501 + dz2 : 0.196246 d : 0.939199 + dxz : 0.223382 + dyz : 0.145954 + dx2y2 : 0.184846 + dxy : 0.188772 + f0 : 0.084622 f : 0.450105 + f+1 : 0.051582 + f-1 : 0.058333 + f+2 : 0.033506 + f-2 : 0.089341 + f+3 : 0.063271 + f-3 : 0.069449 + 2 O s : 3.310206 s : 3.310206 + pz : 1.375061 p : 3.999486 + px : 1.228681 + py : 1.395744 + dz2 : 0.050739 d : 0.326957 + dxz : 0.055596 + dyz : 0.039887 + dx2y2 : 0.077948 + dxy : 0.102787 + f0 : 0.010699 f : 0.116738 + f+1 : 0.010498 + f-1 : 0.016932 + f+2 : 0.004634 + f-2 : 0.021296 + f+3 : 0.030267 + f-3 : 0.022412 + 3 H s : 0.621839 s : 0.621839 + pz : 0.145824 p : 0.564907 + px : 0.174282 + py : 0.244802 + dz2 : 0.032790 d : 0.392033 + dxz : 0.047470 + dyz : 0.094998 + dx2y2 : 0.116967 + dxy : 0.099808 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3491 8.0000 -0.3491 1.8186 1.8186 -0.0000 + 1 N 6.6476 7.0000 0.3524 2.5640 2.5640 0.0000 + 2 O 8.2522 8.0000 -0.2522 1.7676 1.7676 0.0000 + 3 H 0.7511 1.0000 0.2489 1.0065 1.0065 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8076 B( 0-O , 3-H ) : 0.9507 B( 1-N , 2-O ) : 1.7039 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.445 sec +Sum of individual times .... 1.180 sec ( 81.7%) + +Fock matrix formation .... 0.920 sec ( 63.7%) +Diagonalization .... 0.099 sec ( 6.9%) +Density matrix formation .... 0.008 sec ( 0.5%) +Population analysis .... 0.067 sec ( 4.6%) +Initial guess .... 0.009 sec ( 0.6%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.4%) +DIIS solution .... 0.077 sec ( 5.3%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.204 sec +Reference energy ... -204.710000881 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.373 sec +AO-integral generation ... 0.142 sec +Half transformation ... 0.079 sec +K-integral sorting ... 5.378 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.022 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.029 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.030 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.040 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.346 sec +AO-integral generation ... 0.244 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.049 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.150 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.251 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090114743 +EMP2(bb)= -0.090114743 +EMP2(ab)= -0.516296405 + +Initial guess performed in 0.131 sec +E(0) ... -204.710000881 +E(MP2) ... -0.696525891 +Initial E(tot) ... -205.406526772 + ... 0.188245244 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.406526772 -0.696525891 -0.000000000 0.021677918 2.73 0.000000746 + *** Turning on DIIS *** + 1 -205.378283617 -0.668282736 0.028243155 0.009517730 2.71 0.056472831 + 2 -205.397728590 -0.687727709 -0.019444973 0.004595375 2.78 0.059506462 + 3 -205.401515265 -0.691514385 -0.003786675 0.001680367 2.82 0.073237970 + 4 -205.403073474 -0.693072593 -0.001558209 0.001397928 2.79 0.079684094 + 5 -205.403604441 -0.693603561 -0.000530967 0.000863487 2.89 0.084889069 + 6 -205.403706842 -0.693705962 -0.000102401 0.000532475 2.82 0.087563249 + 7 -205.403752001 -0.693751120 -0.000045159 0.000265841 2.88 0.088878192 + 8 -205.403763683 -0.693762802 -0.000011681 0.000128645 2.89 0.089469620 + 9 -205.403760216 -0.693759335 0.000003466 0.000075181 2.81 0.089675778 + 10 -205.403765753 -0.693764872 -0.000005537 0.000043151 2.79 0.089760575 + 11 -205.403762236 -0.693761355 0.000003517 0.000029363 2.77 0.089755620 + 12 -205.403764560 -0.693763679 -0.000002323 0.000017787 2.79 0.089776265 + 13 -205.403764223 -0.693763342 0.000000336 0.000010268 2.94 0.089771299 + 14 -205.403764618 -0.693763737 -0.000000395 0.000004579 2.80 0.089778479 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.710000881 +E(CORR) ... -0.693763737 +E(TOT) ... -205.403764618 +Singles norm **1/2 ... 0.089778479 ( 0.044889239, 0.044889239) +T1 diagnostic ... 0.021160990 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.056295 + 9a-> 13a 9b-> 13b 0.050166 + 9a-> 13a 8b-> 13b 0.039697 + 8a-> 13a 9b-> 13b 0.039697 + 8b-> 13b -1b-> -1b 0.034275 + 8a-> 13a -1a-> -1a 0.034275 + 11a-> 13a 11b-> 13b 0.030042 + 5a-> 13a 5b-> 13b 0.028438 + 10b-> 13b -1b-> -1b 0.028126 + 10a-> 13a -1a-> -1a 0.028126 + 11a-> 25a 11b-> 25b 0.027136 + 11a-> 25a -1a-> -1a 0.023131 + 11b-> 25b -1b-> -1b 0.023131 + 9a-> 13a 10b-> 13b 0.022094 + 10a-> 13a 9b-> 13b 0.022094 + 8a-> 22a 8b-> 13b 0.020645 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034518066 + alpha-alpha-alpha ... -0.000879697 ( 2.5%) + alpha-alpha-beta ... -0.016379336 ( 47.5%) + alpha-beta -beta ... -0.016379336 ( 47.5%) + beta -beta -beta ... -0.000879697 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034518066 + +Final correlation energy ... -0.728281803 +E(CCSD) ... -205.403764618 +E(CCSD(T)) ... -205.438282684 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210355019 sqrt= 1.100161361 +W(HF) = 0.826203869 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.281190 -0.000000 + 1 N : 0.172207 0.000000 + 2 O : -0.128165 -0.000000 + 3 H : 0.237148 -0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.824197 s : 3.824197 + pz : 1.343262 p : 4.388126 + px : 1.579202 + py : 1.465662 + dz2 : 0.014553 d : 0.060686 + dxz : 0.013156 + dyz : 0.012582 + dx2y2 : 0.012277 + dxy : 0.008118 + f0 : 0.001667 f : 0.008181 + f+1 : 0.001272 + f-1 : 0.001201 + f+2 : 0.001092 + f-2 : 0.001118 + f+3 : 0.001020 + f-3 : 0.000811 + 1 N s : 3.886499 s : 3.886499 + pz : 0.826837 p : 2.740346 + px : 0.836256 + py : 1.077253 + dz2 : 0.036407 d : 0.170145 + dxz : 0.041758 + dyz : 0.025240 + dx2y2 : 0.039094 + dxy : 0.027646 + f0 : 0.006869 f : 0.030804 + f+1 : 0.001934 + f-1 : 0.005237 + f+2 : 0.003198 + f-2 : 0.005669 + f+3 : 0.003146 + f-3 : 0.004749 + 2 O s : 3.860517 s : 3.860517 + pz : 1.590337 p : 4.174424 + px : 1.236892 + py : 1.347195 + dz2 : 0.010743 d : 0.083295 + dxz : 0.012754 + dyz : 0.019163 + dx2y2 : 0.025921 + dxy : 0.014715 + f0 : 0.001445 f : 0.009929 + f+1 : 0.000982 + f-1 : 0.001274 + f+2 : 0.000726 + f-2 : 0.001600 + f+3 : 0.001813 + f-3 : 0.002089 + 3 H s : 0.650969 s : 0.650969 + pz : 0.029099 p : 0.093724 + px : 0.041595 + py : 0.023030 + dz2 : 0.001030 d : 0.018159 + dxz : 0.001518 + dyz : 0.006425 + dx2y2 : 0.006022 + dxy : 0.003165 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.593063 -0.000000 + 1 N : -0.297056 0.000000 + 2 O : 0.286617 -0.000000 + 3 H : -0.582625 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.131379 s : 3.131379 + pz : 1.241543 p : 3.887339 + px : 1.317970 + py : 1.327826 + dz2 : 0.075555 d : 0.301074 + dxz : 0.085555 + dyz : 0.058663 + dx2y2 : 0.032132 + dxy : 0.049169 + f0 : 0.014004 f : 0.087144 + f+1 : 0.019844 + f-1 : 0.014901 + f+2 : 0.013053 + f-2 : 0.015608 + f+3 : 0.006877 + f-3 : 0.002858 + 1 N s : 3.031811 s : 3.031811 + pz : 0.851787 p : 2.879300 + px : 0.876966 + py : 1.150547 + dz2 : 0.200975 d : 0.945908 + dxz : 0.227420 + dyz : 0.140456 + dx2y2 : 0.181302 + dxy : 0.195755 + f0 : 0.080789 f : 0.440037 + f+1 : 0.052394 + f-1 : 0.057659 + f+2 : 0.032821 + f-2 : 0.086284 + f+3 : 0.062380 + f-3 : 0.067710 + 2 O s : 3.312594 s : 3.312594 + pz : 1.331115 p : 3.918419 + px : 1.210467 + py : 1.376836 + dz2 : 0.056823 d : 0.357149 + dxz : 0.060120 + dyz : 0.046095 + dx2y2 : 0.086306 + dxy : 0.107805 + f0 : 0.011670 f : 0.125221 + f+1 : 0.011589 + f-1 : 0.017100 + f+2 : 0.005794 + f-2 : 0.022214 + f+3 : 0.031004 + f-3 : 0.025850 + 3 H s : 0.623700 s : 0.623700 + pz : 0.146998 p : 0.577321 + px : 0.179120 + py : 0.251203 + dz2 : 0.032862 d : 0.381603 + dxz : 0.045794 + dyz : 0.092065 + dx2y2 : 0.113243 + dxy : 0.097639 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2812 8.0000 -0.2812 2.1787 1.7214 0.4573 + 1 N 6.8278 7.0000 0.1722 2.8359 2.3494 0.4865 + 2 O 8.1282 8.0000 -0.1282 2.1564 1.6580 0.4985 + 3 H 0.7629 1.0000 0.2371 1.0239 0.9494 0.0744 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7404 B( 0-O , 3-H ) : 0.8844 B( 1-N , 2-O ) : 1.5527 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 57.505 sec + +Fock Matrix Formation ... 0.204 sec ( 0.4%) +Initial Guess ... 0.131 sec ( 0.2%) +DIIS Solver ... 1.928 sec ( 3.4%) +State Vector Update ... 0.092 sec ( 0.2%) +Sigma-vector construction ... 40.177 sec ( 69.9%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.030 sec ( 0.1% of sigma) + (0-ext) ... 0.074 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.028 sec ( 0.1% of sigma) + (2-ext) ... 1.000 sec ( 2.5% of sigma) + (4-ext) ... 22.231 sec ( 55.3% of sigma) + ... 1.394 sec ( 3.5% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.114 sec ( 0.3% of sigma) + Fock-dressing ... 2.231 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.080 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.211 sec ( 25.4% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.969 sec ( 12.1% of ALL) + I/O of integral and amplitudes ... 0.849 sec ( 12.2% of (T)) + External N**7 contributions ... 4.033 sec ( 57.9% of (T)) + Internal N**7 contributions ... 0.309 sec ( 4.4% of (T)) + N**6 triples energy contributions ... 1.586 sec ( 22.8% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.438282684231 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.030.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.030.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.527879, -0.275394 -0.288204) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.74966 -0.18491 -0.78845 +Nuclear contribution : -1.12317 0.63614 0.65761 + ----------------------------------------- +Total Dipole Moment : -0.37351 0.45122 -0.13084 + ----------------------------------------- +Magnitude (a.u.) : 0.60019 +Magnitude (Debye) : 1.52557 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.732139 0.411513 0.365949 +Rotational constants in MHz : 81907.479678 12336.840936 10970.882676 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.068777 0.313857 0.506947 +x,y,z [Debye]: 0.174819 0.797761 1.288556 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.527879, -0.275394 -0.288204) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.87014 -0.11217 -0.80368 +Nuclear contribution : -1.12317 0.63614 0.65761 + ----------------------------------------- +Total Dipole Moment : -0.25303 0.52396 -0.14607 + ----------------------------------------- +Magnitude (a.u.) : 0.59991 +Magnitude (Debye) : 1.52486 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.732139 0.411513 0.365949 +Rotational constants in MHz : 81907.479678 12336.840936 10970.882676 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.042618 0.385809 0.457420 +x,y,z [Debye]: -0.108327 0.980648 1.162668 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 31 * + * * + * Dihedral ( 2, 1, 0, 3) : 65.45454545 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0360579097 RMS(Int)= 0.0001837030 + Iter 1: RMS(Cart)= 0.0000463863 RMS(Int)= 0.0000000484 + Iter 2: RMS(Cart)= 0.0000000122 RMS(Int)= 0.0000000000 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4693 0.000000 + 2. B(O 2,N 1) 1.1742 0.000000 + 3. B(H 3,O 0) 0.9736 0.000000 + 4. A(N 1,O 0,H 3) 104.4142 0.000000 + 5. A(O 0,N 1,O 2) 112.2585 0.000000 + 6. D(O 2,N 1,O 0,H 3) 65.4545 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.440345 -0.297430 0.718927 + N 0.302059 -0.530106 -0.527521 + O 1.089939 0.314103 -0.740120 + H -0.951652 0.513433 0.548715 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.832132 -0.562060 1.358574 + 1 N 7.0000 0 14.007 0.570809 -1.001755 -0.996871 + 2 O 8.0000 0 15.999 2.059687 0.593568 -1.398624 + 3 H 1.0000 0 1.008 -1.798362 0.970247 1.036921 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.468428412669 0.00000000 0.00000000 + O 2 1 0 1.172576088405 112.39608056 0.00000000 + H 1 2 3 0.971330828622 104.56960132 57.27272713 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.774927547214 0.00000000 0.00000000 + O 2 1 0 2.215847678270 112.39608056 0.00000000 + H 1 2 3 1.835549251531 104.56960132 57.27272713 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2233 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2704 + la=0 lb=0: 552 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.784955371630 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.7849553716 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.702e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7038826082 0.000000000000 0.00146739 0.00004937 0.0163994 0.7000 + 1 -204.7046804326 -0.000797824404 0.00140351 0.00004583 0.0136252 0.7000 + ***Turning on DIIS*** + 2 -204.7053719081 -0.000691475574 0.00387372 0.00012721 0.0111215 0.0000 + 3 -204.7085082037 -0.003136295602 0.00176540 0.00006052 0.0045869 0.0000 + 4 -204.7069284912 0.001579712563 0.00085247 0.00003283 0.0018297 0.0000 + 5 -204.7087077127 -0.001779221502 0.00111967 0.00003987 0.0009773 0.0000 + 6 -204.7081558093 0.000551903373 0.00065998 0.00002579 0.0008227 0.0000 + 7 -204.7075272078 0.000628601506 0.00042948 0.00001612 0.0003814 0.0000 + 8 -204.7085341523 -0.001006944542 0.00025379 0.00001035 0.0002263 0.0000 + 9 -204.7080261501 0.000508002197 0.00014948 0.00000441 0.0000931 0.0000 + 10 -204.7080451226 -0.000018972420 0.00005561 0.00000175 0.0000518 0.0000 + 11 -204.7082337177 -0.000188595127 0.00003320 0.00000084 0.0000257 0.0000 + 12 -204.7081252336 0.000108484136 0.00000782 0.00000023 0.0000065 0.0000 + 13 -204.7081481430 -0.000022909441 0.00000229 0.00000008 0.0000027 0.0000 + 14 -204.7081408425 0.000007300546 0.00000098 0.00000004 0.0000020 0.0000 + 15 -204.7081371829 0.000003659529 0.00000085 0.00000003 0.0000019 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 16 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70814131 Eh -5570.39172 eV + +Components: +Nuclear Repulsion : 68.78495537 Eh 1871.73379 eV +Electronic Energy : -273.49309668 Eh -7442.12551 eV +One Electron Energy: -417.24988263 Eh -11353.94653 eV +Two Electron Energy: 143.75678594 Eh 3911.82102 eV + +Virial components: +Potential Energy : -408.93243754 Eh -11127.61734 eV +Kinetic Energy : 204.22429623 Eh 5557.22562 eV +Virial Ratio : 2.00236918 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -4.1272e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.7022e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.6467e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.0308e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.685355 -562.8771 + 1 1.0000 -20.625423 -561.2463 + 2 1.0000 -15.803765 -430.0423 + 3 1.0000 -1.611040 -43.8386 + 4 1.0000 -1.382906 -37.6308 + 5 1.0000 -0.958214 -26.0743 + 6 1.0000 -0.769817 -20.9478 + 7 1.0000 -0.734478 -19.9862 + 8 1.0000 -0.698235 -18.9999 + 9 1.0000 -0.601509 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2.5317 + 15 0.0000 0.107202 2.9171 + 16 0.0000 0.113358 3.0846 + 17 0.0000 0.155136 4.2215 + 18 0.0000 0.156455 4.2574 + 19 0.0000 0.173958 4.7337 + 20 0.0000 0.178682 4.8622 + 21 0.0000 0.190804 5.1920 + 22 0.0000 0.202264 5.5039 + 23 0.0000 0.235450 6.4069 + 24 0.0000 0.271902 7.3988 + 25 0.0000 0.288717 7.8564 + 26 0.0000 0.309139 8.4121 + 27 0.0000 0.334676 9.1070 + 28 0.0000 0.339359 9.2344 + 29 0.0000 0.357180 9.7194 + 30 0.0000 0.421934 11.4814 + 31 0.0000 0.510542 13.8926 + 32 0.0000 0.532306 14.4848 + 33 0.0000 0.540250 14.7009 + 34 0.0000 0.562095 15.2954 + 35 0.0000 0.602509 16.3951 + 36 0.0000 0.632742 17.2178 + 37 0.0000 0.643645 17.5145 + 38 0.0000 0.704639 19.1742 + 39 0.0000 0.718743 19.5580 + 40 0.0000 0.733241 19.9525 + 41 0.0000 0.743858 20.2414 + 42 0.0000 0.767168 20.8757 + 43 0.0000 0.784171 21.3384 + 44 0.0000 0.811682 22.0870 + 45 0.0000 0.820937 22.3388 + 46 0.0000 0.855095 23.2683 + 47 0.0000 0.881533 23.9877 + 48 0.0000 0.900124 24.4936 + 49 0.0000 0.952348 25.9147 + 50 0.0000 0.971399 26.4331 + 51 0.0000 0.980342 26.6765 + 52 0.0000 0.983783 26.7701 + 53 0.0000 1.020052 27.7570 + 54 0.0000 1.047154 28.4945 + 55 0.0000 1.090600 29.6767 + 56 0.0000 1.157076 31.4856 + 57 0.0000 1.214969 33.0610 + 58 0.0000 1.229665 33.4609 + 59 0.0000 1.281270 34.8651 + 60 0.0000 1.324673 36.0462 + 61 0.0000 1.409159 38.3452 + 62 0.0000 1.462808 39.8050 + 63 0.0000 1.508301 41.0430 + 64 0.0000 1.535967 41.7958 + 65 0.0000 1.581281 43.0289 + 66 0.0000 1.597495 43.4701 + 67 0.0000 1.636141 44.5217 + 68 0.0000 1.652753 44.9737 + 69 0.0000 1.734810 47.2066 + 70 0.0000 1.748150 47.5696 + 71 0.0000 1.785219 48.5783 + 72 0.0000 1.926372 52.4192 + 73 0.0000 1.933667 52.6177 + 74 0.0000 1.969301 53.5874 + 75 0.0000 2.008827 54.6630 + 76 0.0000 2.044815 55.6423 + 77 0.0000 2.087444 56.8023 + 78 0.0000 2.148402 58.4610 + 79 0.0000 2.183631 59.4196 + 80 0.0000 2.265264 61.6410 + 81 0.0000 2.309635 62.8484 + 82 0.0000 2.328636 63.3654 + 83 0.0000 2.370948 64.5168 + 84 0.0000 2.419946 65.8501 + 85 0.0000 2.455942 66.8296 + 86 0.0000 2.463411 67.0328 + 87 0.0000 2.488383 67.7123 + 88 0.0000 2.511228 68.3340 + 89 0.0000 2.553073 69.4726 + 90 0.0000 2.587373 70.4060 + 91 0.0000 2.603887 70.8554 + 92 0.0000 2.664121 72.4944 + 93 0.0000 2.690422 73.2101 + 94 0.0000 2.758883 75.0730 + 95 0.0000 2.805014 76.3283 + 96 0.0000 2.834073 77.1190 + 97 0.0000 2.927557 79.6629 + 98 0.0000 2.968023 80.7640 + 99 0.0000 2.984844 81.2217 + 100 0.0000 3.111891 84.6789 + 101 0.0000 3.170388 86.2706 + 102 0.0000 3.220861 87.6441 + 103 0.0000 3.496387 95.1415 + 104 0.0000 3.698771 100.6487 + 105 0.0000 3.846108 104.6579 + 106 0.0000 4.029586 109.6506 + 107 0.0000 4.161448 113.2388 + 108 0.0000 4.201831 114.3376 + 109 0.0000 4.294664 116.8638 + 110 0.0000 4.369335 118.8956 + 111 0.0000 4.395708 119.6133 + 112 0.0000 4.541454 123.5792 + 113 0.0000 4.618793 125.6838 + 114 0.0000 4.671331 127.1134 + 115 0.0000 4.732447 128.7764 + 116 0.0000 4.822356 131.2230 + 117 0.0000 4.880780 132.8128 + 118 0.0000 4.941831 134.4741 + 119 0.0000 4.975669 135.3948 + 120 0.0000 5.058137 137.6389 + 121 0.0000 5.106663 138.9594 + 122 0.0000 5.177095 140.8759 + 123 0.0000 5.211649 141.8162 + 124 0.0000 5.243931 142.6946 + 125 0.0000 5.284225 143.7911 + 126 0.0000 5.392877 146.7477 + 127 0.0000 5.503939 149.7698 + 128 0.0000 5.517066 150.1270 + 129 0.0000 5.696348 155.0055 + 130 0.0000 5.750856 156.4887 + 131 0.0000 5.963864 162.2850 + 132 0.0000 6.163231 167.7100 + 133 0.0000 6.415396 174.5718 + 134 0.0000 6.484728 176.4584 + 135 0.0000 6.515823 177.3046 + 136 0.0000 6.686445 181.9474 + 137 0.0000 6.709868 182.5848 + 138 0.0000 6.778601 184.4551 + 139 0.0000 6.813816 185.4134 + 140 0.0000 6.851568 186.4406 + 141 0.0000 7.081675 192.7022 + 142 0.0000 7.112669 193.5456 + 143 0.0000 7.139860 194.2855 + 144 0.0000 7.204305 196.0391 + 145 0.0000 7.251071 197.3117 + 146 0.0000 7.275334 197.9719 + 147 0.0000 7.321042 199.2157 + 148 0.0000 7.388298 201.0458 + 149 0.0000 7.459144 202.9736 + 150 0.0000 7.475430 203.4168 + 151 0.0000 7.546822 205.3595 + 152 0.0000 7.580225 206.2684 + 153 0.0000 7.667504 208.6434 + 154 0.0000 7.693021 209.3377 + 155 0.0000 7.902930 215.0497 + 156 0.0000 8.004910 217.8247 + 157 0.0000 8.385391 228.1781 + 158 0.0000 14.015630 381.3847 + 159 0.0000 14.972905 407.4335 + 160 0.0000 15.909430 432.9176 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.354451 0.000000 + 1 N : 0.349250 0.000000 + 2 O : -0.246548 0.000000 + 3 H : 0.251749 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.846456 s : 3.846456 + pz : 1.346074 p : 4.474241 + px : 1.603897 + py : 1.524269 + dz2 : 0.009255 d : 0.029324 + dxz : 0.008283 + dyz : 0.005688 + dx2y2 : 0.004396 + dxy : 0.001703 + f0 : 0.001217 f : 0.004430 + f+1 : 0.000999 + f-1 : 0.000693 + f+2 : 0.000485 + f-2 : 0.000470 + f+3 : 0.000401 + f-3 : 0.000165 + 1 N s : 3.827923 s : 3.827923 + pz : 0.792675 p : 2.650417 + px : 0.784787 + py : 1.072955 + dz2 : 0.028284 d : 0.140635 + dxz : 0.035669 + dyz : 0.019458 + dx2y2 : 0.035410 + dxy : 0.021813 + f0 : 0.007694 f : 0.031775 + f+1 : 0.002267 + f-1 : 0.005194 + f+2 : 0.002863 + f-2 : 0.005861 + f+3 : 0.003155 + f-3 : 0.004741 + 2 O s : 3.876407 s : 3.876407 + pz : 1.687481 p : 4.301586 + px : 1.244474 + py : 1.369631 + dz2 : 0.004929 d : 0.061137 + dxz : 0.006864 + dyz : 0.013544 + dx2y2 : 0.024277 + dxy : 0.011524 + f0 : 0.001064 f : 0.007418 + f+1 : 0.000549 + f-1 : 0.000760 + f+2 : 0.000078 + f-2 : 0.001283 + f+3 : 0.001770 + f-3 : 0.001914 + 3 H s : 0.639311 s : 0.639311 + pz : 0.023626 p : 0.088414 + px : 0.037829 + py : 0.026959 + dz2 : 0.001390 d : 0.020526 + dxz : 0.001982 + dyz : 0.006367 + dx2y2 : 0.008218 + dxy : 0.002568 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.579228 0.000000 + 1 N : -0.252669 0.000000 + 2 O : 0.245817 0.000000 + 3 H : -0.572376 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.126503 s : 3.126503 + pz : 1.245899 p : 3.945114 + px : 1.339543 + py : 1.359672 + dz2 : 0.075195 d : 0.269294 + dxz : 0.076718 + dyz : 0.054664 + dx2y2 : 0.021862 + dxy : 0.040855 + f0 : 0.013923 f : 0.079861 + f+1 : 0.018017 + f-1 : 0.015454 + f+2 : 0.011683 + f-2 : 0.013426 + f+3 : 0.005778 + f-3 : 0.001581 + 1 N s : 3.027241 s : 3.027241 + pz : 0.842727 p : 2.838651 + px : 0.860734 + py : 1.135191 + dz2 : 0.199334 d : 0.937620 + dxz : 0.230559 + dyz : 0.144043 + dx2y2 : 0.173145 + dxy : 0.190539 + f0 : 0.089621 f : 0.449157 + f+1 : 0.053292 + f-1 : 0.058235 + f+2 : 0.031035 + f-2 : 0.088635 + f+3 : 0.063953 + f-3 : 0.064386 + 2 O s : 3.313628 s : 3.313628 + pz : 1.393465 p : 3.997644 + px : 1.231923 + py : 1.372256 + dz2 : 0.050631 d : 0.326296 + dxz : 0.059715 + dyz : 0.037375 + dx2y2 : 0.070567 + dxy : 0.108009 + f0 : 0.011219 f : 0.116614 + f+1 : 0.011672 + f-1 : 0.015696 + f+2 : 0.004449 + f-2 : 0.021443 + f+3 : 0.030338 + f-3 : 0.021797 + 3 H s : 0.620968 s : 0.620968 + pz : 0.144631 p : 0.562777 + px : 0.180496 + py : 0.237650 + dz2 : 0.032190 d : 0.388631 + dxz : 0.053716 + dyz : 0.087940 + dx2y2 : 0.118319 + dxy : 0.096466 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3545 8.0000 -0.3545 1.8137 1.8137 -0.0000 + 1 N 6.6507 7.0000 0.3493 2.5712 2.5712 0.0000 + 2 O 8.2465 8.0000 -0.2465 1.7771 1.7771 -0.0000 + 3 H 0.7483 1.0000 0.2517 1.0018 1.0018 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8055 B( 0-O , 3-H ) : 0.9500 B( 1-N , 2-O ) : 1.7164 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.515 sec +Sum of individual times .... 2.238 sec ( 89.0%) + +Fock matrix formation .... 1.800 sec ( 71.6%) +Diagonalization .... 0.187 sec ( 7.4%) +Density matrix formation .... 0.014 sec ( 0.5%) +Population analysis .... 0.068 sec ( 2.7%) +Initial guess .... 0.009 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.2%) +DIIS solution .... 0.160 sec ( 6.4%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.223 sec +Reference energy ... -204.708140217 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.381 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.388 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.022 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.030 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.017 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.023 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.344 sec +AO-integral generation ... 0.241 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.049 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.154 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.252 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090019597 +EMP2(bb)= -0.090019597 +EMP2(ab)= -0.516332831 + +Initial guess performed in 0.134 sec +E(0) ... -204.708140217 +E(MP2) ... -0.696372025 +Initial E(tot) ... -205.404512242 + ... 0.188281953 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.404512242 -0.696372025 -0.000000000 0.020651119 2.75 0.000002796 + *** Turning on DIIS *** + 1 -205.376512172 -0.668371955 0.028000069 0.009903001 2.72 0.055846048 + 2 -205.395914650 -0.687774433 -0.019402478 0.004318719 2.79 0.058853441 + 3 -205.399709089 -0.691568872 -0.003794438 0.001841493 2.83 0.072231512 + 4 -205.401253258 -0.693113041 -0.001544169 0.001135738 2.84 0.078400857 + 5 -205.401762911 -0.693622694 -0.000509652 0.000718179 2.89 0.083211762 + 6 -205.401855206 -0.693714989 -0.000092295 0.000447846 2.83 0.085586456 + 7 -205.401894602 -0.693754385 -0.000039396 0.000242253 2.89 0.086718024 + 8 -205.401904536 -0.693764319 -0.000009934 0.000151738 2.92 0.087250695 + 9 -205.401901581 -0.693761364 0.000002955 0.000090059 2.81 0.087463529 + 10 -205.401906846 -0.693766629 -0.000005264 0.000049156 2.77 0.087549818 + 11 -205.401903360 -0.693763143 0.000003486 0.000030634 2.80 0.087558603 + 12 -205.401905944 -0.693765727 -0.000002585 0.000018338 2.77 0.087575572 + 13 -205.401905577 -0.693765360 0.000000367 0.000009716 2.87 0.087575715 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.708140217 +E(CORR) ... -0.693765360 +E(TOT) ... -205.401905577 +Singles norm **1/2 ... 0.087575715 ( 0.043787857, 0.043787857) +T1 diagnostic ... 0.020641794 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.057927 + 8a-> 13a 8b-> 13b 0.053699 + 8a-> 13a 9b-> 13b 0.042469 + 9a-> 13a 8b-> 13b 0.042469 + 8a-> 13a -1a-> -1a 0.032200 + 8b-> 13b -1b-> -1b 0.032200 + 11a-> 13a 11b-> 13b 0.030308 + 5a-> 13a 5b-> 13b 0.028730 + 10a-> 13a -1a-> -1a 0.022973 + 10b-> 13b -1b-> -1b 0.022973 + 11a-> 25a 11b-> 25b 0.022484 + 9a-> 22a 9b-> 13b 0.022358 + 9a-> 13a 9b-> 22b 0.022358 + 11a-> 25a -1a-> -1a 0.019870 + 11b-> 25b -1b-> -1b 0.019870 + 8a-> 22a 8b-> 13b 0.019306 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034387328 + alpha-alpha-alpha ... -0.000871676 ( 2.5%) + alpha-alpha-beta ... -0.016321989 ( 47.5%) + alpha-beta -beta ... -0.016321989 ( 47.5%) + beta -beta -beta ... -0.000871676 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034387328 + +Final correlation energy ... -0.728152688 +E(CCSD) ... -205.401905577 +E(CCSD(T)) ... -205.436292905 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209877751 sqrt= 1.099944431 +W(HF) = 0.826529787 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.290490 0.000000 + 1 N : 0.172564 -0.000000 + 2 O : -0.121813 -0.000000 + 3 H : 0.239739 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.827112 s : 3.827112 + pz : 1.322379 p : 4.395394 + px : 1.576304 + py : 1.496712 + dz2 : 0.014695 d : 0.059852 + dxz : 0.013166 + dyz : 0.012633 + dx2y2 : 0.011067 + dxy : 0.008290 + f0 : 0.001732 f : 0.008132 + f+1 : 0.001232 + f-1 : 0.001242 + f+2 : 0.001007 + f-2 : 0.001044 + f+3 : 0.001052 + f-3 : 0.000823 + 1 N s : 3.882846 s : 3.882846 + pz : 0.839921 p : 2.743797 + px : 0.843870 + py : 1.060006 + dz2 : 0.036156 d : 0.170096 + dxz : 0.043336 + dyz : 0.025709 + dx2y2 : 0.038454 + dxy : 0.026441 + f0 : 0.007228 f : 0.030698 + f+1 : 0.002153 + f-1 : 0.005324 + f+2 : 0.003150 + f-2 : 0.005600 + f+3 : 0.003177 + f-3 : 0.004066 + 2 O s : 3.862743 s : 3.862743 + pz : 1.612358 p : 4.166650 + px : 1.215950 + py : 1.338342 + dz2 : 0.010368 d : 0.082569 + dxz : 0.013407 + dyz : 0.018022 + dx2y2 : 0.026583 + dxy : 0.014189 + f0 : 0.001495 f : 0.009851 + f+1 : 0.001013 + f-1 : 0.001196 + f+2 : 0.000668 + f-2 : 0.001614 + f+3 : 0.001914 + f-3 : 0.001952 + 3 H s : 0.648286 s : 0.648286 + pz : 0.027579 p : 0.094142 + px : 0.040740 + py : 0.025822 + dz2 : 0.001147 d : 0.017834 + dxz : 0.001976 + dyz : 0.005621 + dx2y2 : 0.007095 + dxy : 0.001995 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.586800 0.000000 + 1 N : -0.296809 -0.000000 + 2 O : 0.287251 -0.000000 + 3 H : -0.577241 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.131979 s : 3.131979 + pz : 1.234429 p : 3.893978 + px : 1.320796 + py : 1.338752 + dz2 : 0.081044 d : 0.300328 + dxz : 0.083396 + dyz : 0.059828 + dx2y2 : 0.027842 + dxy : 0.048218 + f0 : 0.015664 f : 0.086915 + f+1 : 0.019688 + f-1 : 0.015761 + f+2 : 0.012450 + f-2 : 0.014345 + f+3 : 0.006637 + f-3 : 0.002370 + 1 N s : 3.032658 s : 3.032658 + pz : 0.863669 p : 2.879986 + px : 0.895052 + py : 1.121265 + dz2 : 0.204655 d : 0.944879 + dxz : 0.234063 + dyz : 0.139170 + dx2y2 : 0.169211 + dxy : 0.197779 + f0 : 0.085837 f : 0.439285 + f+1 : 0.054145 + f-1 : 0.057556 + f+2 : 0.030439 + f-2 : 0.085342 + f+3 : 0.062733 + f-3 : 0.063234 + 2 O s : 3.316195 s : 3.316195 + pz : 1.347068 p : 3.915819 + px : 1.215077 + py : 1.353675 + dz2 : 0.056620 d : 0.355771 + dxz : 0.064021 + dyz : 0.043242 + dx2y2 : 0.079071 + dxy : 0.112816 + f0 : 0.012136 f : 0.124964 + f+1 : 0.012676 + f-1 : 0.015868 + f+2 : 0.005421 + f-2 : 0.022396 + f+3 : 0.031511 + f-3 : 0.024956 + 3 H s : 0.622491 s : 0.622491 + pz : 0.145831 p : 0.576189 + px : 0.185831 + py : 0.244528 + dz2 : 0.032429 d : 0.378561 + dxz : 0.051758 + dyz : 0.085313 + dx2y2 : 0.114170 + dxy : 0.094890 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2905 8.0000 -0.2905 2.1662 1.7101 0.4561 + 1 N 6.8274 7.0000 0.1726 2.8399 2.3507 0.4892 + 2 O 8.1218 8.0000 -0.1218 2.1635 1.6639 0.4996 + 3 H 0.7603 1.0000 0.2397 1.0206 0.9462 0.0744 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7327 B( 0-O , 3-H ) : 0.8856 B( 1-N , 2-O ) : 1.5647 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 54.616 sec + +Fock Matrix Formation ... 0.223 sec ( 0.4%) +Initial Guess ... 0.134 sec ( 0.2%) +DIIS Solver ... 1.824 sec ( 3.3%) +State Vector Update ... 0.083 sec ( 0.2%) +Sigma-vector construction ... 37.561 sec ( 68.8%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.023 sec ( 0.1% of sigma) + (0-ext) ... 0.068 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (2-ext) ... 0.934 sec ( 2.5% of sigma) + (4-ext) ... 20.721 sec ( 55.2% of sigma) + ... 1.355 sec ( 3.6% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.106 sec ( 0.3% of sigma) + Fock-dressing ... 2.121 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.074 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.496 sec ( 25.3% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.825 sec ( 12.5% of ALL) + I/O of integral and amplitudes ... 0.840 sec ( 12.3% of (T)) + External N**7 contributions ... 3.909 sec ( 57.3% of (T)) + Internal N**7 contributions ... 0.312 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.683 sec ( 24.7% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.436292905183 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.009838689 0.000415594 0.002192901 + 2 N : -0.010133287 0.001762685 -0.001039449 + 3 O : 0.006944327 -0.000592104 0.001866688 + 4 H : -0.006649729 -0.001586175 -0.003020140 + +Norm of the cartesian gradient ... 0.017792336 +RMS gradient ... 0.005136205 +MAX gradient ... 0.010133287 + +------- +TIMINGS +------- + +Total numerical gradient time ... 357.239 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: -490.92 cm**-1 ***imaginary mode*** + 7: 587.91 cm**-1 + 8: 795.60 cm**-1 + 9: 1191.14 cm**-1 + 10: 1670.28 cm**-1 + 11: 3693.00 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 0.043138 0.430039 -0.020828 0.009736 -0.028454 -0.033217 + 1 0.034473 0.122194 0.137005 0.057122 0.038773 0.051910 + 2 0.065874 -0.390564 0.198848 -0.051557 0.056521 -0.010416 + 3 -0.038364 -0.245053 0.151279 0.053296 -0.431628 -0.000495 + 4 0.036974 -0.136491 -0.237953 -0.049700 -0.570296 0.000355 + 5 -0.077009 0.117104 -0.422233 -0.040055 0.024751 0.000271 + 6 0.038067 -0.225306 -0.146288 -0.030320 0.416716 0.000531 + 7 -0.032194 0.003638 0.048476 -0.012343 0.460664 0.000171 + 8 0.022175 0.326040 0.197998 0.029802 -0.093697 -0.000413 + 9 -0.755787 0.155697 0.550323 -0.413887 -0.164661 0.525670 + 10 -0.549958 -0.100547 0.362604 -0.020127 -0.002352 -0.831565 + 11 -0.327411 -0.603135 -0.431483 0.901888 0.246125 0.168118 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 7: 587.91 0.015706 79.37 0.008337 (-0.071642 -0.021211 0.052481) + 8: 795.60 0.043294 218.79 0.016982 ( 0.089923 -0.003771 -0.094240) + 9: 1191.14 0.003519 17.78 0.000922 (-0.015951 0.014339 0.021491) + 10: 1670.28 0.031645 159.92 0.005912 (-0.056881 -0.016918 0.048894) + 11: 3693.00 0.011012 55.65 0.000931 ( 0.023429 -0.018358 -0.006676) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 7 +The total number of vibrations considered is 5 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 587.91 E(vib) ... 0.10 +freq. 795.60 E(vib) ... 0.05 +freq. 1191.14 E(vib) ... 0.01 +freq. 1670.28 E(vib) ... 0.00 +freq. 3693.00 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.43629291 Eh +Zero point energy ... 0.01808392 Eh 11.35 kcal/mol +Thermal vibrational correction ... 0.00026621 Eh 0.17 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.41511024 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00309875 Eh 1.94 kcal/mol +Non-thermal (ZPE) correction 0.01808392 Eh 11.35 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02118267 Eh 13.29 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.41511024 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.41416603 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.734544 0.409127 0.365827 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00034739 Eh 0.22 kcal/mol +Rotational entropy ... 0.00993256 Eh 6.23 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02808227 Eh 17.62 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00993256 Eh 6.23 kcal/mol| +| sn= 2 | S(rot)= 0.00927810 Eh 5.82 kcal/mol| +| sn= 3 | S(rot)= 0.00889527 Eh 5.58 kcal/mol| +| sn= 4 | S(rot)= 0.00862364 Eh 5.41 kcal/mol| +| sn= 5 | S(rot)= 0.00841296 Eh 5.28 kcal/mol| +| sn= 6 | S(rot)= 0.00824081 Eh 5.17 kcal/mol| +| sn= 7 | S(rot)= 0.00809527 Eh 5.08 kcal/mol| +| sn= 8 | S(rot)= 0.00796919 Eh 5.00 kcal/mol| +| sn= 9 | S(rot)= 0.00785798 Eh 4.93 kcal/mol| +| sn=10 | S(rot)= 0.00775850 Eh 4.87 kcal/mol| +| sn=11 | S(rot)= 0.00766851 Eh 4.81 kcal/mol| +| sn=12 | S(rot)= 0.00758636 Eh 4.76 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.41416603 Eh +Total entropy correction ... -0.02808227 Eh -17.62 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44224829 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00595539 Eh -3.74 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.436292907 Eh +Current gradient norm .... 0.017792336 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + -0.025558313 0.107635109 0.179609898 0.478220984 0.500604614 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999629529 +Lowest eigenvalues of augmented Hessian: + -0.000112706 0.103991171 0.179430549 0.477785710 0.500359846 +Length of the computed step .... 0.027227818 +The final length of the internal step .... 0.027227818 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0111157100 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0052160871 RMS(Int)= 0.0111142935 + Iter 1: RMS(Cart)= 0.0000117123 RMS(Int)= 0.0000173872 + Iter 2: RMS(Cart)= 0.0000000610 RMS(Int)= 0.0000000941 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0022530205 0.0001000000 NO + MAX gradient 0.0038963170 0.0003000000 NO + RMS step 0.0111157100 0.0020000000 NO + MAX step 0.0247305516 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0131 Max(Angles) 0.24 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4693 -0.002499 0.0131 1.4824 + 2. B(O 2,N 1) 1.1742 0.003896 -0.0043 1.1698 + 3. B(H 3,O 0) 0.9736 0.002699 -0.0030 0.9706 + 4. A(N 1,O 0,H 3) 104.41 -0.000237 -0.24 104.18 + 5. A(O 0,N 1,O 2) 112.26 0.001301 -0.22 112.04 + 6. D(O 2,N 1,O 0,H 3) 65.45 0.012415 0.00 65.45 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.443992 -0.295572 0.723775 + N 0.306277 -0.530314 -0.533029 + O 1.089982 0.313053 -0.740507 + H -0.952266 0.512832 0.549761 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.839024 -0.558550 1.367737 + 1 N 7.0000 0 14.007 0.578780 -1.002148 -1.007278 + 2 O 8.0000 0 15.999 2.059767 0.591585 -1.399356 + 3 H 1.0000 0 1.008 -1.799522 0.969113 1.038897 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.482418367759 0.00000000 0.00000000 + O 2 1 0 1.169832462400 112.04064120 0.00000000 + H 1 2 3 0.970639572689 104.17679977 65.45454554 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.801364730959 0.00000000 0.00000000 + O 2 1 0 2.210662976507 112.04064120 0.00000000 + H 1 2 3 1.834242967128 104.17679977 65.45454554 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2233 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2703 + la=0 lb=0: 552 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.669702817213 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.714e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7076936438 0.000000000000 0.00036188 0.00001010 0.0018464 0.7000 + 1 -204.7077219752 -0.000028331409 0.00029670 0.00000855 0.0015254 0.7000 + ***Turning on DIIS*** + 2 -204.7077454390 -0.000023463754 0.00075753 0.00002241 0.0012245 0.0000 + 3 -204.7072119176 0.000533521395 0.00025456 0.00001057 0.0003989 0.0000 + 4 -204.7079716074 -0.000759689806 0.00010684 0.00000363 0.0001207 0.0000 + 5 -204.7079271925 0.000044414930 0.00004679 0.00000129 0.0000655 0.0000 + 6 -204.7076786210 0.000248571443 0.00002558 0.00000065 0.0000525 0.0000 + 7 -204.7078490838 -0.000170462798 0.00000933 0.00000026 0.0000124 0.0000 + 8 -204.7078251031 0.000023980756 0.00000218 0.00000010 0.0000035 0.0000 + 9 -204.7078144391 0.000010663955 0.00000086 0.00000004 0.0000015 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 10 CYCLES * + ***************************************************** + +Total Energy : -204.70782751 Eh -5570.38318 eV + Last Energy change ... -1.3074e-05 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.5598e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.210 sec +Reference energy ... -204.707822012 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.369 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.376 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.025 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.037 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.036 s ( 0.000 ms/b) + 159120 b 0 skpd 0.020 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.023 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.351 sec +AO-integral generation ... 0.246 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.154 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.252 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090051011 +EMP2(bb)= -0.090051011 +EMP2(ab)= -0.516662759 + +Initial guess performed in 0.133 sec +E(0) ... -204.707822012 +E(MP2) ... -0.696764781 +Initial E(tot) ... -205.404586792 + ... 0.188685905 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.404586792 -0.696764781 -0.000000000 0.020494235 2.76 0.000001388 + *** Turning on DIIS *** + 1 -205.376381319 -0.668559307 0.028205474 0.009597482 2.71 0.056045731 + 2 -205.395850078 -0.688028066 -0.019468759 0.004247268 2.77 0.058970844 + 3 -205.399652128 -0.691830117 -0.003802050 0.001779572 2.78 0.072383777 + 4 -205.401200444 -0.693378433 -0.001548316 0.001173674 2.80 0.078557643 + 5 -205.401713037 -0.693891025 -0.000512592 0.000739078 2.83 0.083410655 + 6 -205.401806360 -0.693984348 -0.000093323 0.000461598 2.86 0.085839392 + 7 -205.401846995 -0.694024984 -0.000040636 0.000247051 2.96 0.087022340 + 8 -205.401857413 -0.694035402 -0.000010418 0.000149273 2.92 0.087575226 + 9 -205.401854291 -0.694032280 0.000003122 0.000089110 2.86 0.087788797 + 10 -205.401859739 -0.694037728 -0.000005448 0.000048632 2.80 0.087878626 + 11 -205.401856134 -0.694034122 0.000003606 0.000030530 2.80 0.087885141 + 12 -205.401858838 -0.694036827 -0.000002704 0.000018067 2.84 0.087903857 + 13 -205.401858424 -0.694036412 0.000000414 0.000009965 2.85 0.087902301 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.707822012 +E(CORR) ... -0.694036412 +E(TOT) ... -205.401858424 +Singles norm **1/2 ... 0.087902301 ( 0.043951151, 0.043951151) +T1 diagnostic ... 0.020718771 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.056052 + 9a-> 13a 9b-> 13b 0.055463 + 9a-> 13a 8b-> 13b 0.042701 + 8a-> 13a 9b-> 13b 0.042701 + 8a-> 13a -1a-> -1a 0.031616 + 8b-> 13b -1b-> -1b 0.031616 + 11a-> 13a 11b-> 13b 0.029571 + 5a-> 13a 5b-> 13b 0.029111 + 11a-> 25a 11b-> 25b 0.026018 + 10a-> 13a -1a-> -1a 0.023969 + 10b-> 13b -1b-> -1b 0.023969 + 9a-> 13a 9b-> 22b 0.021479 + 9a-> 22a 9b-> 13b 0.021479 + 11a-> 25a -1a-> -1a 0.021180 + 11b-> 25b -1b-> -1b 0.021180 + 8a-> 13a 8b-> 22b 0.020304 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034492037 + alpha-alpha-alpha ... -0.000871909 ( 2.5%) + alpha-alpha-beta ... -0.016374109 ( 47.5%) + alpha-beta -beta ... -0.016374109 ( 47.5%) + beta -beta -beta ... -0.000871909 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034492037 + +Final correlation energy ... -0.728528449 +E(CCSD) ... -205.401858424 +E(CCSD(T)) ... -205.436350461 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210350279 sqrt= 1.100159206 +W(HF) = 0.826207105 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 55.234 sec + +Fock Matrix Formation ... 0.210 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 1.819 sec ( 3.3%) +State Vector Update ... 0.083 sec ( 0.2%) +Sigma-vector construction ... 37.641 sec ( 68.1%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.025 sec ( 0.1% of sigma) + (0-ext) ... 0.069 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (2-ext) ... 0.931 sec ( 2.5% of sigma) + (4-ext) ... 20.768 sec ( 55.2% of sigma) + ... 1.508 sec ( 4.0% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.107 sec ( 0.3% of sigma) + Fock-dressing ... 2.152 sec ( 5.7% of sigma) + (ik|jl)-dressing ... 0.073 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.387 sec ( 24.9% of sigma) + Pair energies ... 0.006 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.787 sec ( 12.3% of ALL) + I/O of integral and amplitudes ... 0.796 sec ( 11.7% of (T)) + External N**7 contributions ... 3.897 sec ( 57.4% of (T)) + Internal N**7 contributions ... 0.308 sec ( 4.5% of (T)) + N**6 triples energy contributions ... 1.686 sec ( 24.8% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.436350460518 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.007157700 0.003350532 0.003350175 + 2 N : -0.005979296 0.003431521 -0.003965995 + 3 O : 0.003833344 -0.003108934 0.002939946 + 4 H : -0.005011748 -0.003673119 -0.002324126 + +Norm of the cartesian gradient ... 0.014627136 +RMS gradient ... 0.004222490 +MAX gradient ... 0.007157700 + +------- +TIMINGS +------- + +Total numerical gradient time ... 360.070 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.436350461 Eh +Current gradient norm .... 0.014627136 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999997718 +Lowest eigenvalues of augmented Hessian: + -0.000000554 0.098214565 0.175742268 0.479230048 0.502778487 +Length of the computed step .... 0.002136271 +The final length of the internal step .... 0.002136271 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0008721291 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0004848416 RMS(Int)= 0.0008721334 + Iter 1: RMS(Cart)= 0.0000000339 RMS(Int)= 0.0000000618 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000575537 0.0000050000 NO + RMS gradient 0.0001357772 0.0001000000 NO + MAX gradient 0.0002750204 0.0003000000 YES + RMS step 0.0008721291 0.0020000000 YES + MAX step 0.0020999084 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0011 Max(Angles) 0.02 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4824 -0.000275 0.0011 1.4835 + 2. B(O 2,N 1) 1.1698 -0.000184 -0.0000 1.1698 + 3. B(H 3,O 0) 0.9706 -0.000019 0.0000 0.9707 + 4. A(N 1,O 0,H 3) 104.18 -0.000022 -0.02 104.16 + 5. A(O 0,N 1,O 2) 112.04 -0.000013 -0.01 112.03 + 6. D(O 2,N 1,O 0,H 3) 65.45 0.011806 -0.00 65.45 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.444327 -0.295538 0.724248 + N 0.306590 -0.530395 -0.533458 + O 1.090216 0.313045 -0.740702 + H -0.952478 0.512888 0.549912 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.839656 -0.558486 1.368631 + 1 N 7.0000 0 14.007 0.579371 -1.002302 -1.008090 + 2 O 8.0000 0 15.999 2.060209 0.591569 -1.399725 + 3 H 1.0000 0 1.008 -1.799922 0.969219 1.039184 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.483529591429 0.00000000 0.00000000 + O 2 1 0 1.169790920804 112.03215944 0.00000000 + H 1 2 3 0.970651362779 104.15650493 65.45454554 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.803464639369 0.00000000 0.00000000 + O 2 1 0 2.210584474268 112.03215944 0.00000000 + H 1 2 3 1.834265247170 104.15650493 65.45454554 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2233 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2703 + la=0 lb=0: 552 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.648709777674 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.716e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7077237002 0.000000000000 0.00003204 0.00000075 0.0001456 0.7000 + 1 -204.7077238304 -0.000000130240 0.00002545 0.00000063 0.0001146 0.7000 + ***Turning on DIIS*** + 2 -204.7077239393 -0.000000108917 0.00006613 0.00000168 0.0000891 0.0000 + 3 -204.7077444352 -0.000020495845 0.00002412 0.00000074 0.0000237 0.0000 + 4 -204.7077125552 0.000031879910 0.00000876 0.00000024 0.0000074 0.0000 + 5 -204.7077191955 -0.000006640289 0.00000356 0.00000009 0.0000027 0.0000 + 6 -204.7077297962 -0.000010600658 0.00000134 0.00000004 0.0000019 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + +Total Energy : -204.70772548 Eh -5570.38040 eV + Last Energy change ... 4.3143e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.4594e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.205 sec +Reference energy ... -204.707724301 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.363 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.370 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.024 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.025 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.037 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.036 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.348 sec +AO-integral generation ... 0.244 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.049 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.154 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.252 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090062362 +EMP2(bb)= -0.090062362 +EMP2(ab)= -0.516741443 + +Initial guess performed in 0.132 sec +E(0) ... -204.707724301 +E(MP2) ... -0.696866168 +Initial E(tot) ... -205.404590469 + ... 0.188782535 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.404590469 -0.696866168 -0.000000000 0.020495368 2.71 0.000001199 + *** Turning on DIIS *** + 1 -205.376337520 -0.668613219 0.028252948 0.009587657 2.72 0.056088447 + 2 -205.395822716 -0.688098415 -0.019485195 0.004245485 2.79 0.059004198 + 3 -205.399627498 -0.691903197 -0.003804782 0.001777835 2.84 0.072428026 + 4 -205.401177581 -0.693453280 -0.001550083 0.001176564 2.80 0.078606637 + 5 -205.401691118 -0.693966817 -0.000513537 0.000740883 2.90 0.083467079 + 6 -205.401784597 -0.694060296 -0.000093480 0.000462942 2.82 0.085901270 + 7 -205.401825369 -0.694101068 -0.000040771 0.000247739 2.85 0.087089041 + 8 -205.401835848 -0.694111547 -0.000010479 0.000149312 2.90 0.087644278 + 9 -205.401832710 -0.694108409 0.000003138 0.000089181 2.83 0.087858458 + 10 -205.401838188 -0.694113887 -0.000005478 0.000048679 2.78 0.087948740 + 11 -205.401834564 -0.694110263 0.000003624 0.000030575 2.79 0.087955156 + 12 -205.401837281 -0.694112980 -0.000002717 0.000018093 2.79 0.087974010 + 13 -205.401836864 -0.694112563 0.000000417 0.000010006 2.82 0.087972357 + 14 -205.401837430 -0.694113128 -0.000000566 0.000004489 2.85 0.087979822 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.707724301 +E(CORR) ... -0.694113128 +E(TOT) ... -205.401837430 +Singles norm **1/2 ... 0.087979822 ( 0.043989911, 0.043989911) +T1 diagnostic ... 0.020737043 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.056214 + 9a-> 13a 9b-> 13b 0.055364 + 8a-> 13a 9b-> 13b 0.042746 + 9a-> 13a 8b-> 13b 0.042746 + 8b-> 13b -1b-> -1b 0.031600 + 8a-> 13a -1a-> -1a 0.031600 + 11a-> 13a 11b-> 13b 0.029526 + 5a-> 13a 5b-> 13b 0.029153 + 11a-> 25a 11b-> 25b 0.026148 + 10a-> 13a -1a-> -1a 0.024015 + 10b-> 13b -1b-> -1b 0.024015 + 9a-> 13a 9b-> 22b 0.021424 + 9a-> 22a 9b-> 13b 0.021424 + 11a-> 25a -1a-> -1a 0.021220 + 11b-> 25b -1b-> -1b 0.021220 + 8a-> 22a 8b-> 13b 0.020352 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034513864 + alpha-alpha-alpha ... -0.000872127 ( 2.5%) + alpha-alpha-beta ... -0.016384805 ( 47.5%) + alpha-beta -beta ... -0.016384805 ( 47.5%) + beta -beta -beta ... -0.000872127 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034513864 + +Final correlation energy ... -0.728626992 +E(CCSD) ... -205.401837430 +E(CCSD(T)) ... -205.436351294 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210468312 sqrt= 1.100212848 +W(HF) = 0.826126541 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 57.211 sec + +Fock Matrix Formation ... 0.205 sec ( 0.4%) +Initial Guess ... 0.132 sec ( 0.2%) +DIIS Solver ... 1.750 sec ( 3.1%) +State Vector Update ... 0.094 sec ( 0.2%) +Sigma-vector construction ... 40.354 sec ( 70.5%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.025 sec ( 0.1% of sigma) + (0-ext) ... 0.072 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (2-ext) ... 0.987 sec ( 2.4% of sigma) + (4-ext) ... 22.485 sec ( 55.7% of sigma) + ... 1.432 sec ( 3.5% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.114 sec ( 0.3% of sigma) + Fock-dressing ... 2.310 sec ( 5.7% of sigma) + (ik|jl)-dressing ... 0.078 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.014 sec ( 24.8% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.758 sec ( 11.8% of ALL) + I/O of integral and amplitudes ... 0.671 sec ( 9.9% of (T)) + External N**7 contributions ... 3.878 sec ( 57.4% of (T)) + Internal N**7 contributions ... 0.306 sec ( 4.5% of (T)) + N**6 triples energy contributions ... 1.541 sec ( 22.8% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.436351293602 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.006999393 0.003453583 0.003472900 + 2 N : -0.005857745 0.003245339 -0.004139242 + 3 O : 0.003941622 -0.002970058 0.002973533 + 4 H : -0.005083270 -0.003728863 -0.002307191 + +Norm of the cartesian gradient ... 0.014602232 +RMS gradient ... 0.004215301 +MAX gradient ... 0.006999393 + +------- +TIMINGS +------- + +Total numerical gradient time ... 359.940 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.436351294 Eh +Current gradient norm .... 0.014602232 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999394 +Lowest eigenvalues of augmented Hessian: + -0.000000114 0.065021428 0.254095923 0.486789745 0.502361617 +Length of the computed step .... 0.001100684 +The final length of the internal step .... 0.001100684 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0004493523 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0002966657 RMS(Int)= 0.0004493555 + Iter 1: RMS(Cart)= 0.0000001235 RMS(Int)= 0.0000002016 + Iter 2: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000001 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000008331 0.0000050000 YES + RMS gradient 0.0000566729 0.0001000000 YES + MAX gradient 0.0001176449 0.0003000000 YES + RMS step 0.0004493523 0.0020000000 YES + MAX step 0.0009202247 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0003 Max(Angles) 0.05 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4835 -0.000002 0.0003 1.4838 + 2. B(O 2,N 1) 1.1698 -0.000051 0.0000 1.1698 + 3. B(H 3,O 0) 0.9707 -0.000038 0.0001 0.9707 + 4. A(N 1,O 0,H 3) 104.16 0.000118 -0.05 104.10 + 5. A(O 0,N 1,O 2) 112.03 -0.000037 -0.00 112.03 + 6. D(O 2,N 1,O 0,H 3) 65.45 0.011809 0.00 65.45 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.444423 -0.295677 0.724570 + N 0.306513 -0.530345 -0.533532 + O 1.090153 0.313132 -0.740665 + H -0.952242 0.512890 0.549627 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.839838 -0.558748 1.369238 + 1 N 7.0000 0 14.007 0.579226 -1.002207 -1.008229 + 2 O 8.0000 0 15.999 2.060090 0.591734 -1.399653 + 3 H 1.0000 0 1.008 -1.799477 0.969222 1.038644 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.483844250334 0.00000000 0.00000000 + O 2 1 0 1.169807062948 112.03109468 0.00000000 + H 1 2 3 0.970703865086 104.10377993 65.45454554 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.804059258524 0.00000000 0.00000000 + O 2 1 0 2.210614978498 112.03109468 0.00000000 + H 1 2 3 1.834364462152 104.10377993 65.45454554 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2233 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2703 + la=0 lb=0: 552 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.642631161389 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.6426311614 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.717e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7076856469 0.000000000000 0.00001032 0.00000032 0.0000854 0.7000 + 1 -204.7076856745 -0.000000027644 0.00000847 0.00000028 0.0000681 0.7000 + ***Turning on DIIS*** + 2 -204.7076856975 -0.000000023012 0.00002182 0.00000076 0.0000532 0.0000 + 3 -204.7076859221 -0.000000224528 0.00001048 0.00000037 0.0000134 0.0000 + 4 -204.7076842489 0.000001673139 0.00000354 0.00000017 0.0000045 0.0000 + 5 -204.7076836500 0.000000598940 0.00000320 0.00000013 0.0000034 0.0000 + 6 -204.7076873843 -0.000003734330 0.00000382 0.00000016 0.0000029 0.0000 + 7 -204.7076853400 0.000002044321 0.00000274 0.00000010 0.0000012 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70768462 Eh -5570.37929 eV + +Components: +Nuclear Repulsion : 68.64263116 Eh 1867.86095 eV +Electronic Energy : -273.35031578 Eh -7438.24025 eV +One Electron Energy: -416.96114965 Eh -11346.08971 eV +Two Electron Energy: 143.61083387 Eh 3907.84946 eV + +Virial components: +Potential Energy : -408.93679624 Eh -11127.73595 eV +Kinetic Energy : 204.22911162 Eh 5557.35666 eV +Virial Ratio : 2.00234331 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 7.1828e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.0039e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.9048e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.4453e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.688245 -562.9558 + 1 1.0000 -20.622385 -561.1636 + 2 1.0000 -15.805331 -430.0849 + 3 1.0000 -1.615126 -43.9498 + 4 1.0000 -1.378763 -37.5181 + 5 1.0000 -0.958031 -26.0694 + 6 1.0000 -0.769109 -20.9285 + 7 1.0000 -0.735619 -20.0172 + 8 1.0000 -0.698338 -19.0027 + 9 1.0000 -0.604201 -16.4411 + 10 1.0000 -0.531836 -14.4720 + 11 1.0000 -0.462758 -12.5923 + 12 0.0000 0.031013 0.8439 + 13 0.0000 0.066631 1.8131 + 14 0.0000 0.092598 2.5197 + 15 0.0000 0.106852 2.9076 + 16 0.0000 0.113613 3.0916 + 17 0.0000 0.155135 4.2214 + 18 0.0000 0.157174 4.2769 + 19 0.0000 0.173422 4.7190 + 20 0.0000 0.178770 4.8646 + 21 0.0000 0.190691 5.1890 + 22 0.0000 0.201931 5.4948 + 23 0.0000 0.234883 6.3915 + 24 0.0000 0.271123 7.3776 + 25 0.0000 0.285552 7.7703 + 26 0.0000 0.307776 8.3750 + 27 0.0000 0.333459 9.0739 + 28 0.0000 0.339088 9.2270 + 29 0.0000 0.356774 9.7083 + 30 0.0000 0.423276 11.5179 + 31 0.0000 0.510323 13.8866 + 32 0.0000 0.531964 14.4755 + 33 0.0000 0.539997 14.6941 + 34 0.0000 0.561287 15.2734 + 35 0.0000 0.602228 16.3875 + 36 0.0000 0.633123 17.2281 + 37 0.0000 0.645039 17.5524 + 38 0.0000 0.704199 19.1622 + 39 0.0000 0.717856 19.5338 + 40 0.0000 0.733013 19.9463 + 41 0.0000 0.746070 20.3016 + 42 0.0000 0.766358 20.8537 + 43 0.0000 0.784518 21.3478 + 44 0.0000 0.811519 22.0825 + 45 0.0000 0.821223 22.3466 + 46 0.0000 0.854529 23.2529 + 47 0.0000 0.881723 23.9929 + 48 0.0000 0.900202 24.4957 + 49 0.0000 0.952887 25.9294 + 50 0.0000 0.971611 26.4389 + 51 0.0000 0.981116 26.6975 + 52 0.0000 0.984892 26.8003 + 53 0.0000 1.021724 27.8025 + 54 0.0000 1.047067 28.4921 + 55 0.0000 1.091093 29.6902 + 56 0.0000 1.155956 31.4552 + 57 0.0000 1.214863 33.0581 + 58 0.0000 1.228615 33.4323 + 59 0.0000 1.280088 34.8330 + 60 0.0000 1.325954 36.0810 + 61 0.0000 1.411108 38.3982 + 62 0.0000 1.465544 39.8795 + 63 0.0000 1.509302 41.0702 + 64 0.0000 1.532199 41.6933 + 65 0.0000 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80.9642 + 100 0.0000 3.100754 84.3758 + 101 0.0000 3.169256 86.2398 + 102 0.0000 3.225680 87.7752 + 103 0.0000 3.491816 95.0171 + 104 0.0000 3.701354 100.7190 + 105 0.0000 3.842333 104.5552 + 106 0.0000 4.031711 109.7084 + 107 0.0000 4.164206 113.3138 + 108 0.0000 4.207324 114.4871 + 109 0.0000 4.296170 116.9047 + 110 0.0000 4.367429 118.8438 + 111 0.0000 4.393420 119.5510 + 112 0.0000 4.542987 123.6210 + 113 0.0000 4.620054 125.7181 + 114 0.0000 4.668960 127.0488 + 115 0.0000 4.731372 128.7472 + 116 0.0000 4.826134 131.3258 + 117 0.0000 4.881134 132.8224 + 118 0.0000 4.938072 134.3718 + 119 0.0000 4.972088 135.2974 + 120 0.0000 5.056258 137.5878 + 121 0.0000 5.107694 138.9874 + 122 0.0000 5.182320 141.0181 + 123 0.0000 5.207778 141.7108 + 124 0.0000 5.244774 142.7176 + 125 0.0000 5.290499 143.9618 + 126 0.0000 5.392701 146.7428 + 127 0.0000 5.495187 149.5316 + 128 0.0000 5.510809 149.9567 + 129 0.0000 5.700810 155.1269 + 130 0.0000 5.749887 156.4624 + 131 0.0000 5.953714 162.0088 + 132 0.0000 6.163823 167.7262 + 133 0.0000 6.409461 174.4103 + 134 0.0000 6.482323 176.3930 + 135 0.0000 6.513533 177.2422 + 136 0.0000 6.688044 181.9909 + 137 0.0000 6.711726 182.6353 + 138 0.0000 6.779589 184.4820 + 139 0.0000 6.814119 185.4216 + 140 0.0000 6.849555 186.3859 + 141 0.0000 7.076422 192.5592 + 142 0.0000 7.111575 193.5158 + 143 0.0000 7.133233 194.1051 + 144 0.0000 7.210713 196.2135 + 145 0.0000 7.252532 197.3514 + 146 0.0000 7.276149 197.9941 + 147 0.0000 7.329368 199.4422 + 148 0.0000 7.387586 201.0264 + 149 0.0000 7.457873 202.9390 + 150 0.0000 7.473059 203.3523 + 151 0.0000 7.547057 205.3659 + 152 0.0000 7.579287 206.2429 + 153 0.0000 7.658566 208.4002 + 154 0.0000 7.683714 209.0845 + 155 0.0000 7.907210 215.1661 + 156 0.0000 7.982931 217.2266 + 157 0.0000 8.384649 228.1579 + 158 0.0000 14.028544 381.7361 + 159 0.0000 14.946759 406.7220 + 160 0.0000 16.019755 435.9197 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.688245 -562.9558 + 1 1.0000 -20.622385 -561.1636 + 2 1.0000 -15.805331 -430.0849 + 3 1.0000 -1.615126 -43.9498 + 4 1.0000 -1.378763 -37.5181 + 5 1.0000 -0.958031 -26.0694 + 6 1.0000 -0.769109 -20.9285 + 7 1.0000 -0.735619 -20.0172 + 8 1.0000 -0.698338 -19.0027 + 9 1.0000 -0.604201 -16.4411 + 10 1.0000 -0.531836 -14.4720 + 11 1.0000 -0.462758 -12.5923 + 12 0.0000 0.031013 0.8439 + 13 0.0000 0.066631 1.8131 + 14 0.0000 0.092598 2.5197 + 15 0.0000 0.106852 2.9076 + 16 0.0000 0.113613 3.0916 + 17 0.0000 0.155135 4.2214 + 18 0.0000 0.157174 4.2769 + 19 0.0000 0.173422 4.7190 + 20 0.0000 0.178770 4.8646 + 21 0.0000 0.190691 5.1890 + 22 0.0000 0.201931 5.4948 + 23 0.0000 0.234883 6.3915 + 24 0.0000 0.271123 7.3776 + 25 0.0000 0.285552 7.7703 + 26 0.0000 0.307776 8.3750 + 27 0.0000 0.333459 9.0739 + 28 0.0000 0.339088 9.2270 + 29 0.0000 0.356774 9.7083 + 30 0.0000 0.423276 11.5179 + 31 0.0000 0.510323 13.8866 + 32 0.0000 0.531964 14.4755 + 33 0.0000 0.539997 14.6941 + 34 0.0000 0.561287 15.2734 + 35 0.0000 0.602228 16.3875 + 36 0.0000 0.633123 17.2281 + 37 0.0000 0.645039 17.5524 + 38 0.0000 0.704199 19.1622 + 39 0.0000 0.717856 19.5338 + 40 0.0000 0.733013 19.9463 + 41 0.0000 0.746070 20.3016 + 42 0.0000 0.766358 20.8537 + 43 0.0000 0.784518 21.3478 + 44 0.0000 0.811519 22.0825 + 45 0.0000 0.821223 22.3466 + 46 0.0000 0.854529 23.2529 + 47 0.0000 0.881723 23.9929 + 48 0.0000 0.900202 24.4957 + 49 0.0000 0.952887 25.9294 + 50 0.0000 0.971611 26.4389 + 51 0.0000 0.981116 26.6975 + 52 0.0000 0.984892 26.8003 + 53 0.0000 1.021724 27.8025 + 54 0.0000 1.047067 28.4921 + 55 0.0000 1.091093 29.6902 + 56 0.0000 1.155956 31.4552 + 57 0.0000 1.214863 33.0581 + 58 0.0000 1.228615 33.4323 + 59 0.0000 1.280088 34.8330 + 60 0.0000 1.325954 36.0810 + 61 0.0000 1.411108 38.3982 + 62 0.0000 1.465544 39.8795 + 63 0.0000 1.509302 41.0702 + 64 0.0000 1.532199 41.6933 + 65 0.0000 1.581761 43.0419 + 66 0.0000 1.595374 43.4123 + 67 0.0000 1.633999 44.4634 + 68 0.0000 1.652879 44.9771 + 69 0.0000 1.733647 47.1749 + 70 0.0000 1.745859 47.5072 + 71 0.0000 1.782136 48.4944 + 72 0.0000 1.926447 52.4213 + 73 0.0000 1.929621 52.5076 + 74 0.0000 1.968070 53.5539 + 75 0.0000 2.005529 54.5732 + 76 0.0000 2.044559 55.6353 + 77 0.0000 2.084607 56.7250 + 78 0.0000 2.147140 58.4266 + 79 0.0000 2.183662 59.4205 + 80 0.0000 2.263109 61.5823 + 81 0.0000 2.308226 62.8100 + 82 0.0000 2.328634 63.3654 + 83 0.0000 2.370507 64.5048 + 84 0.0000 2.419998 65.8515 + 85 0.0000 2.454148 66.7808 + 86 0.0000 2.464526 67.0632 + 87 0.0000 2.485070 67.6222 + 88 0.0000 2.512073 68.3570 + 89 0.0000 2.553945 69.4964 + 90 0.0000 2.589246 70.4570 + 91 0.0000 2.602046 70.8053 + 92 0.0000 2.666586 72.5615 + 93 0.0000 2.685754 73.0831 + 94 0.0000 2.753776 74.9341 + 95 0.0000 2.798411 76.1486 + 96 0.0000 2.832287 77.0704 + 97 0.0000 2.922908 79.5364 + 98 0.0000 2.965042 80.6829 + 99 0.0000 2.975379 80.9642 + 100 0.0000 3.100754 84.3758 + 101 0.0000 3.169256 86.2398 + 102 0.0000 3.225680 87.7752 + 103 0.0000 3.491816 95.0171 + 104 0.0000 3.701354 100.7190 + 105 0.0000 3.842333 104.5552 + 106 0.0000 4.031711 109.7084 + 107 0.0000 4.164206 113.3138 + 108 0.0000 4.207324 114.4871 + 109 0.0000 4.296170 116.9047 + 110 0.0000 4.367429 118.8438 + 111 0.0000 4.393420 119.5510 + 112 0.0000 4.542987 123.6210 + 113 0.0000 4.620054 125.7181 + 114 0.0000 4.668960 127.0488 + 115 0.0000 4.731372 128.7472 + 116 0.0000 4.826134 131.3258 + 117 0.0000 4.881134 132.8224 + 118 0.0000 4.938072 134.3718 + 119 0.0000 4.972088 135.2974 + 120 0.0000 5.056258 137.5878 + 121 0.0000 5.107694 138.9874 + 122 0.0000 5.182320 141.0181 + 123 0.0000 5.207778 141.7108 + 124 0.0000 5.244774 142.7176 + 125 0.0000 5.290499 143.9618 + 126 0.0000 5.392701 146.7428 + 127 0.0000 5.495187 149.5316 + 128 0.0000 5.510809 149.9567 + 129 0.0000 5.700810 155.1269 + 130 0.0000 5.749887 156.4624 + 131 0.0000 5.953714 162.0088 + 132 0.0000 6.163823 167.7262 + 133 0.0000 6.409461 174.4103 + 134 0.0000 6.482323 176.3930 + 135 0.0000 6.513533 177.2422 + 136 0.0000 6.688044 181.9909 + 137 0.0000 6.711726 182.6353 + 138 0.0000 6.779589 184.4820 + 139 0.0000 6.814119 185.4216 + 140 0.0000 6.849555 186.3859 + 141 0.0000 7.076422 192.5592 + 142 0.0000 7.111575 193.5158 + 143 0.0000 7.133233 194.1051 + 144 0.0000 7.210713 196.2135 + 145 0.0000 7.252532 197.3514 + 146 0.0000 7.276149 197.9941 + 147 0.0000 7.329368 199.4422 + 148 0.0000 7.387586 201.0264 + 149 0.0000 7.457873 202.9390 + 150 0.0000 7.473059 203.3523 + 151 0.0000 7.547057 205.3659 + 152 0.0000 7.579287 206.2429 + 153 0.0000 7.658566 208.4002 + 154 0.0000 7.683714 209.0845 + 155 0.0000 7.907210 215.1661 + 156 0.0000 7.982931 217.2266 + 157 0.0000 8.384649 228.1579 + 158 0.0000 14.028544 381.7361 + 159 0.0000 14.946759 406.7220 + 160 0.0000 16.019755 435.9197 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.361080 0.000000 + 1 N : 0.353063 0.000000 + 2 O : -0.240640 0.000000 + 3 H : 0.248658 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.849686 s : 3.849686 + pz : 1.349138 p : 4.478313 + px : 1.606209 + py : 1.522966 + dz2 : 0.009043 d : 0.028763 + dxz : 0.008283 + dyz : 0.005476 + dx2y2 : 0.004314 + dxy : 0.001647 + f0 : 0.001175 f : 0.004317 + f+1 : 0.000995 + f-1 : 0.000666 + f+2 : 0.000478 + f-2 : 0.000448 + f+3 : 0.000392 + f-3 : 0.000163 + 1 N s : 3.828457 s : 3.828457 + pz : 0.791783 p : 2.646826 + px : 0.786066 + py : 1.068978 + dz2 : 0.027791 d : 0.140153 + dxz : 0.036010 + dyz : 0.019368 + dx2y2 : 0.035410 + dxy : 0.021574 + f0 : 0.007551 f : 0.031502 + f+1 : 0.002291 + f-1 : 0.005118 + f+2 : 0.002806 + f-2 : 0.005864 + f+3 : 0.003138 + f-3 : 0.004733 + 2 O s : 3.875228 s : 3.875228 + pz : 1.683889 p : 4.295998 + px : 1.245550 + py : 1.366559 + dz2 : 0.004919 d : 0.061942 + dxz : 0.006945 + dyz : 0.013759 + dx2y2 : 0.024649 + dxy : 0.011670 + f0 : 0.001083 f : 0.007473 + f+1 : 0.000539 + f-1 : 0.000758 + f+2 : 0.000070 + f-2 : 0.001306 + f+3 : 0.001778 + f-3 : 0.001938 + 3 H s : 0.642059 s : 0.642059 + pz : 0.023967 p : 0.088769 + px : 0.037915 + py : 0.026887 + dz2 : 0.001446 d : 0.020515 + dxz : 0.001948 + dyz : 0.006333 + dx2y2 : 0.008225 + dxy : 0.002562 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.579546 0.000000 + 1 N : -0.243145 0.000000 + 2 O : 0.247865 0.000000 + 3 H : -0.584266 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.130361 s : 3.130361 + pz : 1.244971 p : 3.949630 + px : 1.342134 + py : 1.362526 + dz2 : 0.073374 d : 0.263170 + dxz : 0.075792 + dyz : 0.052805 + dx2y2 : 0.021307 + dxy : 0.039891 + f0 : 0.013405 f : 0.077294 + f+1 : 0.017709 + f-1 : 0.014783 + f+2 : 0.011283 + f-2 : 0.012943 + f+3 : 0.005656 + f-3 : 0.001514 + 1 N s : 3.032060 s : 3.032060 + pz : 0.837697 p : 2.836468 + px : 0.862608 + py : 1.136164 + dz2 : 0.196061 d : 0.929808 + dxz : 0.229159 + dyz : 0.142118 + dx2y2 : 0.172622 + dxy : 0.189849 + f0 : 0.088372 f : 0.444808 + f+1 : 0.052529 + f-1 : 0.057247 + f+2 : 0.030137 + f-2 : 0.088213 + f+3 : 0.063784 + f-3 : 0.064526 + 2 O s : 3.311839 s : 3.311839 + pz : 1.389524 p : 3.994699 + px : 1.233214 + py : 1.371960 + dz2 : 0.050797 d : 0.328557 + dxz : 0.059998 + dyz : 0.037757 + dx2y2 : 0.071268 + dxy : 0.108737 + f0 : 0.011325 f : 0.117041 + f+1 : 0.011600 + f-1 : 0.015713 + f+2 : 0.004314 + f-2 : 0.021515 + f+3 : 0.030521 + f-3 : 0.022053 + 3 H s : 0.624067 s : 0.624067 + pz : 0.147305 p : 0.569359 + px : 0.182418 + py : 0.239636 + dz2 : 0.032386 d : 0.390840 + dxz : 0.053964 + dyz : 0.088700 + dx2y2 : 0.118881 + dxy : 0.096910 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3611 8.0000 -0.3611 1.8174 1.8174 -0.0000 + 1 N 6.6469 7.0000 0.3531 2.5764 2.5764 -0.0000 + 2 O 8.2406 8.0000 -0.2406 1.7854 1.7854 -0.0000 + 3 H 0.7513 1.0000 0.2487 1.0032 1.0032 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8048 B( 0-O , 3-H ) : 0.9530 B( 1-N , 2-O ) : 1.7236 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.468 sec +Sum of individual times .... 1.190 sec ( 81.1%) + +Fock matrix formation .... 0.913 sec ( 62.2%) +Diagonalization .... 0.110 sec ( 7.5%) +Density matrix formation .... 0.008 sec ( 0.5%) +Population analysis .... 0.071 sec ( 4.8%) +Initial guess .... 0.010 sec ( 0.7%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.006 sec ( 0.4%) +DIIS solution .... 0.078 sec ( 5.3%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.208 sec +Reference energy ... -204.707685783 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.388 sec +AO-integral generation ... 0.146 sec +Half transformation ... 0.080 sec +K-integral sorting ... 5.392 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.025 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.037 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.034 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.030 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.352 sec +AO-integral generation ... 0.245 sec +Half transformation ... 0.042 sec +J-integral sorting ... 0.051 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.150 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.254 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090067118 +EMP2(bb)= -0.090067118 +EMP2(ab)= -0.516772028 + +Initial guess performed in 0.133 sec +E(0) ... -204.707685783 +E(MP2) ... -0.696906264 +Initial E(tot) ... -205.404592047 + ... 0.188817931 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.404592047 -0.696906264 -0.000000000 0.020495322 2.79 0.000000952 + *** Turning on DIIS *** + 1 -205.376321624 -0.668635842 0.028270423 0.009590145 2.73 0.056102354 + 2 -205.395812818 -0.688127036 -0.019491194 0.004244908 2.82 0.059015470 + 3 -205.399618675 -0.691932893 -0.003805857 0.001778193 2.80 0.072443196 + 4 -205.401169428 -0.693483645 -0.001550753 0.001177814 2.85 0.078623667 + 5 -205.401683309 -0.693997526 -0.000513881 0.000741709 2.86 0.083486601 + 6 -205.401776842 -0.694091059 -0.000093533 0.000463521 2.85 0.085922513 + 7 -205.401817658 -0.694131875 -0.000040816 0.000248069 2.92 0.087111812 + 8 -205.401828158 -0.694142375 -0.000010500 0.000149317 2.93 0.087667888 + 9 -205.401825015 -0.694139233 0.000003143 0.000089203 2.84 0.087882316 + 10 -205.401830504 -0.694144721 -0.000005489 0.000048698 2.81 0.087972732 + 11 -205.401826874 -0.694141091 0.000003630 0.000030595 2.88 0.087979137 + 12 -205.401829594 -0.694143812 -0.000002720 0.000018112 2.89 0.087998012 + 13 -205.401829176 -0.694143394 0.000000418 0.000010021 2.92 0.087996348 + 14 -205.401829743 -0.694143960 -0.000000566 0.000004498 2.95 0.088003824 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.707685783 +E(CORR) ... -0.694143960 +E(TOT) ... -205.401829743 +Singles norm **1/2 ... 0.088003824 ( 0.044001912, 0.044001912) +T1 diagnostic ... 0.020742700 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.056216 + 9a-> 13a 9b-> 13b 0.055377 + 9a-> 13a 8b-> 13b 0.042760 + 8a-> 13a 9b-> 13b 0.042760 + 8a-> 13a -1a-> -1a 0.031595 + 8b-> 13b -1b-> -1b 0.031595 + 11a-> 13a 11b-> 13b 0.029515 + 5a-> 13a 5b-> 13b 0.029168 + 11a-> 25a 11b-> 25b 0.026217 + 10a-> 13a -1a-> -1a 0.024044 + 10b-> 13b -1b-> -1b 0.024044 + 9a-> 13a 9b-> 22b 0.021422 + 9a-> 22a 9b-> 13b 0.021422 + 11a-> 25a -1a-> -1a 0.021247 + 11b-> 25b -1b-> -1b 0.021247 + 8a-> 13a 8b-> 22b 0.020347 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034521419 + alpha-alpha-alpha ... -0.000872217 ( 2.5%) + alpha-alpha-beta ... -0.016388493 ( 47.5%) + alpha-beta -beta ... -0.016388493 ( 47.5%) + beta -beta -beta ... -0.000872217 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034521419 + +Final correlation energy ... -0.728665379 +E(CCSD) ... -205.401829743 +E(CCSD(T)) ... -205.436351162 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210509672 sqrt= 1.100231645 +W(HF) = 0.826098315 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.297999 -0.000000 + 1 N : 0.176442 0.000000 + 2 O : -0.115514 -0.000000 + 3 H : 0.237072 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.831024 s : 3.831024 + pz : 1.324831 p : 4.399545 + px : 1.579033 + py : 1.495681 + dz2 : 0.014537 d : 0.059391 + dxz : 0.013218 + dyz : 0.012420 + dx2y2 : 0.010979 + dxy : 0.008236 + f0 : 0.001701 f : 0.008039 + f+1 : 0.001226 + f-1 : 0.001221 + f+2 : 0.000999 + f-2 : 0.001028 + f+3 : 0.001044 + f-3 : 0.000821 + 1 N s : 3.882551 s : 3.882551 + pz : 0.840770 p : 2.741255 + px : 0.844666 + py : 1.055819 + dz2 : 0.035645 d : 0.169330 + dxz : 0.043464 + dyz : 0.025639 + dx2y2 : 0.038430 + dxy : 0.026151 + f0 : 0.007098 f : 0.030421 + f+1 : 0.002183 + f-1 : 0.005248 + f+2 : 0.003098 + f-2 : 0.005584 + f+3 : 0.003156 + f-3 : 0.004055 + 2 O s : 3.861830 s : 3.861830 + pz : 1.607618 p : 4.160545 + px : 1.217459 + py : 1.335468 + dz2 : 0.010352 d : 0.083260 + dxz : 0.013499 + dyz : 0.018225 + dx2y2 : 0.026893 + dxy : 0.014290 + f0 : 0.001507 f : 0.009880 + f+1 : 0.001002 + f-1 : 0.001193 + f+2 : 0.000661 + f-2 : 0.001632 + f+3 : 0.001918 + f-3 : 0.001966 + 3 H s : 0.650541 s : 0.650541 + pz : 0.027936 p : 0.094650 + px : 0.040914 + py : 0.025800 + dz2 : 0.001189 d : 0.017738 + dxz : 0.001938 + dyz : 0.005559 + dx2y2 : 0.007080 + dxy : 0.001972 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.587050 0.000000 + 1 N : -0.287776 -0.000000 + 2 O : 0.289314 -0.000000 + 3 H : -0.588588 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.135627 s : 3.135627 + pz : 1.233459 p : 3.898664 + px : 1.323671 + py : 1.341535 + dz2 : 0.079234 d : 0.294328 + dxz : 0.082559 + dyz : 0.058032 + dx2y2 : 0.027317 + dxy : 0.047185 + f0 : 0.015056 f : 0.084330 + f+1 : 0.019419 + f-1 : 0.015116 + f+2 : 0.012076 + f-2 : 0.013850 + f+3 : 0.006519 + f-3 : 0.002294 + 1 N s : 3.037262 s : 3.037262 + pz : 0.860052 p : 2.878685 + px : 0.896647 + py : 1.121986 + dz2 : 0.201452 d : 0.936711 + dxz : 0.232111 + dyz : 0.137303 + dx2y2 : 0.168759 + dxy : 0.197086 + f0 : 0.084626 f : 0.435118 + f+1 : 0.053465 + f-1 : 0.056585 + f+2 : 0.029619 + f-2 : 0.084836 + f+3 : 0.062599 + f-3 : 0.063387 + 2 O s : 3.314388 s : 3.314388 + pz : 1.342573 p : 3.912961 + px : 1.216797 + py : 1.353591 + dz2 : 0.056765 d : 0.357876 + dxz : 0.064255 + dyz : 0.043613 + dx2y2 : 0.079717 + dxy : 0.113525 + f0 : 0.012269 f : 0.125461 + f+1 : 0.012594 + f-1 : 0.015888 + f+2 : 0.005277 + f-2 : 0.022514 + f+3 : 0.031687 + f-3 : 0.025232 + 3 H s : 0.625277 s : 0.625277 + pz : 0.148328 p : 0.582827 + px : 0.187898 + py : 0.246601 + dz2 : 0.032608 d : 0.380484 + dxz : 0.051982 + dyz : 0.085983 + dx2y2 : 0.114653 + dxy : 0.095259 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2980 8.0000 -0.2980 2.1709 1.7113 0.4597 + 1 N 6.8236 7.0000 0.1764 2.8442 2.3539 0.4902 + 2 O 8.1155 8.0000 -0.1155 2.1719 1.6735 0.4984 + 3 H 0.7629 1.0000 0.2371 1.0215 0.9470 0.0746 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7293 B( 0-O , 3-H ) : 0.8883 B( 1-N , 2-O ) : 1.5729 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 58.745 sec + +Fock Matrix Formation ... 0.208 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 1.985 sec ( 3.4%) +State Vector Update ... 0.089 sec ( 0.2%) +Sigma-vector construction ... 40.753 sec ( 69.4%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.024 sec ( 0.1% of sigma) + (0-ext) ... 0.074 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.028 sec ( 0.1% of sigma) + (2-ext) ... 1.007 sec ( 2.5% of sigma) + (4-ext) ... 22.436 sec ( 55.1% of sigma) + ... 1.546 sec ( 3.8% of sigma) + ... 0.003 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.118 sec ( 0.3% of sigma) + Fock-dressing ... 2.352 sec ( 5.8% of sigma) + (ik|jl)-dressing ... 0.080 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.310 sec ( 25.3% of sigma) + Pair energies ... 0.006 sec ( 0.0% of sigma) +Total Time for computing (T) ... 7.068 sec ( 12.0% of ALL) + I/O of integral and amplitudes ... 0.914 sec ( 12.9% of (T)) + External N**7 contributions ... 4.079 sec ( 57.7% of (T)) + Internal N**7 contributions ... 0.330 sec ( 4.7% of (T)) + N**6 triples energy contributions ... 1.689 sec ( 23.9% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.436351161778 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.031.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.031.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.549256, -0.266590 -0.288472) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.78193 -0.17607 -0.83913 +Nuclear contribution : -1.16502 0.61582 0.66104 + ----------------------------------------- +Total Dipole Moment : -0.38309 0.43975 -0.17809 + ----------------------------------------- +Magnitude (a.u.) : 0.60980 +Magnitude (Debye) : 1.54998 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.719063 0.406360 0.363327 +Rotational constants in MHz : 81515.471344 12182.357701 10892.270833 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.052636 0.239180 0.558456 +x,y,z [Debye]: 0.133790 0.607948 1.419482 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.549256, -0.266590 -0.288472) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.91731 -0.10654 -0.85977 +Nuclear contribution : -1.16502 0.61582 0.66104 + ----------------------------------------- +Total Dipole Moment : -0.24770 0.50928 -0.19873 + ----------------------------------------- +Magnitude (a.u.) : 0.60018 +Magnitude (Debye) : 1.52554 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.719063 0.406360 0.363327 +Rotational constants in MHz : 81515.471344 12182.357701 10892.270833 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.070893 0.314179 0.506443 +x,y,z [Debye]: -0.180195 0.798579 1.287275 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 32 * + * * + * Dihedral ( 2, 1, 0, 3) : 73.63636364 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0370211050 RMS(Int)= 0.0001554900 + Iter 1: RMS(Cart)= 0.0000403111 RMS(Int)= 0.0000000069 + Iter 2: RMS(Cart)= 0.0000000018 RMS(Int)= 0.0000000000 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4846 0.000000 + 2. B(O 2,N 1) 1.1715 0.000000 + 3. B(H 3,O 0) 0.9731 0.000000 + 4. A(N 1,O 0,H 3) 103.9620 0.000000 + 5. A(O 0,N 1,O 2) 111.9030 0.000000 + 6. D(O 2,N 1,O 0,H 3) 73.6364 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.421261 -0.277362 0.734824 + N 0.288552 -0.510440 -0.548120 + O 1.118565 0.293536 -0.740663 + H -0.985855 0.494266 0.553959 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.796067 -0.524139 1.388617 + 1 N 7.0000 0 14.007 0.545284 -0.964591 -1.035797 + 2 O 8.0000 0 15.999 2.113782 0.554703 -1.399651 + 3 H 1.0000 0 1.008 -1.862997 0.934027 1.046831 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.483844250334 0.00000000 0.00000000 + O 2 1 0 1.169807062948 112.03109468 0.00000000 + H 1 2 3 0.970703865086 104.10377993 65.45454554 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.804059258524 0.00000000 0.00000000 + O 2 1 0 2.210614978498 112.03109468 0.00000000 + H 1 2 3 1.834364462152 104.10377993 65.45454554 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2231 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2700 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.543652427444 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.5436524274 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.764e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7019103572 0.000000000000 0.00141820 0.00004934 0.0172137 0.7000 + 1 -204.7027316803 -0.000821323064 0.00137102 0.00004570 0.0142895 0.7000 + ***Turning on DIIS*** + 2 -204.7034420046 -0.000710324281 0.00380715 0.00012665 0.0116531 0.0000 + 3 -204.7065729484 -0.003130943812 0.00185809 0.00005997 0.0047099 0.0000 + 4 -204.7050783115 0.001494636828 0.00086965 0.00003251 0.0018556 0.0000 + 5 -204.7068514198 -0.001773108299 0.00088849 0.00002790 0.0010339 0.0000 + 6 -204.7061997060 0.000651713822 0.00087630 0.00003348 0.0008418 0.0000 + 7 -204.7056854378 0.000514268186 0.00048964 0.00001731 0.0003826 0.0000 + 8 -204.7065106695 -0.000825231701 0.00025709 0.00000998 0.0002253 0.0000 + 9 -204.7061146611 0.000396008400 0.00019621 0.00000614 0.0001275 0.0000 + 10 -204.7061878558 -0.000073194712 0.00007828 0.00000249 0.0000564 0.0000 + 11 -204.7063534195 -0.000165563622 0.00003586 0.00000093 0.0000319 0.0000 + 12 -204.7062426072 0.000110812270 0.00000966 0.00000028 0.0000088 0.0000 + 13 -204.7062682299 -0.000025622714 0.00000301 0.00000010 0.0000038 0.0000 + 14 -204.7062595105 0.000008719426 0.00000110 0.00000005 0.0000025 0.0000 + 15 -204.7062597424 -0.000000231897 0.00000114 0.00000003 0.0000024 0.0000 + 16 -204.7062630163 -0.000003273885 0.00000083 0.00000003 0.0000011 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 17 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70626098 Eh -5570.34055 eV + +Components: +Nuclear Repulsion : 68.54365243 Eh 1865.16761 eV +Electronic Energy : -273.24991340 Eh -7435.50816 eV +One Electron Energy: -416.78087676 Eh -11341.18423 eV +Two Electron Energy: 143.53096336 Eh 3905.67607 eV + +Virial components: +Potential Energy : -408.92435472 Eh -11127.39740 eV +Kinetic Energy : 204.21809374 Eh 5557.05685 eV +Virial Ratio : 2.00239042 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.0409e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.6929e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.8518e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.2480e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.688736 -562.9691 + 1 1.0000 -20.621525 -561.1402 + 2 1.0000 -15.804595 -430.0649 + 3 1.0000 -1.612954 -43.8907 + 4 1.0000 -1.377636 -37.4874 + 5 1.0000 -0.957150 -26.0454 + 6 1.0000 -0.768309 -20.9067 + 7 1.0000 -0.733635 -19.9632 + 8 1.0000 -0.698789 -19.0150 + 9 1.0000 -0.602126 -16.3847 + 10 1.0000 -0.531988 -14.4761 + 11 1.0000 -0.462031 -12.5725 + 12 0.0000 0.030665 0.8344 + 13 0.0000 0.065924 1.7939 + 14 0.0000 0.092507 2.5172 + 15 0.0000 0.105780 2.8784 + 16 0.0000 0.113042 3.0760 + 17 0.0000 0.155444 4.2299 + 18 0.0000 0.156650 4.2627 + 19 0.0000 0.174632 4.7520 + 20 0.0000 0.178506 4.8574 + 21 0.0000 0.190249 5.1769 + 22 0.0000 0.201713 5.4889 + 23 0.0000 0.235532 6.4091 + 24 0.0000 0.271809 7.3963 + 25 0.0000 0.289212 7.8699 + 26 0.0000 0.305748 8.3198 + 27 0.0000 0.332748 9.0545 + 28 0.0000 0.336872 9.1667 + 29 0.0000 0.353613 9.6223 + 30 0.0000 0.422825 11.5056 + 31 0.0000 0.508382 13.8338 + 32 0.0000 0.531426 14.4608 + 33 0.0000 0.542664 14.7666 + 34 0.0000 0.563540 15.3347 + 35 0.0000 0.600789 16.3483 + 36 0.0000 0.631466 17.1831 + 37 0.0000 0.643892 17.5212 + 38 0.0000 0.708251 19.2725 + 39 0.0000 0.718220 19.5438 + 40 0.0000 0.734347 19.9826 + 41 0.0000 0.749128 20.3848 + 42 0.0000 0.764994 20.8165 + 43 0.0000 0.786125 21.3915 + 44 0.0000 0.808525 22.0011 + 45 0.0000 0.818732 22.2788 + 46 0.0000 0.857443 23.3322 + 47 0.0000 0.878089 23.8940 + 48 0.0000 0.894950 24.3528 + 49 0.0000 0.958092 26.0710 + 50 0.0000 0.964184 26.2368 + 51 0.0000 0.973947 26.5024 + 52 0.0000 0.987630 26.8748 + 53 0.0000 1.024005 27.8646 + 54 0.0000 1.044385 28.4192 + 55 0.0000 1.093925 29.7672 + 56 0.0000 1.156226 31.4625 + 57 0.0000 1.218309 33.1519 + 58 0.0000 1.236455 33.6457 + 59 0.0000 1.275023 34.6951 + 60 0.0000 1.316963 35.8364 + 61 0.0000 1.408042 38.3148 + 62 0.0000 1.463446 39.8224 + 63 0.0000 1.511460 41.1289 + 64 0.0000 1.532411 41.6990 + 65 0.0000 1.580603 43.0104 + 66 0.0000 1.592336 43.3297 + 67 0.0000 1.633875 44.4600 + 68 0.0000 1.650915 44.9237 + 69 0.0000 1.730701 47.0948 + 70 0.0000 1.753447 47.7137 + 71 0.0000 1.781562 48.4788 + 72 0.0000 1.918456 52.2038 + 73 0.0000 1.926324 52.4179 + 74 0.0000 1.972305 53.6692 + 75 0.0000 2.011046 54.7233 + 76 0.0000 2.042021 55.5662 + 77 0.0000 2.093083 56.9557 + 78 0.0000 2.141293 58.2676 + 79 0.0000 2.189804 59.5876 + 80 0.0000 2.272621 61.8412 + 81 0.0000 2.299911 62.5838 + 82 0.0000 2.331155 63.4339 + 83 0.0000 2.359295 64.1997 + 84 0.0000 2.411918 65.6316 + 85 0.0000 2.455042 66.8051 + 86 0.0000 2.466605 67.1197 + 87 0.0000 2.478138 67.4336 + 88 0.0000 2.513357 68.3919 + 89 0.0000 2.555590 69.5411 + 90 0.0000 2.593731 70.5790 + 91 0.0000 2.597304 70.6762 + 92 0.0000 2.658244 72.3345 + 93 0.0000 2.708810 73.7105 + 94 0.0000 2.751730 74.8784 + 95 0.0000 2.784104 75.7593 + 96 0.0000 2.840434 77.2921 + 97 0.0000 2.922716 79.5311 + 98 0.0000 2.962853 80.6233 + 99 0.0000 2.982730 81.1642 + 100 0.0000 3.091989 84.1373 + 101 0.0000 3.169491 86.2462 + 102 0.0000 3.219798 87.6151 + 103 0.0000 3.490965 94.9940 + 104 0.0000 3.706967 100.8717 + 105 0.0000 3.829326 104.2013 + 106 0.0000 4.035797 109.8196 + 107 0.0000 4.165027 113.3362 + 108 0.0000 4.202811 114.3643 + 109 0.0000 4.280267 116.4720 + 110 0.0000 4.371328 118.9499 + 111 0.0000 4.392374 119.5226 + 112 0.0000 4.531826 123.3173 + 113 0.0000 4.616146 125.6117 + 114 0.0000 4.668127 127.0262 + 115 0.0000 4.719960 128.4366 + 116 0.0000 4.833248 131.5194 + 117 0.0000 4.889054 133.0379 + 118 0.0000 4.932107 134.2094 + 119 0.0000 4.963872 135.0738 + 120 0.0000 5.052980 137.4986 + 121 0.0000 5.106011 138.9416 + 122 0.0000 5.178434 140.9123 + 123 0.0000 5.201542 141.5412 + 124 0.0000 5.239586 142.5764 + 125 0.0000 5.291561 143.9907 + 126 0.0000 5.391493 146.7100 + 127 0.0000 5.501246 149.6965 + 128 0.0000 5.532151 150.5375 + 129 0.0000 5.691728 154.8798 + 130 0.0000 5.741839 156.2434 + 131 0.0000 5.954018 162.0171 + 132 0.0000 6.166361 167.7952 + 133 0.0000 6.419353 174.6795 + 134 0.0000 6.481503 176.3707 + 135 0.0000 6.511169 177.1779 + 136 0.0000 6.690057 182.0457 + 137 0.0000 6.712601 182.6592 + 138 0.0000 6.775695 184.3760 + 139 0.0000 6.815524 185.4598 + 140 0.0000 6.838800 186.0932 + 141 0.0000 7.077239 192.5815 + 142 0.0000 7.108238 193.4250 + 143 0.0000 7.125380 193.8914 + 144 0.0000 7.199303 195.9030 + 145 0.0000 7.252565 197.3523 + 146 0.0000 7.277299 198.0254 + 147 0.0000 7.325807 199.3453 + 148 0.0000 7.384267 200.9361 + 149 0.0000 7.454033 202.8345 + 150 0.0000 7.471118 203.2994 + 151 0.0000 7.555966 205.6083 + 152 0.0000 7.578467 206.2206 + 153 0.0000 7.648238 208.1191 + 154 0.0000 7.695244 209.3982 + 155 0.0000 7.896086 214.8634 + 156 0.0000 7.966749 216.7863 + 157 0.0000 8.390484 228.3167 + 158 0.0000 14.024110 381.6154 + 159 0.0000 14.904002 405.5585 + 160 0.0000 15.949821 434.0167 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.688736 -562.9691 + 1 1.0000 -20.621525 -561.1402 + 2 1.0000 -15.804595 -430.0649 + 3 1.0000 -1.612954 -43.8907 + 4 1.0000 -1.377636 -37.4874 + 5 1.0000 -0.957150 -26.0454 + 6 1.0000 -0.768309 -20.9067 + 7 1.0000 -0.733635 -19.9632 + 8 1.0000 -0.698789 -19.0150 + 9 1.0000 -0.602126 -16.3847 + 10 1.0000 -0.531988 -14.4761 + 11 1.0000 -0.462031 -12.5725 + 12 0.0000 0.030665 0.8344 + 13 0.0000 0.065924 1.7939 + 14 0.0000 0.092507 2.5172 + 15 0.0000 0.105780 2.8784 + 16 0.0000 0.113042 3.0760 + 17 0.0000 0.155444 4.2299 + 18 0.0000 0.156650 4.2627 + 19 0.0000 0.174632 4.7520 + 20 0.0000 0.178506 4.8574 + 21 0.0000 0.190249 5.1769 + 22 0.0000 0.201713 5.4889 + 23 0.0000 0.235532 6.4091 + 24 0.0000 0.271809 7.3963 + 25 0.0000 0.289212 7.8699 + 26 0.0000 0.305748 8.3198 + 27 0.0000 0.332748 9.0545 + 28 0.0000 0.336872 9.1667 + 29 0.0000 0.353613 9.6223 + 30 0.0000 0.422825 11.5056 + 31 0.0000 0.508382 13.8338 + 32 0.0000 0.531426 14.4608 + 33 0.0000 0.542664 14.7666 + 34 0.0000 0.563540 15.3347 + 35 0.0000 0.600789 16.3483 + 36 0.0000 0.631466 17.1831 + 37 0.0000 0.643892 17.5212 + 38 0.0000 0.708251 19.2725 + 39 0.0000 0.718220 19.5438 + 40 0.0000 0.734347 19.9826 + 41 0.0000 0.749128 20.3848 + 42 0.0000 0.764994 20.8165 + 43 0.0000 0.786125 21.3915 + 44 0.0000 0.808525 22.0011 + 45 0.0000 0.818732 22.2788 + 46 0.0000 0.857443 23.3322 + 47 0.0000 0.878089 23.8940 + 48 0.0000 0.894950 24.3528 + 49 0.0000 0.958092 26.0710 + 50 0.0000 0.964184 26.2368 + 51 0.0000 0.973947 26.5024 + 52 0.0000 0.987630 26.8748 + 53 0.0000 1.024005 27.8646 + 54 0.0000 1.044385 28.4192 + 55 0.0000 1.093925 29.7672 + 56 0.0000 1.156226 31.4625 + 57 0.0000 1.218309 33.1519 + 58 0.0000 1.236455 33.6457 + 59 0.0000 1.275023 34.6951 + 60 0.0000 1.316963 35.8364 + 61 0.0000 1.408042 38.3148 + 62 0.0000 1.463446 39.8224 + 63 0.0000 1.511460 41.1289 + 64 0.0000 1.532411 41.6990 + 65 0.0000 1.580603 43.0104 + 66 0.0000 1.592336 43.3297 + 67 0.0000 1.633875 44.4600 + 68 0.0000 1.650915 44.9237 + 69 0.0000 1.730701 47.0948 + 70 0.0000 1.753447 47.7137 + 71 0.0000 1.781562 48.4788 + 72 0.0000 1.918456 52.2038 + 73 0.0000 1.926324 52.4179 + 74 0.0000 1.972305 53.6692 + 75 0.0000 2.011046 54.7233 + 76 0.0000 2.042021 55.5662 + 77 0.0000 2.093083 56.9557 + 78 0.0000 2.141293 58.2676 + 79 0.0000 2.189804 59.5876 + 80 0.0000 2.272621 61.8412 + 81 0.0000 2.299911 62.5838 + 82 0.0000 2.331155 63.4339 + 83 0.0000 2.359295 64.1997 + 84 0.0000 2.411918 65.6316 + 85 0.0000 2.455042 66.8051 + 86 0.0000 2.466605 67.1197 + 87 0.0000 2.478138 67.4336 + 88 0.0000 2.513357 68.3919 + 89 0.0000 2.555590 69.5411 + 90 0.0000 2.593731 70.5790 + 91 0.0000 2.597304 70.6762 + 92 0.0000 2.658244 72.3345 + 93 0.0000 2.708810 73.7105 + 94 0.0000 2.751730 74.8784 + 95 0.0000 2.784104 75.7593 + 96 0.0000 2.840434 77.2921 + 97 0.0000 2.922716 79.5311 + 98 0.0000 2.962853 80.6233 + 99 0.0000 2.982730 81.1642 + 100 0.0000 3.091989 84.1373 + 101 0.0000 3.169491 86.2462 + 102 0.0000 3.219798 87.6151 + 103 0.0000 3.490965 94.9940 + 104 0.0000 3.706967 100.8717 + 105 0.0000 3.829326 104.2013 + 106 0.0000 4.035797 109.8196 + 107 0.0000 4.165027 113.3362 + 108 0.0000 4.202811 114.3643 + 109 0.0000 4.280267 116.4720 + 110 0.0000 4.371328 118.9499 + 111 0.0000 4.392374 119.5226 + 112 0.0000 4.531826 123.3173 + 113 0.0000 4.616146 125.6117 + 114 0.0000 4.668127 127.0262 + 115 0.0000 4.719960 128.4366 + 116 0.0000 4.833248 131.5194 + 117 0.0000 4.889054 133.0379 + 118 0.0000 4.932107 134.2094 + 119 0.0000 4.963872 135.0738 + 120 0.0000 5.052980 137.4986 + 121 0.0000 5.106011 138.9416 + 122 0.0000 5.178434 140.9123 + 123 0.0000 5.201542 141.5412 + 124 0.0000 5.239586 142.5764 + 125 0.0000 5.291561 143.9907 + 126 0.0000 5.391493 146.7100 + 127 0.0000 5.501246 149.6965 + 128 0.0000 5.532151 150.5375 + 129 0.0000 5.691728 154.8798 + 130 0.0000 5.741839 156.2434 + 131 0.0000 5.954018 162.0171 + 132 0.0000 6.166361 167.7952 + 133 0.0000 6.419353 174.6795 + 134 0.0000 6.481503 176.3707 + 135 0.0000 6.511169 177.1779 + 136 0.0000 6.690057 182.0457 + 137 0.0000 6.712601 182.6592 + 138 0.0000 6.775695 184.3760 + 139 0.0000 6.815524 185.4598 + 140 0.0000 6.838800 186.0932 + 141 0.0000 7.077239 192.5815 + 142 0.0000 7.108238 193.4250 + 143 0.0000 7.125380 193.8914 + 144 0.0000 7.199303 195.9030 + 145 0.0000 7.252565 197.3523 + 146 0.0000 7.277299 198.0254 + 147 0.0000 7.325807 199.3453 + 148 0.0000 7.384267 200.9361 + 149 0.0000 7.454033 202.8345 + 150 0.0000 7.471118 203.2994 + 151 0.0000 7.555966 205.6083 + 152 0.0000 7.578467 206.2206 + 153 0.0000 7.648238 208.1191 + 154 0.0000 7.695244 209.3982 + 155 0.0000 7.896086 214.8634 + 156 0.0000 7.966749 216.7863 + 157 0.0000 8.390484 228.3167 + 158 0.0000 14.024110 381.6154 + 159 0.0000 14.904002 405.5585 + 160 0.0000 15.949821 434.0167 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.365021 0.000000 + 1 N : 0.350512 0.000000 + 2 O : -0.236609 0.000000 + 3 H : 0.251119 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.853744 s : 3.853744 + pz : 1.329459 p : 4.479022 + px : 1.592790 + py : 1.556774 + dz2 : 0.009550 d : 0.027932 + dxz : 0.008168 + dyz : 0.005334 + dx2y2 : 0.002988 + dxy : 0.001891 + f0 : 0.001291 f : 0.004323 + f+1 : 0.000944 + f-1 : 0.000711 + f+2 : 0.000377 + f-2 : 0.000387 + f+3 : 0.000393 + f-3 : 0.000220 + 1 N s : 3.824742 s : 3.824742 + pz : 0.808428 p : 2.653867 + px : 0.804258 + py : 1.041181 + dz2 : 0.027659 d : 0.139500 + dxz : 0.037032 + dyz : 0.019364 + dx2y2 : 0.035232 + dxy : 0.020212 + f0 : 0.007856 f : 0.031379 + f+1 : 0.002583 + f-1 : 0.005224 + f+2 : 0.002634 + f-2 : 0.005757 + f+3 : 0.003351 + f-3 : 0.003975 + 2 O s : 3.876738 s : 3.876738 + pz : 1.706986 p : 4.290847 + px : 1.227886 + py : 1.355974 + dz2 : 0.004692 d : 0.061596 + dxz : 0.007651 + dyz : 0.012201 + dx2y2 : 0.025850 + dxy : 0.011202 + f0 : 0.001116 f : 0.007429 + f+1 : 0.000576 + f-1 : 0.000689 + f+2 : 0.000009 + f-2 : 0.001317 + f+3 : 0.001978 + f-3 : 0.001744 + 3 H s : 0.640440 s : 0.640440 + pz : 0.022563 p : 0.088166 + px : 0.037124 + py : 0.028479 + dz2 : 0.001491 d : 0.020275 + dxz : 0.002544 + dyz : 0.005518 + dx2y2 : 0.009163 + dxy : 0.001558 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.575353 0.000000 + 1 N : -0.244077 0.000000 + 2 O : 0.246908 0.000000 + 3 H : -0.578184 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.131567 s : 3.131567 + pz : 1.237000 p : 3.953055 + px : 1.340741 + py : 1.375314 + dz2 : 0.078852 d : 0.262839 + dxz : 0.073736 + dyz : 0.053327 + dx2y2 : 0.017997 + dxy : 0.038926 + f0 : 0.015197 f : 0.077186 + f+1 : 0.017466 + f-1 : 0.015373 + f+2 : 0.010770 + f-2 : 0.011690 + f+3 : 0.005168 + f-3 : 0.001522 + 1 N s : 3.032796 s : 3.032796 + pz : 0.851789 p : 2.839054 + px : 0.889981 + py : 1.097284 + dz2 : 0.198828 d : 0.928450 + dxz : 0.237118 + dyz : 0.139376 + dx2y2 : 0.162080 + dxy : 0.191047 + f0 : 0.092735 f : 0.443777 + f+1 : 0.054327 + f-1 : 0.057131 + f+2 : 0.028660 + f-2 : 0.086549 + f+3 : 0.064165 + f-3 : 0.060210 + 2 O s : 3.315044 s : 3.315044 + pz : 1.406854 p : 3.993324 + px : 1.241456 + py : 1.345013 + dz2 : 0.050613 d : 0.327836 + dxz : 0.064594 + dyz : 0.034935 + dx2y2 : 0.065106 + dxy : 0.112588 + f0 : 0.011835 f : 0.116888 + f+1 : 0.012808 + f-1 : 0.014372 + f+2 : 0.004585 + f-2 : 0.021344 + f+3 : 0.029975 + f-3 : 0.021970 + 3 H s : 0.623252 s : 0.623252 + pz : 0.145785 p : 0.566766 + px : 0.189008 + py : 0.231972 + dz2 : 0.031943 d : 0.388166 + dxz : 0.060831 + dyz : 0.081152 + dx2y2 : 0.119969 + dxy : 0.094272 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3650 8.0000 -0.3650 1.8136 1.8136 -0.0000 + 1 N 6.6495 7.0000 0.3505 2.5832 2.5832 -0.0000 + 2 O 8.2366 8.0000 -0.2366 1.7934 1.7934 -0.0000 + 3 H 0.7489 1.0000 0.2511 0.9987 0.9987 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8040 B( 0-O , 3-H ) : 0.9522 B( 1-N , 2-O ) : 1.7344 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.651 sec +Sum of individual times .... 2.346 sec ( 88.5%) + +Fock matrix formation .... 1.875 sec ( 70.7%) +Diagonalization .... 0.200 sec ( 7.6%) +Density matrix formation .... 0.015 sec ( 0.5%) +Population analysis .... 0.071 sec ( 2.7%) +Initial guess .... 0.012 sec ( 0.5%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.007 sec ( 0.3%) +DIIS solution .... 0.173 sec ( 6.5%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.203 sec +Reference energy ... -204.706261860 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.391 sec +AO-integral generation ... 0.143 sec +Half transformation ... 0.079 sec +K-integral sorting ... 5.398 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.024 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.027 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.030 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.045 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.030 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.350 sec +AO-integral generation ... 0.246 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.049 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.158 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.255 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090006486 +EMP2(bb)= -0.090006486 +EMP2(ab)= -0.516890242 + +Initial guess performed in 0.133 sec +E(0) ... -204.706261860 +E(MP2) ... -0.696903214 +Initial E(tot) ... -205.403165074 + ... 0.188952292 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.403165074 -0.696903214 -0.000000000 0.019731000 2.75 0.000002022 + *** Turning on DIIS *** + 1 -205.375036015 -0.668774155 0.028129059 0.010676140 2.73 0.055618967 + 2 -205.394510585 -0.688248725 -0.019474570 0.004031033 2.78 0.058487932 + 3 -205.398324698 -0.692062838 -0.003814113 0.002026172 2.83 0.071604559 + 4 -205.399865456 -0.693603596 -0.001540758 0.000857909 2.80 0.077527460 + 5 -205.400360873 -0.694099013 -0.000495418 0.000529527 2.89 0.082016657 + 6 -205.400444308 -0.694182448 -0.000083435 0.000345612 2.83 0.084136422 + 7 -205.400478699 -0.694216839 -0.000034391 0.000248956 2.88 0.085107643 + 8 -205.400487007 -0.694225146 -0.000008308 0.000169808 2.90 0.085563723 + 9 -205.400484109 -0.694222249 0.000002898 0.000104996 2.81 0.085760384 + 10 -205.400489300 -0.694227440 -0.000005191 0.000054623 2.79 0.085850995 + 11 -205.400485813 -0.694223953 0.000003487 0.000029665 2.83 0.085872257 + 12 -205.400488326 -0.694226466 -0.000002513 0.000016947 2.78 0.085887939 + 13 -205.400488239 -0.694226379 0.000000087 0.000009818 2.85 0.085891164 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.706261860 +E(CORR) ... -0.694226379 +E(TOT) ... -205.400488239 +Singles norm **1/2 ... 0.085891164 ( 0.042945582, 0.042945582) +T1 diagnostic ... 0.020244741 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.061678 + 8a-> 13a 8b-> 13b 0.054060 + 8a-> 13a 9b-> 13b 0.045020 + 9a-> 13a 8b-> 13b 0.045020 + 8b-> 13b -1b-> -1b 0.029984 + 8a-> 13a -1a-> -1a 0.029984 + 11a-> 13a 11b-> 13b 0.029606 + 5a-> 13a 5b-> 13b 0.029437 + 9a-> 22a 9b-> 13b 0.023718 + 9a-> 13a 9b-> 22b 0.023718 + 11a-> 25a 11b-> 25b 0.021386 + 8a-> 22a 8b-> 13b 0.019115 + 8a-> 13a 8b-> 22b 0.019115 + 11b-> 25b -1b-> -1b 0.018203 + 11a-> 25a -1a-> -1a 0.018203 + 11a-> 26a -1a-> -1a 0.018019 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034429953 + alpha-alpha-alpha ... -0.000865685 ( 2.5%) + alpha-alpha-beta ... -0.016349292 ( 47.5%) + alpha-beta -beta ... -0.016349292 ( 47.5%) + beta -beta -beta ... -0.000865685 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034429953 + +Final correlation energy ... -0.728656332 +E(CCSD) ... -205.400488239 +E(CCSD(T)) ... -205.434918192 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210091829 sqrt= 1.100041740 +W(HF) = 0.826383565 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.305065 -0.000000 + 1 N : 0.176737 0.000000 + 2 O : -0.110801 -0.000000 + 3 H : 0.239130 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.833310 s : 3.833310 + pz : 1.307155 p : 4.405169 + px : 1.569332 + py : 1.528682 + dz2 : 0.014742 d : 0.058552 + dxz : 0.013163 + dyz : 0.012306 + dx2y2 : 0.009958 + dxy : 0.008384 + f0 : 0.001763 f : 0.008034 + f+1 : 0.001193 + f-1 : 0.001255 + f+2 : 0.000924 + f-2 : 0.000983 + f+3 : 0.001040 + f-3 : 0.000876 + 1 N s : 3.879694 s : 3.879694 + pz : 0.854315 p : 2.744369 + px : 0.853814 + py : 1.036239 + dz2 : 0.035395 d : 0.168907 + dxz : 0.044920 + dyz : 0.026072 + dx2y2 : 0.037452 + dxy : 0.025068 + f0 : 0.007401 f : 0.030294 + f+1 : 0.002434 + f-1 : 0.005337 + f+2 : 0.003019 + f-2 : 0.005475 + f+3 : 0.003218 + f-3 : 0.003409 + 2 O s : 3.863253 s : 3.863253 + pz : 1.628164 p : 4.154967 + px : 1.202185 + py : 1.324618 + dz2 : 0.010116 d : 0.082758 + dxz : 0.014251 + dyz : 0.017014 + dx2y2 : 0.027345 + dxy : 0.014032 + f0 : 0.001546 f : 0.009823 + f+1 : 0.001039 + f-1 : 0.001133 + f+2 : 0.000619 + f-2 : 0.001641 + f+3 : 0.002034 + f-3 : 0.001810 + 3 H s : 0.648623 s : 0.648623 + pz : 0.026439 p : 0.094758 + px : 0.039649 + py : 0.028670 + dz2 : 0.001257 d : 0.017490 + dxz : 0.002419 + dyz : 0.004825 + dx2y2 : 0.007992 + dxy : 0.000997 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.581297 -0.000000 + 1 N : -0.287601 -0.000000 + 2 O : 0.289659 0.000000 + 3 H : -0.583356 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.136402 s : 3.136402 + pz : 1.227134 p : 3.904366 + px : 1.324242 + py : 1.352990 + dz2 : 0.084618 d : 0.293761 + dxz : 0.080422 + dyz : 0.058568 + dx2y2 : 0.023924 + dxy : 0.046229 + f0 : 0.016795 f : 0.084173 + f+1 : 0.019217 + f-1 : 0.015710 + f+2 : 0.011475 + f-2 : 0.012669 + f+3 : 0.006007 + f-3 : 0.002300 + 1 N s : 3.038066 s : 3.038066 + pz : 0.872113 p : 2.879463 + px : 0.918255 + py : 1.089095 + dz2 : 0.204680 d : 0.935859 + dxz : 0.239576 + dyz : 0.135505 + dx2y2 : 0.157860 + dxy : 0.198237 + f0 : 0.089102 f : 0.434213 + f+1 : 0.055195 + f-1 : 0.056435 + f+2 : 0.028196 + f-2 : 0.082944 + f+3 : 0.062732 + f-3 : 0.059610 + 2 O s : 3.317757 s : 3.317757 + pz : 1.357578 p : 3.910858 + px : 1.226425 + py : 1.326856 + dz2 : 0.056518 d : 0.356527 + dxz : 0.068594 + dyz : 0.040586 + dx2y2 : 0.073533 + dxy : 0.117296 + f0 : 0.012733 f : 0.125199 + f+1 : 0.013716 + f-1 : 0.014584 + f+2 : 0.005382 + f-2 : 0.022381 + f+3 : 0.031708 + f-3 : 0.024697 + 3 H s : 0.624193 s : 0.624193 + pz : 0.146797 p : 0.581012 + px : 0.194848 + py : 0.239366 + dz2 : 0.032354 d : 0.378151 + dxz : 0.058581 + dyz : 0.078704 + dx2y2 : 0.115411 + dxy : 0.093101 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3051 8.0000 -0.3051 2.1601 1.7013 0.4587 + 1 N 6.8233 7.0000 0.1767 2.8484 2.3558 0.4927 + 2 O 8.1108 8.0000 -0.1108 2.1783 1.6787 0.4996 + 3 H 0.7609 1.0000 0.2391 1.0185 0.9440 0.0746 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7232 B( 0-O , 3-H ) : 0.8891 B( 1-N , 2-O ) : 1.5837 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 54.620 sec + +Fock Matrix Formation ... 0.203 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 1.832 sec ( 3.4%) +State Vector Update ... 0.083 sec ( 0.2%) +Sigma-vector construction ... 37.529 sec ( 68.7%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.021 sec ( 0.1% of sigma) + (0-ext) ... 0.068 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (2-ext) ... 0.933 sec ( 2.5% of sigma) + (4-ext) ... 20.725 sec ( 55.2% of sigma) + ... 1.320 sec ( 3.5% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.108 sec ( 0.3% of sigma) + Fock-dressing ... 2.152 sec ( 5.7% of sigma) + (ik|jl)-dressing ... 0.074 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.461 sec ( 25.2% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.831 sec ( 12.5% of ALL) + I/O of integral and amplitudes ... 0.810 sec ( 11.9% of (T)) + External N**7 contributions ... 3.904 sec ( 57.2% of (T)) + Internal N**7 contributions ... 0.311 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.587 sec ( 23.2% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.434918192104 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.006568560 -0.000361249 0.001135741 + 2 N : -0.007493804 0.000603396 0.000207565 + 3 O : 0.005786645 0.000349464 0.000498055 + 4 H : -0.004861400 -0.000591611 -0.001841360 + +Norm of the cartesian gradient ... 0.012742053 +RMS gradient ... 0.003678314 +MAX gradient ... 0.007493804 + +------- +TIMINGS +------- + +Total numerical gradient time ... 346.645 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: -538.45 cm**-1 ***imaginary mode*** + 7: 562.31 cm**-1 + 8: 786.46 cm**-1 + 9: 1156.73 cm**-1 + 10: 1670.34 cm**-1 + 11: 3704.26 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 -0.048098 -0.455298 0.022381 0.004095 -0.024170 -0.036750 + 1 -0.037169 -0.109797 0.158142 0.050151 0.034874 0.049433 + 2 -0.051632 0.456450 0.202051 -0.052160 0.059230 -0.010942 + 3 0.042606 0.267809 0.132087 0.046999 -0.477957 -0.000459 + 4 -0.041658 0.121957 -0.260878 -0.047442 -0.554817 0.000182 + 5 0.064175 -0.170670 -0.480523 -0.032830 0.014362 0.000103 + 6 -0.035217 0.233826 -0.168095 -0.021043 0.449864 0.000510 + 7 0.035245 -0.002501 0.048503 -0.007441 0.450530 0.000260 + 8 -0.022175 -0.337741 0.245331 0.023149 -0.083195 -0.000381 + 9 0.730340 -0.206223 0.477321 -0.384105 -0.115007 0.581578 + 10 0.609400 0.087706 0.345242 -0.018640 0.005298 -0.791244 + 11 0.279697 0.487450 -0.423598 0.916674 0.180805 0.178284 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 7: 562.31 0.019613 99.12 0.010885 ( 0.078035 0.017276 -0.067058) + 8: 786.46 0.038192 193.01 0.015154 ( 0.081066 -0.005859 -0.092458) + 9: 1156.73 0.005030 25.42 0.001357 (-0.020168 0.014425 0.027243) + 10: 1670.34 0.032656 165.03 0.006101 (-0.057756 -0.015969 0.050102) + 11: 3704.26 0.011229 56.75 0.000946 ( 0.024082 -0.017766 -0.007101) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 7 +The total number of vibrations considered is 5 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 562.31 E(vib) ... 0.11 +freq. 786.46 E(vib) ... 0.05 +freq. 1156.73 E(vib) ... 0.01 +freq. 1670.34 E(vib) ... 0.00 +freq. 3704.26 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.43491819 Eh +Zero point energy ... 0.01795217 Eh 11.27 kcal/mol +Thermal vibrational correction ... 0.00028668 Eh 0.18 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.41384679 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00311923 Eh 1.96 kcal/mol +Non-thermal (ZPE) correction 0.01795217 Eh 11.27 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02107140 Eh 13.22 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.41384679 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.41290258 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.725130 0.404033 0.363012 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00037716 Eh 0.24 kcal/mol +Rotational entropy ... 0.00994375 Eh 6.24 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02812322 Eh 17.65 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00994375 Eh 6.24 kcal/mol| +| sn= 2 | S(rot)= 0.00928929 Eh 5.83 kcal/mol| +| sn= 3 | S(rot)= 0.00890646 Eh 5.59 kcal/mol| +| sn= 4 | S(rot)= 0.00863483 Eh 5.42 kcal/mol| +| sn= 5 | S(rot)= 0.00842415 Eh 5.29 kcal/mol| +| sn= 6 | S(rot)= 0.00825200 Eh 5.18 kcal/mol| +| sn= 7 | S(rot)= 0.00810646 Eh 5.09 kcal/mol| +| sn= 8 | S(rot)= 0.00798038 Eh 5.01 kcal/mol| +| sn= 9 | S(rot)= 0.00786917 Eh 4.94 kcal/mol| +| sn=10 | S(rot)= 0.00776969 Eh 4.88 kcal/mol| +| sn=11 | S(rot)= 0.00767970 Eh 4.82 kcal/mol| +| sn=12 | S(rot)= 0.00759755 Eh 4.77 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.41290258 Eh +Total entropy correction ... -0.02812322 Eh -17.65 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44102581 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00610761 Eh -3.83 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.434918192 Eh +Current gradient norm .... 0.012742053 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + -0.030668292 0.101158884 0.172835953 0.474487139 0.498484124 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999751420 +Lowest eigenvalues of augmented Hessian: + -0.000084900 0.098826744 0.172840052 0.473884519 0.498364505 +Length of the computed step .... 0.022301249 +The final length of the internal step .... 0.022301249 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0091044469 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0041064366 RMS(Int)= 0.0091021849 + Iter 1: RMS(Cart)= 0.0000099436 RMS(Int)= 0.0000154573 + Iter 2: RMS(Cart)= 0.0000000512 RMS(Int)= 0.0000000756 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0022583026 0.0001000000 NO + MAX gradient 0.0042581289 0.0003000000 NO + RMS step 0.0091044469 0.0020000000 NO + MAX step 0.0193237922 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0102 Max(Angles) 0.24 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4846 -0.001576 0.0102 1.4948 + 2. B(O 2,N 1) 1.1715 0.004258 -0.0041 1.1674 + 3. B(H 3,O 0) 0.9731 0.002694 -0.0029 0.9702 + 4. A(N 1,O 0,H 3) 103.96 -0.000018 -0.23 103.73 + 5. A(O 0,N 1,O 2) 111.90 0.001652 -0.24 111.66 + 6. D(O 2,N 1,O 0,H 3) 73.64 0.008002 -0.00 73.64 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.423781 -0.275714 0.738672 + N 0.291598 -0.510673 -0.552683 + O 1.117532 0.292804 -0.740109 + H -0.985348 0.493583 0.554119 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.800830 -0.521024 1.395889 + 1 N 7.0000 0 14.007 0.551041 -0.965032 -1.044420 + 2 O 8.0000 0 15.999 2.111829 0.553318 -1.398603 + 3 H 1.0000 0 1.008 -1.862037 0.932737 1.047134 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.494848439548 0.00000000 0.00000000 + O 2 1 0 1.167419793421 111.65950849 0.00000000 + H 1 2 3 0.970172836005 103.72787924 73.63636337 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.824854162465 0.00000000 0.00000000 + O 2 1 0 2.206103692884 111.65950849 0.00000000 + H 1 2 3 1.833360962619 103.72787924 73.63636337 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.1 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2231 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2700 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.487104265258 Eh + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.771e-04 +Time for diagonalization ... 0.006 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.004 sec +Total time needed ... 0.011 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7060507423 0.000000000000 0.00027568 0.00000840 0.0016662 0.7000 + 1 -204.7060708720 -0.000020129652 0.00022566 0.00000709 0.0013652 0.7000 + ***Turning on DIIS*** + 2 -204.7060874606 -0.000016588589 0.00057516 0.00001853 0.0010886 0.0000 + 3 -204.7054793923 0.000608068239 0.00021974 0.00000852 0.0003407 0.0000 + 4 -204.7063117953 -0.000832403004 0.00007098 0.00000290 0.0000930 0.0000 + 5 -204.7062166722 0.000095123130 0.00003706 0.00000113 0.0000475 0.0000 + 6 -204.7059772869 0.000239385297 0.00001795 0.00000050 0.0000368 0.0000 + 7 -204.7061731924 -0.000195905509 0.00000866 0.00000022 0.0000125 0.0000 + 8 -204.7061516830 0.000021509443 0.00000192 0.00000009 0.0000032 0.0000 + 9 -204.7061340385 0.000017644448 0.00000076 0.00000003 0.0000016 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 10 CYCLES * + ***************************************************** + +Total Energy : -204.70614618 Eh -5570.33743 eV + Last Energy change ... -1.2146e-05 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.8376e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 4 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.494 sec +Reference energy ... -204.706141124 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 10.313 sec +AO-integral generation ... 0.208 sec +Half transformation ... 0.115 sec +K-integral sorting ... 8.096 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.071 s ( 0.000 ms/b) + 377910 b 0 skpd 0.078 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.078 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.078 s ( 0.001 ms/b) +: 159120 b 0 skpd 0.052 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.088 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.065 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.061 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.099 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.059 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.836 sec +AO-integral generation ... 0.649 sec +Half transformation ... 0.084 sec +J-integral sorting ... 0.071 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.247 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.355 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090018857 +EMP2(bb)= -0.090018857 +EMP2(ab)= -0.517054259 + +Initial guess performed in 0.169 sec +E(0) ... -204.706141124 +E(MP2) ... -0.697091973 +Initial E(tot) ... -205.403233097 + ... 0.189152048 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.403233097 -0.697091973 -0.000000000 0.019606905 5.48 0.000001789 + *** Turning on DIIS *** + 1 -205.374988321 -0.668847197 0.028244776 0.010313363 7.45 0.055721442 + 2 -205.394493491 -0.688352367 -0.019505170 0.003972977 5.85 0.058531268 + 3 -205.398308245 -0.692167121 -0.003814753 0.001949901 6.50 0.071650922 + 4 -205.399849010 -0.693707886 -0.001540765 0.000856918 4.83 0.077564014 + 5 -205.400344250 -0.694203126 -0.000495240 0.000540038 5.39 0.082063375 + 6 -205.400427865 -0.694286741 -0.000083615 0.000342043 5.75 0.084209366 + 7 -205.400462873 -0.694321749 -0.000035008 0.000245082 6.00 0.085209850 + 8 -205.400471401 -0.694330277 -0.000008528 0.000167100 5.28 0.085677111 + 9 -205.400468399 -0.694327275 0.000003002 0.000103779 6.34 0.085872482 + 10 -205.400473638 -0.694332514 -0.000005239 0.000054045 6.61 0.085963941 + 11 -205.400470088 -0.694328964 0.000003550 0.000029481 5.66 0.085983782 + 12 -205.400472696 -0.694331572 -0.000002608 0.000016760 5.43 0.085999938 + 13 -205.400472574 -0.694331450 0.000000122 0.000009589 5.94 0.086002473 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.706141124 +E(CORR) ... -0.694331450 +E(TOT) ... -205.400472574 +Singles norm **1/2 ... 0.086002473 ( 0.043001236, 0.043001236) +T1 diagnostic ... 0.020270977 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.058946 + 8a-> 13a 8b-> 13b 0.056054 + 8a-> 13a 9b-> 13b 0.044975 + 9a-> 13a 8b-> 13b 0.044975 + 5a-> 13a 5b-> 13b 0.029683 + 8a-> 13a -1a-> -1a 0.029498 + 8b-> 13b -1b-> -1b 0.029498 + 11a-> 13a 11b-> 13b 0.028955 + 9a-> 13a 9b-> 22b 0.022792 + 9a-> 22a 9b-> 13b 0.022792 + 11a-> 25a 11b-> 25b 0.022112 + 8a-> 22a 8b-> 13b 0.019993 + 8a-> 13a 8b-> 22b 0.019993 + 11a-> 24a 11b-> 25b 0.019098 + 11a-> 25a 11b-> 24b 0.019098 + 11b-> 24b -1b-> -1b 0.018418 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034488506 + alpha-alpha-alpha ... -0.000865414 ( 2.5%) + alpha-alpha-beta ... -0.016378839 ( 47.5%) + alpha-beta -beta ... -0.016378839 ( 47.5%) + beta -beta -beta ... -0.000865414 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034488506 + +Final correlation energy ... -0.728819956 +E(CCSD) ... -205.400472574 +E(CCSD(T)) ... -205.434961080 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210280012 sqrt= 1.100127271 +W(HF) = 0.826255074 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 111.160 sec + +Fock Matrix Formation ... 0.494 sec ( 0.4%) +Initial Guess ... 0.169 sec ( 0.2%) +DIIS Solver ... 4.633 sec ( 4.2%) +State Vector Update ... 0.238 sec ( 0.2%) +Sigma-vector construction ... 77.639 sec ( 69.8%) + <0|H|D> ... 0.005 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.035 sec ( 0.0% of sigma) + (0-ext) ... 0.110 sec ( 0.1% of sigma) + (2-ext Fock) ... 0.038 sec ( 0.0% of sigma) + (2-ext) ... 1.381 sec ( 1.8% of sigma) + (4-ext) ... 46.558 sec ( 60.0% of sigma) + ... 3.886 sec ( 5.0% of sigma) + ... 0.005 sec ( 0.0% of sigma) + (1-ext) ... 0.013 sec ( 0.0% of sigma) + (1-ext) ... 0.194 sec ( 0.2% of sigma) + Fock-dressing ... 5.199 sec ( 6.7% of sigma) + (ik|jl)-dressing ... 0.129 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 16.354 sec ( 21.1% of sigma) + Pair energies ... 0.023 sec ( 0.0% of sigma) +Total Time for computing (T) ... 14.442 sec ( 13.0% of ALL) + I/O of integral and amplitudes ... 2.323 sec ( 16.1% of (T)) + External N**7 contributions ... 5.930 sec ( 41.1% of (T)) + Internal N**7 contributions ... 0.643 sec ( 4.5% of (T)) + N**6 triples energy contributions ... 2.643 sec ( 18.3% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.434961079740 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.004379392 0.002379808 0.001879750 + 2 N : -0.003639942 0.002434859 -0.002389217 + 3 O : 0.002381011 -0.002204527 0.001782899 + 4 H : -0.003120462 -0.002610140 -0.001273432 + +Norm of the cartesian gradient ... 0.009227227 +RMS gradient ... 0.002663671 +MAX gradient ... 0.004379392 + +------- +TIMINGS +------- + +Total numerical gradient time ... 622.246 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.434961080 Eh +Current gradient norm .... 0.009227227 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999656 +Lowest eigenvalues of augmented Hessian: + -0.000000098 0.096272100 0.171047780 0.475178190 0.499838961 +Length of the computed step .... 0.000829923 +The final length of the internal step .... 0.000829923 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0003388147 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0002213350 RMS(Int)= 0.0003388164 + Iter 1: RMS(Cart)= 0.0000000042 RMS(Int)= 0.0000000067 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000428876 0.0000050000 NO + RMS gradient 0.0000694556 0.0001000000 YES + MAX gradient 0.0001187426 0.0003000000 YES + RMS step 0.0003388147 0.0020000000 YES + MAX step 0.0008272976 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0004 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4948 -0.000115 0.0004 1.4953 + 2. B(O 2,N 1) 1.1674 -0.000119 0.0000 1.1674 + 3. B(H 3,O 0) 0.9702 -0.000021 0.0000 0.9702 + 4. A(N 1,O 0,H 3) 103.73 -0.000022 -0.00 103.73 + 5. A(O 0,N 1,O 2) 111.66 -0.000026 -0.00 111.66 + 6. D(O 2,N 1,O 0,H 3) 73.64 0.007590 -0.00 73.64 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.423921 -0.275696 0.738849 + N 0.291734 -0.510710 -0.552851 + O 1.117674 0.292794 -0.740225 + H -0.985486 0.493612 0.554228 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.801095 -0.520991 1.396221 + 1 N 7.0000 0 14.007 0.551297 -0.965101 -1.044737 + 2 O 8.0000 0 15.999 2.112098 0.553300 -1.398823 + 3 H 1.0000 0 1.008 -1.862299 0.932792 1.047338 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.495286226561 0.00000000 0.00000000 + O 2 1 0 1.167434911897 111.65893014 0.00000000 + H 1 2 3 0.970193710566 103.72539705 73.63636337 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.825681460024 0.00000000 0.00000000 + O 2 1 0 2.206132262663 111.65893014 0.00000000 + H 1 2 3 1.833400409822 103.72539705 73.63636337 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.1 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2231 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2700 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.477604361538 Eh + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.4776043615 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.772e-04 +Time for diagonalization ... 0.005 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.007 sec +Total time needed ... 0.013 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7060965399 0.000000000000 0.00001378 0.00000029 0.0000594 0.7000 + 1 -204.7060965580 -0.000000018051 0.00001021 0.00000025 0.0000466 0.7000 + ***Turning on DIIS*** + 2 -204.7060965731 -0.000000015111 0.00002515 0.00000065 0.0000360 0.0000 + 3 -204.7061114120 -0.000014838913 0.00001058 0.00000028 0.0000091 0.0000 + 4 -204.7060908376 0.000020574344 0.00000342 0.00000010 0.0000031 0.0000 + 5 -204.7060920990 -0.000001261411 0.00000159 0.00000004 0.0000012 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 6 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70609970 Eh -5570.33616 eV + +Components: +Nuclear Repulsion : 68.47760436 Eh 1863.37035 eV +Electronic Energy : -273.18370406 Eh -7433.70651 eV +One Electron Energy: -416.64275878 Eh -11337.42585 eV +Two Electron Energy: 143.45905471 Eh 3903.71934 eV + +Virial components: +Potential Energy : -408.93421178 Eh -11127.66562 eV +Kinetic Energy : 204.22811208 Eh 5557.32946 eV +Virial Ratio : 2.00234046 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -7.6044e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.8083e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.6709e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.3760e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.690846 -563.0265 + 1 1.0000 -20.618989 -561.0712 + 2 1.0000 -15.805699 -430.0949 + 3 1.0000 -1.616980 -44.0003 + 4 1.0000 -1.374610 -37.4050 + 5 1.0000 -0.957077 -26.0434 + 6 1.0000 -0.768129 -20.9019 + 7 1.0000 -0.734909 -19.9979 + 8 1.0000 -0.699238 -19.0272 + 9 1.0000 -0.604362 -16.4455 + 10 1.0000 -0.530622 -14.4390 + 11 1.0000 -0.460865 -12.5408 + 12 0.0000 0.031017 0.8440 + 13 0.0000 0.066101 1.7987 + 14 0.0000 0.092157 2.5077 + 15 0.0000 0.105498 2.8707 + 16 0.0000 0.113214 3.0807 + 17 0.0000 0.155445 4.2299 + 18 0.0000 0.157225 4.2783 + 19 0.0000 0.174274 4.7422 + 20 0.0000 0.178484 4.8568 + 21 0.0000 0.190176 5.1750 + 22 0.0000 0.201489 5.4828 + 23 0.0000 0.235047 6.3959 + 24 0.0000 0.270460 7.3596 + 25 0.0000 0.287468 7.8224 + 26 0.0000 0.305047 8.3007 + 27 0.0000 0.332338 9.0434 + 28 0.0000 0.336546 9.1579 + 29 0.0000 0.353489 9.6189 + 30 0.0000 0.424115 11.5408 + 31 0.0000 0.508248 13.8301 + 32 0.0000 0.531123 14.4526 + 33 0.0000 0.542355 14.7582 + 34 0.0000 0.562910 15.3176 + 35 0.0000 0.600535 16.3414 + 36 0.0000 0.631941 17.1960 + 37 0.0000 0.645423 17.5629 + 38 0.0000 0.707815 19.2606 + 39 0.0000 0.717817 19.5328 + 40 0.0000 0.734015 19.9736 + 41 0.0000 0.750794 20.4301 + 42 0.0000 0.764172 20.7942 + 43 0.0000 0.786655 21.4060 + 44 0.0000 0.808339 21.9960 + 45 0.0000 0.819422 22.2976 + 46 0.0000 0.857130 23.3237 + 47 0.0000 0.878371 23.9017 + 48 0.0000 0.895083 24.3565 + 49 0.0000 0.958617 26.0853 + 50 0.0000 0.964471 26.2446 + 51 0.0000 0.974642 26.5214 + 52 0.0000 0.988448 26.8970 + 53 0.0000 1.025362 27.9015 + 54 0.0000 1.044825 28.4311 + 55 0.0000 1.094573 29.7848 + 56 0.0000 1.155441 31.4411 + 57 0.0000 1.218298 33.1516 + 58 0.0000 1.235710 33.6254 + 59 0.0000 1.273918 34.6651 + 60 0.0000 1.318477 35.8776 + 61 0.0000 1.409956 38.3669 + 62 0.0000 1.465294 39.8727 + 63 0.0000 1.512117 41.1468 + 64 0.0000 1.530551 41.6484 + 65 0.0000 1.580131 42.9975 + 66 0.0000 1.591791 43.3148 + 67 0.0000 1.632298 44.4171 + 68 0.0000 1.651256 44.9330 + 69 0.0000 1.730140 47.0795 + 70 0.0000 1.751241 47.6537 + 71 0.0000 1.779443 48.4211 + 72 0.0000 1.915066 52.1116 + 73 0.0000 1.926646 52.4267 + 74 0.0000 1.972218 53.6668 + 75 0.0000 2.008089 54.6429 + 76 0.0000 2.041968 55.5648 + 77 0.0000 2.091806 56.9209 + 78 0.0000 2.139950 58.2310 + 79 0.0000 2.189574 59.5813 + 80 0.0000 2.271524 61.8113 + 81 0.0000 2.299071 62.5609 + 82 0.0000 2.331826 63.4522 + 83 0.0000 2.359059 64.1933 + 84 0.0000 2.412050 65.6352 + 85 0.0000 2.453559 66.7647 + 86 0.0000 2.467043 67.1317 + 87 0.0000 2.477142 67.4065 + 88 0.0000 2.512627 68.3720 + 89 0.0000 2.557560 69.5947 + 90 0.0000 2.594715 70.6058 + 91 0.0000 2.597698 70.6870 + 92 0.0000 2.661376 72.4197 + 93 0.0000 2.704252 73.5864 + 94 0.0000 2.749121 74.8074 + 95 0.0000 2.778944 75.6189 + 96 0.0000 2.838509 77.2398 + 97 0.0000 2.919982 79.4568 + 98 0.0000 2.960333 80.5548 + 99 0.0000 2.977664 81.0264 + 100 0.0000 3.083223 83.8988 + 101 0.0000 3.168632 86.2229 + 102 0.0000 3.223719 87.7218 + 103 0.0000 3.487885 94.9102 + 104 0.0000 3.709979 100.9537 + 105 0.0000 3.827013 104.1383 + 106 0.0000 4.038448 109.8918 + 107 0.0000 4.167989 113.4168 + 108 0.0000 4.208481 114.5186 + 109 0.0000 4.282513 116.5331 + 110 0.0000 4.369313 118.8950 + 111 0.0000 4.392704 119.5316 + 112 0.0000 4.533744 123.3695 + 113 0.0000 4.617935 125.6604 + 114 0.0000 4.665802 126.9629 + 115 0.0000 4.721733 128.4849 + 116 0.0000 4.836403 131.6052 + 117 0.0000 4.888623 133.0262 + 118 0.0000 4.930336 134.1613 + 119 0.0000 4.962341 135.0322 + 120 0.0000 5.051435 137.4565 + 121 0.0000 5.107240 138.9751 + 122 0.0000 5.183365 141.0465 + 123 0.0000 5.199084 141.4743 + 124 0.0000 5.240542 142.6024 + 125 0.0000 5.298570 144.1814 + 126 0.0000 5.391946 146.7223 + 127 0.0000 5.494991 149.5263 + 128 0.0000 5.527103 150.4001 + 129 0.0000 5.697054 155.0247 + 130 0.0000 5.743475 156.2879 + 131 0.0000 5.945290 161.7796 + 132 0.0000 6.168020 167.8403 + 133 0.0000 6.415124 174.5644 + 134 0.0000 6.479957 176.3286 + 135 0.0000 6.509814 177.1410 + 136 0.0000 6.691819 182.0936 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-20.9019 + 7 1.0000 -0.734909 -19.9979 + 8 1.0000 -0.699238 -19.0272 + 9 1.0000 -0.604362 -16.4455 + 10 1.0000 -0.530622 -14.4390 + 11 1.0000 -0.460865 -12.5408 + 12 0.0000 0.031017 0.8440 + 13 0.0000 0.066101 1.7987 + 14 0.0000 0.092157 2.5077 + 15 0.0000 0.105498 2.8707 + 16 0.0000 0.113214 3.0807 + 17 0.0000 0.155445 4.2299 + 18 0.0000 0.157225 4.2783 + 19 0.0000 0.174274 4.7422 + 20 0.0000 0.178484 4.8568 + 21 0.0000 0.190176 5.1750 + 22 0.0000 0.201489 5.4828 + 23 0.0000 0.235047 6.3959 + 24 0.0000 0.270460 7.3596 + 25 0.0000 0.287468 7.8224 + 26 0.0000 0.305047 8.3007 + 27 0.0000 0.332338 9.0434 + 28 0.0000 0.336546 9.1579 + 29 0.0000 0.353489 9.6189 + 30 0.0000 0.424115 11.5408 + 31 0.0000 0.508248 13.8301 + 32 0.0000 0.531123 14.4526 + 33 0.0000 0.542355 14.7582 + 34 0.0000 0.562910 15.3176 + 35 0.0000 0.600535 16.3414 + 36 0.0000 0.631941 17.1960 + 37 0.0000 0.645423 17.5629 + 38 0.0000 0.707815 19.2606 + 39 0.0000 0.717817 19.5328 + 40 0.0000 0.734015 19.9736 + 41 0.0000 0.750794 20.4301 + 42 0.0000 0.764172 20.7942 + 43 0.0000 0.786655 21.4060 + 44 0.0000 0.808339 21.9960 + 45 0.0000 0.819422 22.2976 + 46 0.0000 0.857130 23.3237 + 47 0.0000 0.878371 23.9017 + 48 0.0000 0.895083 24.3565 + 49 0.0000 0.958617 26.0853 + 50 0.0000 0.964471 26.2446 + 51 0.0000 0.974642 26.5214 + 52 0.0000 0.988448 26.8970 + 53 0.0000 1.025362 27.9015 + 54 0.0000 1.044825 28.4311 + 55 0.0000 1.094573 29.7848 + 56 0.0000 1.155441 31.4411 + 57 0.0000 1.218298 33.1516 + 58 0.0000 1.235710 33.6254 + 59 0.0000 1.273918 34.6651 + 60 0.0000 1.318477 35.8776 + 61 0.0000 1.409956 38.3669 + 62 0.0000 1.465294 39.8727 + 63 0.0000 1.512117 41.1468 + 64 0.0000 1.530551 41.6484 + 65 0.0000 1.580131 42.9975 + 66 0.0000 1.591791 43.3148 + 67 0.0000 1.632298 44.4171 + 68 0.0000 1.651256 44.9330 + 69 0.0000 1.730140 47.0795 + 70 0.0000 1.751241 47.6537 + 71 0.0000 1.779443 48.4211 + 72 0.0000 1.915066 52.1116 + 73 0.0000 1.926646 52.4267 + 74 0.0000 1.972218 53.6668 + 75 0.0000 2.008089 54.6429 + 76 0.0000 2.041968 55.5648 + 77 0.0000 2.091806 56.9209 + 78 0.0000 2.139950 58.2310 + 79 0.0000 2.189574 59.5813 + 80 0.0000 2.271524 61.8113 + 81 0.0000 2.299071 62.5609 + 82 0.0000 2.331826 63.4522 + 83 0.0000 2.359059 64.1933 + 84 0.0000 2.412050 65.6352 + 85 0.0000 2.453559 66.7647 + 86 0.0000 2.467043 67.1317 + 87 0.0000 2.477142 67.4065 + 88 0.0000 2.512627 68.3720 + 89 0.0000 2.557560 69.5947 + 90 0.0000 2.594715 70.6058 + 91 0.0000 2.597698 70.6870 + 92 0.0000 2.661376 72.4197 + 93 0.0000 2.704252 73.5864 + 94 0.0000 2.749121 74.8074 + 95 0.0000 2.778944 75.6189 + 96 0.0000 2.838509 77.2398 + 97 0.0000 2.919982 79.4568 + 98 0.0000 2.960333 80.5548 + 99 0.0000 2.977664 81.0264 + 100 0.0000 3.083223 83.8988 + 101 0.0000 3.168632 86.2229 + 102 0.0000 3.223719 87.7218 + 103 0.0000 3.487885 94.9102 + 104 0.0000 3.709979 100.9537 + 105 0.0000 3.827013 104.1383 + 106 0.0000 4.038448 109.8918 + 107 0.0000 4.167989 113.4168 + 108 0.0000 4.208481 114.5186 + 109 0.0000 4.282513 116.5331 + 110 0.0000 4.369313 118.8950 + 111 0.0000 4.392704 119.5316 + 112 0.0000 4.533744 123.3695 + 113 0.0000 4.617935 125.6604 + 114 0.0000 4.665802 126.9629 + 115 0.0000 4.721733 128.4849 + 116 0.0000 4.836403 131.6052 + 117 0.0000 4.888623 133.0262 + 118 0.0000 4.930336 134.1613 + 119 0.0000 4.962341 135.0322 + 120 0.0000 5.051435 137.4565 + 121 0.0000 5.107240 138.9751 + 122 0.0000 5.183365 141.0465 + 123 0.0000 5.199084 141.4743 + 124 0.0000 5.240542 142.6024 + 125 0.0000 5.298570 144.1814 + 126 0.0000 5.391946 146.7223 + 127 0.0000 5.494991 149.5263 + 128 0.0000 5.527103 150.4001 + 129 0.0000 5.697054 155.0247 + 130 0.0000 5.743475 156.2879 + 131 0.0000 5.945290 161.7796 + 132 0.0000 6.168020 167.8403 + 133 0.0000 6.415124 174.5644 + 134 0.0000 6.479957 176.3286 + 135 0.0000 6.509814 177.1410 + 136 0.0000 6.691819 182.0936 + 137 0.0000 6.714650 182.7149 + 138 0.0000 6.776850 184.4075 + 139 0.0000 6.816285 185.4805 + 140 0.0000 6.839029 186.0994 + 141 0.0000 7.072841 192.4618 + 142 0.0000 7.107140 193.3951 + 143 0.0000 7.122186 193.8045 + 144 0.0000 7.206111 196.0883 + 145 0.0000 7.254611 197.4080 + 146 0.0000 7.279423 198.0832 + 147 0.0000 7.334274 199.5758 + 148 0.0000 7.384747 200.9492 + 149 0.0000 7.454291 202.8416 + 150 0.0000 7.470311 203.2775 + 151 0.0000 7.557915 205.6613 + 152 0.0000 7.577135 206.1843 + 153 0.0000 7.644176 208.0086 + 154 0.0000 7.690105 209.2584 + 155 0.0000 7.899966 214.9690 + 156 0.0000 7.952548 216.3998 + 157 0.0000 8.391583 228.3466 + 158 0.0000 14.042154 382.1064 + 159 0.0000 14.902829 405.5266 + 160 0.0000 16.059817 437.0098 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.369459 0.000000 + 1 N : 0.353158 0.000000 + 2 O : -0.231761 0.000000 + 3 H : 0.248062 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.855885 s : 3.855885 + pz : 1.331733 p : 4.481893 + px : 1.594507 + py : 1.555653 + dz2 : 0.009390 d : 0.027450 + dxz : 0.008123 + dyz : 0.005180 + dx2y2 : 0.002929 + dxy : 0.001828 + f0 : 0.001258 f : 0.004231 + f+1 : 0.000937 + f-1 : 0.000690 + f+2 : 0.000370 + f-2 : 0.000373 + f+3 : 0.000385 + f-3 : 0.000218 + 1 N s : 3.825393 s : 3.825393 + pz : 0.807394 p : 2.650929 + px : 0.805220 + py : 1.038314 + dz2 : 0.027333 d : 0.139323 + dxz : 0.037356 + dyz : 0.019308 + dx2y2 : 0.035291 + dxy : 0.020034 + f0 : 0.007761 f : 0.031198 + f+1 : 0.002603 + f-1 : 0.005163 + f+2 : 0.002584 + f-2 : 0.005765 + f+3 : 0.003333 + f-3 : 0.003990 + 2 O s : 3.875552 s : 3.875552 + pz : 1.704156 p : 4.286509 + px : 1.229066 + py : 1.353286 + dz2 : 0.004683 d : 0.062230 + dxz : 0.007710 + dyz : 0.012361 + dx2y2 : 0.026148 + dxy : 0.011328 + f0 : 0.001132 f : 0.007471 + f+1 : 0.000569 + f-1 : 0.000689 + f+2 : 0.000000 + f-2 : 0.001334 + f+3 : 0.001987 + f-3 : 0.001760 + 3 H s : 0.643001 s : 0.643001 + pz : 0.022879 p : 0.088615 + px : 0.037234 + py : 0.028501 + dz2 : 0.001540 d : 0.020322 + dxz : 0.002524 + dyz : 0.005508 + dx2y2 : 0.009184 + dxy : 0.001567 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.576372 0.000000 + 1 N : -0.237052 0.000000 + 2 O : 0.249021 0.000000 + 3 H : -0.588341 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.133899 s : 3.133899 + pz : 1.236061 p : 3.955946 + px : 1.342771 + py : 1.377114 + dz2 : 0.077406 d : 0.258418 + dxz : 0.073056 + dyz : 0.052025 + dx2y2 : 0.017620 + dxy : 0.038310 + f0 : 0.014793 f : 0.075365 + f+1 : 0.017237 + f-1 : 0.014879 + f+2 : 0.010484 + f-2 : 0.011401 + f+3 : 0.005094 + f-3 : 0.001476 + 1 N s : 3.035967 s : 3.035967 + pz : 0.847527 p : 2.837240 + px : 0.891599 + py : 1.098114 + dz2 : 0.196401 d : 0.923002 + dxz : 0.236073 + dyz : 0.137991 + dx2y2 : 0.161881 + dxy : 0.190657 + f0 : 0.091910 f : 0.440843 + f+1 : 0.053710 + f-1 : 0.056362 + f+2 : 0.027917 + f-2 : 0.086422 + f+3 : 0.064117 + f-3 : 0.060405 + 2 O s : 3.313049 s : 3.313049 + pz : 1.403390 p : 3.990658 + px : 1.242715 + py : 1.344554 + dz2 : 0.050739 d : 0.329900 + dxz : 0.064951 + dyz : 0.035313 + dx2y2 : 0.065744 + dxy : 0.113154 + f0 : 0.011954 f : 0.117371 + f+1 : 0.012741 + f-1 : 0.014395 + f+2 : 0.004457 + f-2 : 0.021464 + f+3 : 0.030160 + f-3 : 0.022201 + 3 H s : 0.625832 s : 0.625832 + pz : 0.148083 p : 0.572458 + px : 0.190682 + py : 0.233693 + dz2 : 0.032113 d : 0.390050 + dxz : 0.061131 + dyz : 0.081764 + dx2y2 : 0.120492 + dxy : 0.094550 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3695 8.0000 -0.3695 1.8164 1.8164 0.0000 + 1 N 6.6468 7.0000 0.3532 2.5866 2.5866 0.0000 + 2 O 8.2318 8.0000 -0.2318 1.7995 1.7995 0.0000 + 3 H 0.7519 1.0000 0.2481 1.0003 1.0003 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8030 B( 0-O , 3-H ) : 0.9550 B( 1-N , 2-O ) : 1.7397 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.586 sec +Sum of individual times .... 2.109 sec ( 81.5%) + +Fock matrix formation .... 1.773 sec ( 68.5%) +Diagonalization .... 0.112 sec ( 4.3%) +Density matrix formation .... 0.013 sec ( 0.5%) +Population analysis .... 0.103 sec ( 4.0%) +Initial guess .... 0.018 sec ( 0.7%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.010 sec ( 0.4%) +DIIS solution .... 0.090 sec ( 3.5%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.605 sec +Reference energy ... -204.706096623 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 10.240 sec +AO-integral generation ... 0.348 sec +Half transformation ... 0.177 sec +K-integral sorting ... 8.001 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.069 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.056 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.071 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.084 s ( 0.001 ms/b) + 159120 b 0 skpd 0.041 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.080 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.071 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.053 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.092 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.057 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.771 sec +AO-integral generation ... 0.583 sec +Half transformation ... 0.095 sec +J-integral sorting ... 0.072 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.211 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.357 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090024200 +EMP2(bb)= -0.090024200 +EMP2(ab)= -0.517089957 + +Initial guess performed in 0.168 sec +E(0) ... -204.706096623 +E(MP2) ... -0.697138357 +Initial E(tot) ... -205.403234980 + ... 0.189196251 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.403234980 -0.697138357 -0.000000000 0.019610181 4.92 0.000001156 + *** Turning on DIIS *** + 1 -205.374968285 -0.668871662 0.028266696 0.010309190 5.83 0.055741612 + 2 -205.394481028 -0.688384405 -0.019512743 0.003972982 6.34 0.058547570 + 3 -205.398297045 -0.692200422 -0.003816017 0.001949145 6.07 0.071672351 + 4 -205.399838664 -0.693742041 -0.001541620 0.000862043 5.78 0.077587807 + 5 -205.400334337 -0.694237714 -0.000495672 0.000540434 5.86 0.082090302 + 6 -205.400418012 -0.694321389 -0.000083675 0.000342344 5.23 0.084238305 + 7 -205.400453070 -0.694356447 -0.000035058 0.000245307 5.21 0.085240515 + 8 -205.400461621 -0.694364998 -0.000008551 0.000167265 5.89 0.085708723 + 9 -205.400458612 -0.694361990 0.000003008 0.000103901 5.20 0.085904436 + 10 -205.400463865 -0.694367243 -0.000005253 0.000054110 5.19 0.085996133 + 11 -205.400460307 -0.694363684 0.000003559 0.000029515 5.16 0.086016009 + 12 -205.400462921 -0.694366298 -0.000002614 0.000016777 5.42 0.086032216 + 13 -205.400462798 -0.694366175 0.000000122 0.000009601 5.20 0.086034744 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.706096623 +E(CORR) ... -0.694366175 +E(TOT) ... -205.400462798 +Singles norm **1/2 ... 0.086034744 ( 0.043017372, 0.043017372) +T1 diagnostic ... 0.020278584 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.058903 + 8a-> 13a 8b-> 13b 0.056121 + 8a-> 13a 9b-> 13b 0.044994 + 9a-> 13a 8b-> 13b 0.044994 + 5a-> 13a 5b-> 13b 0.029699 + 8b-> 13b -1b-> -1b 0.029498 + 8a-> 13a -1a-> -1a 0.029498 + 11a-> 13a 11b-> 13b 0.028938 + 9a-> 13a 9b-> 22b 0.022766 + 9a-> 22a 9b-> 13b 0.022766 + 11a-> 25a 11b-> 25b 0.022078 + 8a-> 22a 8b-> 13b 0.020010 + 8a-> 13a 8b-> 22b 0.020010 + 11a-> 24a 11b-> 25b 0.019213 + 11a-> 25a 11b-> 24b 0.019213 + 11a-> 24a 11b-> 24b 0.018571 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034498327 + alpha-alpha-alpha ... -0.000865513 ( 2.5%) + alpha-alpha-beta ... -0.016383650 ( 47.5%) + alpha-beta -beta ... -0.016383650 ( 47.5%) + beta -beta -beta ... -0.000865513 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034498327 + +Final correlation energy ... -0.728864502 +E(CCSD) ... -205.400462798 +E(CCSD(T)) ... -205.434961125 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210331936 sqrt= 1.100150870 +W(HF) = 0.826219626 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.310188 0.000000 + 1 N : 0.179537 -0.000000 + 2 O : -0.105860 0.000000 + 3 H : 0.236511 -0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.836073 s : 3.836073 + pz : 1.308841 p : 4.407985 + px : 1.571329 + py : 1.527815 + dz2 : 0.014632 d : 0.058170 + dxz : 0.013163 + dyz : 0.012151 + dx2y2 : 0.009897 + dxy : 0.008327 + f0 : 0.001738 f : 0.007960 + f+1 : 0.001185 + f-1 : 0.001239 + f+2 : 0.000917 + f-2 : 0.000974 + f+3 : 0.001033 + f-3 : 0.000874 + 1 N s : 3.879600 s : 3.879600 + pz : 0.854840 p : 2.742318 + px : 0.854402 + py : 1.033076 + dz2 : 0.035035 d : 0.168439 + dxz : 0.045045 + dyz : 0.026026 + dx2y2 : 0.037492 + dxy : 0.024841 + f0 : 0.007315 f : 0.030106 + f+1 : 0.002459 + f-1 : 0.005276 + f+2 : 0.002974 + f-2 : 0.005468 + f+3 : 0.003197 + f-3 : 0.003419 + 2 O s : 3.862299 s : 3.862299 + pz : 1.624523 p : 4.150381 + px : 1.203695 + py : 1.322163 + dz2 : 0.010105 d : 0.083331 + dxz : 0.014328 + dyz : 0.017178 + dx2y2 : 0.027601 + dxy : 0.014120 + f0 : 0.001557 f : 0.009849 + f+1 : 0.001033 + f-1 : 0.001131 + f+2 : 0.000613 + f-2 : 0.001654 + f+3 : 0.002040 + f-3 : 0.001820 + 3 H s : 0.650730 s : 0.650730 + pz : 0.026742 p : 0.095296 + px : 0.039819 + py : 0.028735 + dz2 : 0.001294 d : 0.017463 + dxz : 0.002391 + dyz : 0.004791 + dx2y2 : 0.007992 + dxy : 0.000994 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.582315 0.000000 + 1 N : -0.280905 0.000000 + 2 O : 0.291635 -0.000000 + 3 H : -0.593045 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.138578 s : 3.138578 + pz : 1.226096 p : 3.907329 + px : 1.326462 + py : 1.354771 + dz2 : 0.083202 d : 0.289441 + dxz : 0.079800 + dyz : 0.057306 + dx2y2 : 0.023569 + dxy : 0.045564 + f0 : 0.016331 f : 0.082337 + f+1 : 0.019014 + f-1 : 0.015233 + f+2 : 0.011208 + f-2 : 0.012367 + f+3 : 0.005936 + f-3 : 0.002248 + 1 N s : 3.041026 s : 3.041026 + pz : 0.869122 p : 2.878414 + px : 0.919655 + py : 1.089637 + dz2 : 0.202266 d : 0.930055 + dxz : 0.238064 + dyz : 0.134171 + dx2y2 : 0.157711 + dxy : 0.197843 + f0 : 0.088288 f : 0.431411 + f+1 : 0.054651 + f-1 : 0.055686 + f+2 : 0.027513 + f-2 : 0.082744 + f+3 : 0.062720 + f-3 : 0.059807 + 2 O s : 3.315743 s : 3.315743 + pz : 1.353774 p : 3.908387 + px : 1.228004 + py : 1.326610 + dz2 : 0.056633 d : 0.358490 + dxz : 0.068924 + dyz : 0.040968 + dx2y2 : 0.074126 + dxy : 0.117839 + f0 : 0.012876 f : 0.125745 + f+1 : 0.013644 + f-1 : 0.014610 + f+2 : 0.005248 + f-2 : 0.022542 + f+3 : 0.031882 + f-3 : 0.024942 + 3 H s : 0.626524 s : 0.626524 + pz : 0.148923 p : 0.586711 + px : 0.196633 + py : 0.241155 + dz2 : 0.032511 d : 0.379810 + dxz : 0.058852 + dyz : 0.079250 + dx2y2 : 0.115862 + dxy : 0.093335 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3102 8.0000 -0.3102 2.1634 1.7021 0.4613 + 1 N 6.8205 7.0000 0.1795 2.8506 2.3578 0.4928 + 2 O 8.1059 8.0000 -0.1059 2.1842 1.6860 0.4982 + 3 H 0.7635 1.0000 0.2365 1.0197 0.9451 0.0746 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7201 B( 0-O , 3-H ) : 0.8915 B( 1-N , 2-O ) : 1.5898 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 106.602 sec + +Fock Matrix Formation ... 0.605 sec ( 0.6%) +Initial Guess ... 0.168 sec ( 0.2%) +DIIS Solver ... 4.761 sec ( 4.5%) +State Vector Update ... 0.263 sec ( 0.2%) +Sigma-vector construction ... 72.256 sec ( 67.8%) + <0|H|D> ... 0.007 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.038 sec ( 0.1% of sigma) + (0-ext) ... 0.111 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.038 sec ( 0.1% of sigma) + (2-ext) ... 1.412 sec ( 2.0% of sigma) + (4-ext) ... 42.827 sec ( 59.3% of sigma) + ... 3.649 sec ( 5.0% of sigma) + ... 0.005 sec ( 0.0% of sigma) + (1-ext) ... 0.012 sec ( 0.0% of sigma) + (1-ext) ... 0.191 sec ( 0.3% of sigma) + Fock-dressing ... 4.662 sec ( 6.5% of sigma) + (ik|jl)-dressing ... 0.135 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 15.566 sec ( 21.5% of sigma) + Pair energies ... 0.023 sec ( 0.0% of sigma) +Total Time for computing (T) ... 15.105 sec ( 14.2% of ALL) + I/O of integral and amplitudes ... 1.536 sec ( 10.2% of (T)) + External N**7 contributions ... 6.888 sec ( 45.6% of (T)) + Internal N**7 contributions ... 0.639 sec ( 4.2% of (T)) + N**6 triples energy contributions ... 2.485 sec ( 16.5% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.434961125028 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.032.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.032.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.570471, -0.256546 -0.289697) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.80577 -0.16988 -0.88048 +Nuclear contribution : -1.20650 0.59266 0.66610 + ----------------------------------------- +Total Dipole Moment : -0.40074 0.42278 -0.21438 + ----------------------------------------- +Magnitude (a.u.) : 0.62072 +Magnitude (Debye) : 1.57774 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.712254 0.402596 0.361595 +Rotational constants in MHz : 81311.318706 12069.511753 10840.356332 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.050344 0.155037 0.598933 +x,y,z [Debye]: 0.127965 0.394074 1.522366 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.570471, -0.256546 -0.289697) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.95419 -0.10433 -0.90560 +Nuclear contribution : -1.20650 0.59266 0.66610 + ----------------------------------------- +Total Dipole Moment : -0.25231 0.48834 -0.23950 + ----------------------------------------- +Magnitude (a.u.) : 0.59958 +Magnitude (Debye) : 1.52400 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.712254 0.402596 0.361595 +Rotational constants in MHz : 81311.318706 12069.511753 10840.356332 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.083418 0.233982 0.545698 +x,y,z [Debye]: -0.212032 0.594736 1.387053 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 33 * + * * + * Dihedral ( 2, 1, 0, 3) : 81.81818182 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0378408692 RMS(Int)= 0.0001131078 + Iter 1: RMS(Cart)= 0.0000299727 RMS(Int)= 0.0000000632 + Iter 2: RMS(Cart)= 0.0000000167 RMS(Int)= 0.0000000000 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4959 0.000000 + 2. B(O 2,N 1) 1.1692 0.000000 + 3. B(H 3,O 0) 0.9727 0.000000 + 4. A(N 1,O 0,H 3) 103.5972 0.000000 + 5. A(O 0,N 1,O 2) 111.5405 0.000000 + 6. D(O 2,N 1,O 0,H 3) 81.8182 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.401978 -0.255347 0.747189 + N 0.274956 -0.488624 -0.566280 + O 1.146228 0.271207 -0.741113 + H -1.019205 0.472764 0.560204 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.759629 -0.482536 1.411982 + 1 N 7.0000 0 14.007 0.519592 -0.923365 -1.070114 + 2 O 8.0000 0 15.999 2.166056 0.512507 -1.400501 + 3 H 1.0000 0 1.008 -1.926017 0.893394 1.058633 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.495286226561 0.00000000 0.00000000 + O 2 1 0 1.167434911897 111.65893014 0.00000000 + H 1 2 3 0.970193710566 103.72539705 73.63636337 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.825681460024 0.00000000 0.00000000 + O 2 1 0 2.206132262663 111.65893014 0.00000000 + H 1 2 3 1.833400409822 103.72539705 73.63636337 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.1 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2229 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2697 + la=0 lb=0: 549 shell pairs + la=1 lb=0: 535 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.377732430180 Eh + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.3777324302 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.821e-04 +Time for diagonalization ... 0.006 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.004 sec +Total time needed ... 0.011 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7007029756 0.000000000000 0.00148329 0.00004971 0.0179213 0.7000 + 1 -204.7015465897 -0.000843614116 0.00141799 0.00004591 0.0148656 0.7000 + ***Turning on DIIS*** + 2 -204.7022746757 -0.000728086009 0.00400869 0.00012697 0.0121130 0.0000 + 3 -204.7054237168 -0.003149041133 0.00194282 0.00005947 0.0047992 0.0000 + 4 -204.7039759261 0.001447790708 0.00091172 0.00003206 0.0018650 0.0000 + 5 -204.7057607126 -0.001784786544 0.00092270 0.00002747 0.0010779 0.0000 + 6 -204.7050605099 0.000700202726 0.00091143 0.00003288 0.0008310 0.0000 + 7 -204.7045712891 0.000489220836 0.00049515 0.00001672 0.0003726 0.0000 + 8 -204.7054083923 -0.000837103251 0.00026184 0.00000964 0.0002166 0.0000 + 9 -204.7049828855 0.000425506824 0.00019132 0.00000613 0.0001282 0.0000 + 10 -204.7050627631 -0.000079877588 0.00007727 0.00000257 0.0000602 0.0000 + 11 -204.7052262434 -0.000163480274 0.00003686 0.00000097 0.0000312 0.0000 + 12 -204.7051185754 0.000107668024 0.00000947 0.00000028 0.0000096 0.0000 + 13 -204.7051437578 -0.000025182454 0.00000287 0.00000010 0.0000041 0.0000 + 14 -204.7051358968 0.000007861017 0.00000118 0.00000005 0.0000028 0.0000 + 15 -204.7051362262 -0.000000329389 0.00000120 0.00000003 0.0000025 0.0000 + 16 -204.7051390392 -0.000002813010 0.00000089 0.00000003 0.0000012 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 17 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70513744 Eh -5570.30998 eV + +Components: +Nuclear Repulsion : 68.37773243 Eh 1860.65269 eV +Electronic Energy : -273.08286987 Eh -7430.96267 eV +One Electron Energy: -416.45981664 Eh -11332.44774 eV +Two Electron Energy: 143.37694677 Eh 3901.48507 eV + +Virial components: +Potential Energy : -408.91995435 Eh -11127.27766 eV +Kinetic Energy : 204.21481691 Eh 5556.96768 eV +Virial Ratio : 2.00240100 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.5990e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.9229e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.7947e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.1918e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.691033 -563.0316 + 1 1.0000 -20.618651 -561.0620 + 2 1.0000 -15.805162 -430.0803 + 3 1.0000 -1.614668 -43.9373 + 4 1.0000 -1.373704 -37.3804 + 5 1.0000 -0.956275 -26.0216 + 6 1.0000 -0.767475 -20.8841 + 7 1.0000 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0.0000 0.030715 0.8358 + 13 0.0000 0.065708 1.7880 + 14 0.0000 0.092080 2.5056 + 15 0.0000 0.104509 2.8438 + 16 0.0000 0.112965 3.0739 + 17 0.0000 0.155448 4.2299 + 18 0.0000 0.156884 4.2690 + 19 0.0000 0.174664 4.7528 + 20 0.0000 0.179077 4.8729 + 21 0.0000 0.189926 5.1681 + 22 0.0000 0.201261 5.4766 + 23 0.0000 0.235670 6.4129 + 24 0.0000 0.270395 7.3578 + 25 0.0000 0.291698 7.9375 + 26 0.0000 0.301703 8.2098 + 27 0.0000 0.331832 9.0296 + 28 0.0000 0.334388 9.0992 + 29 0.0000 0.352144 9.5823 + 30 0.0000 0.423669 11.5286 + 31 0.0000 0.506584 13.7849 + 32 0.0000 0.530292 14.4300 + 33 0.0000 0.543825 14.7982 + 34 0.0000 0.566350 15.4112 + 35 0.0000 0.599826 16.3221 + 36 0.0000 0.630461 17.1557 + 37 0.0000 0.644995 17.5512 + 38 0.0000 0.709633 19.3101 + 39 0.0000 0.716620 19.5002 + 40 0.0000 0.736625 20.0446 + 41 0.0000 0.754225 20.5235 + 42 0.0000 0.761989 20.7348 + 43 0.0000 0.788329 21.4515 + 44 0.0000 0.807290 21.9675 + 45 0.0000 0.816775 22.2256 + 46 0.0000 0.860327 23.4107 + 47 0.0000 0.872749 23.7487 + 48 0.0000 0.892890 24.2968 + 49 0.0000 0.953249 25.9392 + 50 0.0000 0.961597 26.1664 + 51 0.0000 0.975228 26.5373 + 52 0.0000 0.990528 26.9536 + 53 0.0000 1.027461 27.9586 + 54 0.0000 1.043448 28.3937 + 55 0.0000 1.099057 29.9069 + 56 0.0000 1.154853 31.4252 + 57 0.0000 1.221526 33.2394 + 58 0.0000 1.247353 33.9422 + 59 0.0000 1.264985 34.4220 + 60 0.0000 1.313745 35.7488 + 61 0.0000 1.407775 38.3075 + 62 0.0000 1.458307 39.6826 + 63 0.0000 1.516374 41.2626 + 64 0.0000 1.530558 41.6486 + 65 0.0000 1.572816 42.7985 + 66 0.0000 1.589786 43.2603 + 67 0.0000 1.631901 44.4063 + 68 0.0000 1.649524 44.8858 + 69 0.0000 1.723970 46.9116 + 70 0.0000 1.763402 47.9846 + 71 0.0000 1.781107 48.4664 + 72 0.0000 1.904867 51.8341 + 73 0.0000 1.923993 52.3545 + 74 0.0000 1.979397 53.8621 + 75 0.0000 2.012901 54.7738 + 76 0.0000 2.041744 55.5587 + 77 0.0000 2.095498 57.0214 + 78 0.0000 2.136807 58.1455 + 79 0.0000 2.195799 59.7507 + 80 0.0000 2.274434 61.8905 + 81 0.0000 2.290337 62.3232 + 82 0.0000 2.332353 63.4666 + 83 0.0000 2.352445 64.0133 + 84 0.0000 2.406233 65.4769 + 85 0.0000 2.453459 66.7620 + 86 0.0000 2.465774 67.0971 + 87 0.0000 2.476562 67.3907 + 88 0.0000 2.510546 68.3154 + 89 0.0000 2.561568 69.7038 + 90 0.0000 2.584326 70.3231 + 91 0.0000 2.599062 70.7241 + 92 0.0000 2.661748 72.4298 + 93 0.0000 2.726070 74.1801 + 94 0.0000 2.750929 74.8566 + 95 0.0000 2.768003 75.3212 + 96 0.0000 2.843932 77.3873 + 97 0.0000 2.910640 79.2025 + 98 0.0000 2.959189 80.5236 + 99 0.0000 2.985197 81.2313 + 100 0.0000 3.073275 83.6281 + 101 0.0000 3.167876 86.2023 + 102 0.0000 3.220133 87.6243 + 103 0.0000 3.487976 94.9126 + 104 0.0000 3.715587 101.1063 + 105 0.0000 3.816386 103.8491 + 106 0.0000 4.042446 110.0005 + 107 0.0000 4.168154 113.4212 + 108 0.0000 4.196980 114.2056 + 109 0.0000 4.280157 116.4690 + 110 0.0000 4.366659 118.8228 + 111 0.0000 4.391585 119.5011 + 112 0.0000 4.521572 123.0382 + 113 0.0000 4.609277 125.4248 + 114 0.0000 4.664672 126.9322 + 115 0.0000 4.715076 128.3037 + 116 0.0000 4.836958 131.6203 + 117 0.0000 4.896110 133.2299 + 118 0.0000 4.929357 134.1346 + 119 0.0000 4.954419 134.8166 + 120 0.0000 5.050024 137.4181 + 121 0.0000 5.104551 138.9019 + 122 0.0000 5.180004 140.9551 + 123 0.0000 5.195893 141.3874 + 124 0.0000 5.231926 142.3679 + 125 0.0000 5.302145 144.2787 + 126 0.0000 5.386268 146.5678 + 127 0.0000 5.491622 149.4346 + 128 0.0000 5.551124 151.0538 + 129 0.0000 5.690773 154.8538 + 130 0.0000 5.737372 156.1218 + 131 0.0000 5.942127 161.6935 + 132 0.0000 6.170971 167.9206 + 133 0.0000 6.422098 174.7542 + 134 0.0000 6.480247 176.3365 + 135 0.0000 6.506846 177.0603 + 136 0.0000 6.694469 182.1658 + 137 0.0000 6.718668 182.8243 + 138 0.0000 6.771631 184.2655 + 139 0.0000 6.815988 185.4725 + 140 0.0000 6.828594 185.8155 + 141 0.0000 7.073998 192.4933 + 142 0.0000 7.103507 193.2963 + 143 0.0000 7.118176 193.6954 + 144 0.0000 7.193798 195.7532 + 145 0.0000 7.253577 197.3799 + 146 0.0000 7.278624 198.0614 + 147 0.0000 7.331114 199.4898 + 148 0.0000 7.381988 200.8741 + 149 0.0000 7.453074 202.8085 + 150 0.0000 7.465083 203.1352 + 151 0.0000 7.563661 205.8177 + 152 0.0000 7.572479 206.0576 + 153 0.0000 7.635744 207.7792 + 154 0.0000 7.703615 209.6260 + 155 0.0000 7.890539 214.7125 + 156 0.0000 7.940586 216.0743 + 157 0.0000 8.392857 228.3812 + 158 0.0000 14.033933 381.8827 + 159 0.0000 14.854785 404.2193 + 160 0.0000 15.978636 434.8008 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.372424 0.000000 + 1 N : 0.351734 0.000000 + 2 O : -0.229839 0.000000 + 3 H : 0.250529 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.859369 s : 3.859369 + pz : 1.315806 p : 4.482140 + px : 1.575379 + py : 1.590955 + dz2 : 0.009878 d : 0.026636 + dxz : 0.007970 + dyz : 0.004919 + dx2y2 : 0.001901 + dxy : 0.001967 + f0 : 0.001371 f : 0.004279 + f+1 : 0.000888 + f-1 : 0.000727 + f+2 : 0.000287 + f-2 : 0.000341 + f+3 : 0.000353 + f-3 : 0.000312 + 1 N s : 3.822670 s : 3.822670 + pz : 0.822411 p : 2.656241 + px : 0.825107 + py : 1.008722 + dz2 : 0.027287 d : 0.138317 + dxz : 0.038190 + dyz : 0.019250 + dx2y2 : 0.034511 + dxy : 0.019079 + f0 : 0.008017 f : 0.031039 + f+1 : 0.002890 + f-1 : 0.005261 + f+2 : 0.002435 + f-2 : 0.005589 + f+3 : 0.003583 + f-3 : 0.003263 + 2 O s : 3.876371 s : 3.876371 + pz : 1.725673 p : 4.283915 + px : 1.216582 + py : 1.341661 + dz2 : 0.004585 d : 0.062104 + dxz : 0.008510 + dyz : 0.010786 + dx2y2 : 0.026945 + dxy : 0.011277 + f0 : 0.001154 f : 0.007449 + f+1 : 0.000613 + f-1 : 0.000636 + f+2 : -0.000031 + f-2 : 0.001323 + f+3 : 0.002207 + f-3 : 0.001546 + 3 H s : 0.641514 s : 0.641514 + pz : 0.021577 p : 0.087823 + px : 0.036158 + py : 0.030089 + dz2 : 0.001514 d : 0.020134 + dxz : 0.003141 + dyz : 0.004777 + dx2y2 : 0.009851 + dxy : 0.000851 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.572535 0.000000 + 1 N : -0.237721 0.000000 + 2 O : 0.247809 0.000000 + 3 H : -0.582622 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.135230 s : 3.135230 + pz : 1.229324 p : 3.958637 + px : 1.339052 + py : 1.390261 + dz2 : 0.082597 d : 0.258278 + dxz : 0.071105 + dyz : 0.051985 + dx2y2 : 0.015365 + dxy : 0.037226 + f0 : 0.016600 f : 0.075321 + f+1 : 0.017008 + f-1 : 0.015206 + f+2 : 0.009999 + f-2 : 0.010289 + f+3 : 0.004362 + f-3 : 0.001857 + 1 N s : 3.036693 s : 3.036693 + pz : 0.860502 p : 2.839341 + px : 0.922109 + py : 1.056730 + dz2 : 0.198845 d : 0.921926 + dxz : 0.244611 + dyz : 0.134450 + dx2y2 : 0.153107 + dxy : 0.190914 + f0 : 0.095705 f : 0.439760 + f+1 : 0.055508 + f-1 : 0.056247 + f+2 : 0.027684 + f-2 : 0.083609 + f+3 : 0.064008 + f-3 : 0.057000 + 2 O s : 3.315983 s : 3.315983 + pz : 1.419418 p : 3.989908 + px : 1.255154 + py : 1.315336 + dz2 : 0.050496 d : 0.329130 + dxz : 0.069895 + dyz : 0.032179 + dx2y2 : 0.061307 + dxy : 0.115252 + f0 : 0.012433 f : 0.117170 + f+1 : 0.013959 + f-1 : 0.012988 + f+2 : 0.005211 + f-2 : 0.020898 + f+3 : 0.029092 + f-3 : 0.022590 + 3 H s : 0.625070 s : 0.625070 + pz : 0.146276 p : 0.569470 + px : 0.197571 + py : 0.225623 + dz2 : 0.031844 d : 0.388083 + dxz : 0.068430 + dyz : 0.073847 + dx2y2 : 0.121038 + dxy : 0.092924 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3724 8.0000 -0.3724 1.8146 1.8146 -0.0000 + 1 N 6.6483 7.0000 0.3517 2.5923 2.5923 -0.0000 + 2 O 8.2298 8.0000 -0.2298 1.8055 1.8055 -0.0000 + 3 H 0.7495 1.0000 0.2505 0.9957 0.9957 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8038 B( 0-O , 3-H ) : 0.9542 B( 1-N , 2-O ) : 1.7479 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 7 sec + +Total time .... 7.484 sec +Sum of individual times .... 6.806 sec ( 90.9%) + +Fock matrix formation .... 5.851 sec ( 78.2%) +Diagonalization .... 0.408 sec ( 5.5%) +Density matrix formation .... 0.031 sec ( 0.4%) +Population analysis .... 0.144 sec ( 1.9%) +Initial guess .... 0.019 sec ( 0.3%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.011 sec ( 0.1%) +DIIS solution .... 0.353 sec ( 4.7%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.492 sec +Reference energy ... -204.705138079 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 9.341 sec +AO-integral generation ... 0.379 sec +Half transformation ... 0.174 sec +K-integral sorting ... 7.628 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.056 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.066 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.064 s ( 0.000 ms/b) + 151164 b 0 skpd 0.079 s ( 0.001 ms/b) +: 159120 b 0 skpd 0.035 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.083 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.063 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.056 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.094 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.053 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.748 sec +AO-integral generation ... 0.568 sec +Half transformation ... 0.083 sec +J-integral sorting ... 0.074 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.271 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.368 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090009895 +EMP2(bb)= -0.090009895 +EMP2(ab)= -0.517318043 + +Initial guess performed in 0.165 sec +E(0) ... -204.705138079 +E(MP2) ... -0.697337834 +Initial E(tot) ... -205.402475913 + ... 0.189463403 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.402475913 -0.697337834 -0.000000000 0.019137665 5.98 0.000002090 + *** Turning on DIIS *** + 1 -205.374215800 -0.669077721 0.028260113 0.011053764 5.33 0.055480751 + 2 -205.393746832 -0.688608753 -0.019531033 0.003832710 5.45 0.058238613 + 3 -205.397573493 -0.692435414 -0.003826661 0.002121997 5.71 0.071159351 + 4 -205.399111758 -0.693973679 -0.001538265 0.000882566 5.47 0.076891711 + 5 -205.399596030 -0.694457952 -0.000484272 0.000447510 4.99 0.081126408 + 6 -205.399672271 -0.694534192 -0.000076240 0.000335071 6.02 0.083029588 + 7 -205.399702220 -0.694564142 -0.000029950 0.000250445 5.91 0.083852237 + 8 -205.399708797 -0.694570718 -0.000006576 0.000179069 5.94 0.084218602 + 9 -205.399705857 -0.694567778 0.000002939 0.000117479 6.22 0.084377229 + 10 -205.399710602 -0.694572523 -0.000004745 0.000059162 6.04 0.084465437 + 11 -205.399707116 -0.694569037 0.000003486 0.000025574 6.03 0.084496282 + 12 -205.399709640 -0.694571562 -0.000002525 0.000013164 4.88 0.084513213 + 13 -205.399709757 -0.694571679 -0.000000117 0.000009083 5.99 0.084516820 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.705138079 +E(CORR) ... -0.694571679 +E(TOT) ... -205.399709757 +Singles norm **1/2 ... 0.084516820 ( 0.042258410, 0.042258410) +T1 diagnostic ... 0.019920806 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.063272 + 8a-> 13a 8b-> 13b 0.054431 + 8a-> 13a 9b-> 13b 0.046675 + 9a-> 13a 8b-> 13b 0.046675 + 5a-> 13a 5b-> 13b 0.029919 + 11a-> 13a 11b-> 13b 0.028898 + 8a-> 13a -1a-> -1a 0.028427 + 8b-> 13b -1b-> -1b 0.028427 + 9a-> 13a 9b-> 22b 0.024270 + 9a-> 22a 9b-> 13b 0.024270 + 11a-> 25a 11b-> 25b 0.022249 + 11a-> 24a 11b-> 24b 0.020318 + 11a-> 25a 11b-> 24b 0.020126 + 11a-> 24a 11b-> 25b 0.020126 + 11b-> 24b -1b-> -1b 0.018979 + 11a-> 24a -1a-> -1a 0.018979 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034468301 + alpha-alpha-alpha ... -0.000861480 ( 2.5%) + alpha-alpha-beta ... -0.016372671 ( 47.5%) + alpha-beta -beta ... -0.016372671 ( 47.5%) + beta -beta -beta ... -0.000861480 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034468301 + +Final correlation energy ... -0.729039980 +E(CCSD) ... -205.399709757 +E(CCSD(T)) ... -205.434178059 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210179897 sqrt= 1.100081768 +W(HF) = 0.826323427 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.314925 0.000000 + 1 N : 0.179823 -0.000000 + 2 O : -0.103349 0.000000 + 3 H : 0.238450 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.837920 s : 3.837920 + pz : 1.294653 p : 4.411644 + px : 1.555340 + py : 1.561651 + dz2 : 0.014857 d : 0.057364 + dxz : 0.013065 + dyz : 0.011945 + dx2y2 : 0.009090 + dxy : 0.008408 + f0 : 0.001799 f : 0.007997 + f+1 : 0.001159 + f-1 : 0.001267 + f+2 : 0.000856 + f-2 : 0.000955 + f+3 : 0.000997 + f-3 : 0.000965 + 1 N s : 3.877543 s : 3.877543 + pz : 0.868012 p : 2.745003 + px : 0.865144 + py : 1.011847 + dz2 : 0.034818 d : 0.167669 + dxz : 0.046311 + dyz : 0.026396 + dx2y2 : 0.036089 + dxy : 0.024055 + f0 : 0.007575 f : 0.029962 + f+1 : 0.002713 + f-1 : 0.005361 + f+2 : 0.002889 + f-2 : 0.005313 + f+3 : 0.003258 + f-3 : 0.002852 + 2 O s : 3.863157 s : 3.863157 + pz : 1.643620 p : 4.147305 + px : 1.193488 + py : 1.310197 + dz2 : 0.009985 d : 0.083069 + dxz : 0.015198 + dyz : 0.015925 + dx2y2 : 0.027771 + dxy : 0.014191 + f0 : 0.001587 f : 0.009817 + f+1 : 0.001077 + f-1 : 0.001085 + f+2 : 0.000593 + f-2 : 0.001652 + f+3 : 0.002165 + f-3 : 0.001660 + 3 H s : 0.649228 s : 0.649228 + pz : 0.025342 p : 0.095037 + px : 0.038101 + py : 0.031594 + dz2 : 0.001309 d : 0.017285 + dxz : 0.002895 + dyz : 0.004146 + dx2y2 : 0.008642 + dxy : 0.000293 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.577401 0.000000 + 1 N : -0.280914 0.000000 + 2 O : 0.291404 -0.000000 + 3 H : -0.587891 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.139599 s : 3.139599 + pz : 1.220914 p : 3.911620 + px : 1.324624 + py : 1.366082 + dz2 : 0.088391 d : 0.289124 + dxz : 0.077765 + dyz : 0.057258 + dx2y2 : 0.021268 + dxy : 0.044442 + f0 : 0.018090 f : 0.082257 + f+1 : 0.018819 + f-1 : 0.015587 + f+2 : 0.010655 + f-2 : 0.011287 + f+3 : 0.005164 + f-3 : 0.002654 + 1 N s : 3.041808 s : 3.041808 + pz : 0.880885 p : 2.879276 + px : 0.944246 + py : 1.054145 + dz2 : 0.205048 d : 0.929461 + dxz : 0.246141 + dyz : 0.131780 + dx2y2 : 0.148702 + dxy : 0.197790 + f0 : 0.092232 f : 0.430370 + f+1 : 0.056312 + f-1 : 0.055507 + f+2 : 0.027229 + f-2 : 0.079755 + f+3 : 0.062474 + f-3 : 0.056861 + 2 O s : 3.318800 s : 3.318800 + pz : 1.367650 p : 3.907077 + px : 1.241902 + py : 1.297525 + dz2 : 0.056346 d : 0.357248 + dxz : 0.073581 + dyz : 0.037767 + dx2y2 : 0.069594 + dxy : 0.119961 + f0 : 0.013319 f : 0.125471 + f+1 : 0.014783 + f-1 : 0.013256 + f+2 : 0.005858 + f-2 : 0.022019 + f+3 : 0.031446 + f-3 : 0.024790 + 3 H s : 0.625582 s : 0.625582 + pz : 0.147086 p : 0.584196 + px : 0.203695 + py : 0.233416 + dz2 : 0.032441 d : 0.378113 + dxz : 0.065886 + dyz : 0.071581 + dx2y2 : 0.116178 + dxy : 0.092027 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3149 8.0000 -0.3149 2.1566 1.6956 0.4609 + 1 N 6.8202 7.0000 0.1798 2.8549 2.3600 0.4949 + 2 O 8.1033 8.0000 -0.1033 2.1896 1.6901 0.4995 + 3 H 0.7615 1.0000 0.2385 1.0166 0.9420 0.0746 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7168 B( 0-O , 3-H ) : 0.8919 B( 1-N , 2-O ) : 1.5981 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 106.311 sec + +Fock Matrix Formation ... 0.492 sec ( 0.5%) +Initial Guess ... 0.165 sec ( 0.2%) +DIIS Solver ... 5.250 sec ( 4.9%) +State Vector Update ... 0.233 sec ( 0.2%) +Sigma-vector construction ... 74.458 sec ( 70.0%) + <0|H|D> ... 0.006 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.038 sec ( 0.1% of sigma) + (0-ext) ... 0.111 sec ( 0.1% of sigma) + (2-ext Fock) ... 0.042 sec ( 0.1% of sigma) + (2-ext) ... 1.541 sec ( 2.1% of sigma) + (4-ext) ... 44.294 sec ( 59.5% of sigma) + ... 4.025 sec ( 5.4% of sigma) + ... 0.005 sec ( 0.0% of sigma) + (1-ext) ... 0.014 sec ( 0.0% of sigma) + (1-ext) ... 0.203 sec ( 0.3% of sigma) + Fock-dressing ... 4.778 sec ( 6.4% of sigma) + (ik|jl)-dressing ... 0.152 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 15.659 sec ( 21.0% of sigma) + Pair energies ... 0.028 sec ( 0.0% of sigma) +Total Time for computing (T) ... 13.191 sec ( 12.4% of ALL) + I/O of integral and amplitudes ... 1.271 sec ( 9.6% of (T)) + External N**7 contributions ... 5.501 sec ( 41.7% of (T)) + Internal N**7 contributions ... 0.446 sec ( 3.4% of (T)) + N**6 triples energy contributions ... 2.288 sec ( 17.3% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.434178058715 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.003373606 -0.001408019 0.000090980 + 2 N : -0.004619411 -0.000777103 0.001315518 + 3 O : 0.004213570 0.001390882 -0.000650572 + 4 H : -0.002967765 0.000794240 -0.000755925 + +Norm of the cartesian gradient ... 0.008195565 +RMS gradient ... 0.002365856 +MAX gradient ... 0.004619411 + +------- +TIMINGS +------- + +Total numerical gradient time ... 588.400 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: -558.96 cm**-1 ***imaginary mode*** + 7: 551.21 cm**-1 + 8: 782.67 cm**-1 + 9: 1129.67 cm**-1 + 10: 1689.39 cm**-1 + 11: 3713.37 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 -0.051504 0.461304 -0.069590 -0.002202 -0.025753 -0.040214 + 1 -0.039400 0.091830 -0.186897 0.042501 0.027858 0.046640 + 2 -0.036973 -0.504800 -0.208591 -0.054139 0.067248 -0.011231 + 3 0.045537 -0.283412 -0.112730 0.040166 -0.518877 -0.000483 + 4 -0.046714 -0.112709 0.295634 -0.044103 -0.526989 -0.000025 + 5 0.050383 0.217818 0.560650 -0.022406 0.006776 -0.000001 + 6 -0.032379 -0.230692 0.192579 -0.010732 0.484932 0.000502 + 7 0.038304 0.009321 -0.052122 -0.002911 0.433004 0.000382 + 8 -0.021552 0.337462 -0.304292 0.015122 -0.080040 -0.000353 + 9 0.698618 0.277977 -0.385606 -0.352848 -0.077883 0.637018 + 10 0.666513 -0.039288 -0.314368 -0.015521 0.008147 -0.745977 + 11 0.228794 -0.370772 0.349807 0.930646 0.108866 0.183866 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 7: 551.21 0.023498 118.75 0.013303 (-0.082384 -0.012717 0.079715) + 8: 782.67 0.032272 163.09 0.012867 (-0.071017 0.007585 0.088126) + 9: 1129.67 0.007351 37.15 0.002031 (-0.024870 0.014658 0.034601) + 10: 1689.39 0.033210 167.83 0.006135 (-0.057918 -0.014761 0.050619) + 11: 3713.37 0.011417 57.70 0.000959 ( 0.024692 -0.017111 -0.007552) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 7 +The total number of vibrations considered is 5 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 551.21 E(vib) ... 0.12 +freq. 782.67 E(vib) ... 0.05 +freq. 1129.67 E(vib) ... 0.01 +freq. 1689.39 E(vib) ... 0.00 +freq. 3713.37 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.43417806 Eh +Zero point energy ... 0.01792076 Eh 11.25 kcal/mol +Thermal vibrational correction ... 0.00029687 Eh 0.19 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.41312789 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00312941 Eh 1.96 kcal/mol +Non-thermal (ZPE) correction 0.01792076 Eh 11.25 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02105017 Eh 13.21 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.41312789 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.41218368 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.722032 0.400419 0.361030 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00039194 Eh 0.25 kcal/mol +Rotational entropy ... 0.00995111 Eh 6.24 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02814536 Eh 17.66 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00995111 Eh 6.24 kcal/mol| +| sn= 2 | S(rot)= 0.00929665 Eh 5.83 kcal/mol| +| sn= 3 | S(rot)= 0.00891382 Eh 5.59 kcal/mol| +| sn= 4 | S(rot)= 0.00864220 Eh 5.42 kcal/mol| +| sn= 5 | S(rot)= 0.00843151 Eh 5.29 kcal/mol| +| sn= 6 | S(rot)= 0.00825936 Eh 5.18 kcal/mol| +| sn= 7 | S(rot)= 0.00811382 Eh 5.09 kcal/mol| +| sn= 8 | S(rot)= 0.00798774 Eh 5.01 kcal/mol| +| sn= 9 | S(rot)= 0.00787653 Eh 4.94 kcal/mol| +| sn=10 | S(rot)= 0.00777705 Eh 4.88 kcal/mol| +| sn=11 | S(rot)= 0.00768706 Eh 4.82 kcal/mol| +| sn=12 | S(rot)= 0.00760491 Eh 4.77 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.41218368 Eh +Total entropy correction ... -0.02814536 Eh -17.66 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44032904 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00615098 Eh -3.86 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.434178059 Eh +Current gradient norm .... 0.008195565 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + -0.032361742 0.096662647 0.164057736 0.469664794 0.497313961 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999838624 +Lowest eigenvalues of augmented Hessian: + -0.000062982 0.095807926 0.164054285 0.469078684 0.497316506 +Length of the computed step .... 0.017967455 +The final length of the internal step .... 0.017967455 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0073351829 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0034010823 RMS(Int)= 0.0073324089 + Iter 1: RMS(Cart)= 0.0000085925 RMS(Int)= 0.0000143502 + Iter 2: RMS(Cart)= 0.0000000464 RMS(Int)= 0.0000000634 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0021598453 0.0001000000 NO + MAX gradient 0.0041412833 0.0003000000 NO + RMS step 0.0073351829 0.0020000000 NO + MAX step 0.0144277720 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0076 Max(Angles) 0.29 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4959 -0.000863 0.0076 1.5036 + 2. B(O 2,N 1) 1.1692 0.004141 -0.0035 1.1657 + 3. B(H 3,O 0) 0.9727 0.002623 -0.0028 0.9699 + 4. A(N 1,O 0,H 3) 103.60 0.000353 -0.29 103.31 + 5. A(O 0,N 1,O 2) 111.54 0.001757 -0.24 111.30 + 6. D(O 2,N 1,O 0,H 3) 81.82 0.003140 0.00 81.82 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.403614 -0.254127 0.750396 + N 0.276719 -0.488700 -0.569786 + O 1.144432 0.270840 -0.739912 + H -1.017536 0.471988 0.559301 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.762720 -0.480230 1.418044 + 1 N 7.0000 0 14.007 0.522923 -0.923510 -1.076739 + 2 O 8.0000 0 15.999 2.162663 0.511813 -1.398230 + 3 H 1.0000 0 1.008 -1.922864 0.891927 1.056925 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.503581737846 0.00000000 0.00000000 + O 2 1 0 1.165662902890 111.30365011 0.00000000 + H 1 2 3 0.969875936809 103.30963883 81.81818178 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.841357704495 0.00000000 0.00000000 + O 2 1 0 2.202783650934 111.30365011 0.00000000 + H 1 2 3 1.832799904450 103.30963883 81.81818178 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.1 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.1 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2229 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2697 + la=0 lb=0: 549 shell pairs + la=1 lb=0: 535 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.362086281964 Eh + +SHARK setup successfully completed in 0.5 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.823e-04 +Time for diagonalization ... 0.005 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.005 sec +Total time needed ... 0.024 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7050846865 0.000000000000 0.00020558 0.00000688 0.0014030 0.7000 + 1 -204.7050982694 -0.000013582848 0.00016803 0.00000579 0.0011415 0.7000 + ***Turning on DIIS*** + 2 -204.7051094035 -0.000011134117 0.00043356 0.00001547 0.0009045 0.0000 + 3 -204.7045459150 0.000563488494 0.00015899 0.00000631 0.0002510 0.0000 + 4 -204.7052521484 -0.000706233397 0.00004648 0.00000210 0.0000614 0.0000 + 5 -204.7052854333 -0.000033284928 0.00002141 0.00000089 0.0000567 0.0000 + 6 -204.7050292679 0.000256165402 0.00001235 0.00000047 0.0000201 0.0000 + 7 -204.7051894026 -0.000160134661 0.00000594 0.00000023 0.0000099 0.0000 + 8 -204.7051479071 0.000041495486 0.00000353 0.00000014 0.0000046 0.0000 + 9 -204.7051429189 0.000004988149 0.00000295 0.00000010 0.0000028 0.0000 + 10 -204.7051523869 -0.000009467961 0.00000211 0.00000007 0.0000023 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + +Total Energy : -204.70514233 Eh -5570.31011 eV + Last Energy change ... 1.0056e-05 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.4049e-06 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 9 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.767 sec +Reference energy ... -204.705145137 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 15.154 sec +AO-integral generation ... 0.358 sec +Half transformation ... 0.173 sec +K-integral sorting ... 11.138 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.075 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.101 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.093 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.115 s ( 0.001 ms/b) +: 159120 b 0 skpd 0.061 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.105 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.091 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.077 s ( 0.001 ms/b) + 87516 b 0 skpd 0.131 s ( 0.002 ms/b) +: 27846 b 0 skpd 0.073 s ( 0.003 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 1.051 sec +AO-integral generation ... 0.832 sec +Half transformation ... 0.093 sec +J-integral sorting ... 0.092 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.301 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.432 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090009403 +EMP2(bb)= -0.090009403 +EMP2(ab)= -0.517368719 + +Initial guess performed in 0.207 sec +E(0) ... -204.705145137 +E(MP2) ... -0.697387526 +Initial E(tot) ... -205.402532662 + ... 0.189521109 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.402532662 -0.697387526 -0.000000000 0.019035140 8.75 0.000001714 + *** Turning on DIIS *** + 1 -205.374222862 -0.669077725 0.028309800 0.010716611 8.11 0.055515683 + 2 -205.393760351 -0.688615214 -0.019537489 0.003786209 7.43 0.058234524 + 3 -205.397583597 -0.692438460 -0.003823246 0.002049537 7.74 0.071141135 + 4 -205.399119475 -0.693974338 -0.001535878 0.000940211 7.07 0.076857975 + 5 -205.399602004 -0.694456867 -0.000482529 0.000444418 7.81 0.081087241 + 6 -205.399678070 -0.694532933 -0.000076066 0.000332612 7.95 0.083002039 + 7 -205.399708304 -0.694563167 -0.000030234 0.000247595 7.92 0.083840902 + 8 -205.399714973 -0.694569837 -0.000006670 0.000176814 7.36 0.084213525 + 9 -205.399711975 -0.694566838 0.000002999 0.000116314 8.37 0.084370669 + 10 -205.399716702 -0.694571565 -0.000004727 0.000058797 8.04 0.084458110 + 11 -205.399713191 -0.694568055 0.000003510 0.000025508 9.68 0.084488050 + 12 -205.399715754 -0.694570617 -0.000002563 0.000012794 6.17 0.084504850 + 13 -205.399715865 -0.694570728 -0.000000110 0.000008919 6.87 0.084508292 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.705145137 +E(CORR) ... -0.694570728 +E(TOT) ... -205.399715865 +Singles norm **1/2 ... 0.084508292 ( 0.042254146, 0.042254146) +T1 diagnostic ... 0.019918795 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.060817 + 8a-> 13a 8b-> 13b 0.055942 + 8a-> 13a 9b-> 13b 0.046483 + 9a-> 13a 8b-> 13b 0.046483 + 5a-> 13a 5b-> 13b 0.030068 + 11a-> 13a 11b-> 13b 0.028369 + 8b-> 13b -1b-> -1b 0.028034 + 8a-> 13a -1a-> -1a 0.028034 + 11a-> 24a 11b-> 24b 0.024065 + 9a-> 22a 9b-> 13b 0.023481 + 9a-> 13a 9b-> 22b 0.023481 + 11a-> 25a 11b-> 25b 0.022664 + 11a-> 25a 11b-> 24b 0.022182 + 11a-> 24a 11b-> 25b 0.022182 + 11b-> 24b -1b-> -1b 0.020234 + 11a-> 24a -1a-> -1a 0.020234 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034493823 + alpha-alpha-alpha ... -0.000860960 ( 2.5%) + alpha-alpha-beta ... -0.016385952 ( 47.5%) + alpha-beta -beta ... -0.016385952 ( 47.5%) + beta -beta -beta ... -0.000860960 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034493823 + +Final correlation energy ... -0.729064550 +E(CCSD) ... -205.399715865 +E(CCSD(T)) ... -205.434209687 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210190018 sqrt= 1.100086369 +W(HF) = 0.826316516 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 145.239 sec + +Fock Matrix Formation ... 0.767 sec ( 0.5%) +Initial Guess ... 0.207 sec ( 0.1%) +DIIS Solver ... 6.506 sec ( 4.5%) +State Vector Update ... 0.364 sec ( 0.3%) +Sigma-vector construction ... 102.410 sec ( 70.5%) + <0|H|D> ... 0.008 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.048 sec ( 0.0% of sigma) + (0-ext) ... 0.183 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.066 sec ( 0.1% of sigma) + (2-ext) ... 2.347 sec ( 2.3% of sigma) + (4-ext) ... 61.378 sec ( 59.9% of sigma) + ... 5.149 sec ( 5.0% of sigma) + ... 0.007 sec ( 0.0% of sigma) + (1-ext) ... 0.022 sec ( 0.0% of sigma) + (1-ext) ... 0.264 sec ( 0.3% of sigma) + Fock-dressing ... 6.125 sec ( 6.0% of sigma) + (ik|jl)-dressing ... 0.190 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 22.091 sec ( 21.6% of sigma) + Pair energies ... 0.035 sec ( 0.0% of sigma) +Total Time for computing (T) ... 15.589 sec ( 10.7% of ALL) + I/O of integral and amplitudes ... 2.178 sec ( 14.0% of (T)) + External N**7 contributions ... 9.557 sec ( 61.3% of (T)) + Internal N**7 contributions ... 0.864 sec ( 5.5% of (T)) + N**6 triples energy contributions ... 2.811 sec ( 18.0% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.434209687204 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.001577080 0.000991934 0.000585017 + 2 N : -0.001289485 0.001042074 -0.000814975 + 3 O : 0.000846205 -0.000940121 0.000625522 + 4 H : -0.001133800 -0.001093886 -0.000395565 + +Norm of the cartesian gradient ... 0.003443249 +RMS gradient ... 0.000993980 +MAX gradient ... 0.001577080 + +------- +TIMINGS +------- + +Total numerical gradient time ... 931.220 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.434209687 Eh +Current gradient norm .... 0.003443249 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999918 +Lowest eigenvalues of augmented Hessian: + -0.000000024 0.094234365 0.163716415 0.468232273 0.499731600 +Length of the computed step .... 0.000405602 +The final length of the internal step .... 0.000405602 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0001655864 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0000846596 RMS(Int)= 0.0001655865 + Iter 1: RMS(Cart)= 0.0000000033 RMS(Int)= 0.0000000044 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000316286 0.0000050000 NO + RMS gradient 0.0000381989 0.0001000000 YES + MAX gradient 0.0000737744 0.0003000000 YES + RMS step 0.0001655864 0.0020000000 YES + MAX step 0.0003804302 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0002 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.5036 -0.000050 0.0002 1.5038 + 2. B(O 2,N 1) 1.1657 -0.000074 0.0000 1.1657 + 3. B(H 3,O 0) 0.9699 -0.000023 0.0000 0.9699 + 4. A(N 1,O 0,H 3) 103.31 0.000002 -0.01 103.30 + 5. A(O 0,N 1,O 2) 111.30 0.000015 -0.00 111.30 + 6. D(O 2,N 1,O 0,H 3) 81.82 0.002895 -0.00 81.82 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.403658 -0.254131 0.750495 + N 0.276754 -0.488731 -0.569871 + O 1.144467 0.270855 -0.739932 + H -1.017562 0.472007 0.559307 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.762802 -0.480238 1.418231 + 1 N 7.0000 0 14.007 0.522989 -0.923568 -1.076899 + 2 O 8.0000 0 15.999 2.162729 0.511842 -1.398268 + 3 H 1.0000 0 1.008 -1.922914 0.891964 1.056937 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.503783052853 0.00000000 0.00000000 + O 2 1 0 1.165683324312 111.29966187 0.00000000 + H 1 2 3 0.969900905627 103.30356844 81.81818178 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.841738134724 0.00000000 0.00000000 + O 2 1 0 2.202822241830 111.29966187 0.00000000 + H 1 2 3 1.832847088677 103.30356844 81.81818178 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.1 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2229 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2697 + la=0 lb=0: 549 shell pairs + la=1 lb=0: 535 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.357766856732 Eh + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.3577668567 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.824e-04 +Time for diagonalization ... 0.005 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.006 sec +Total time needed ... 0.030 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7051217371 0.000000000000 0.00000632 0.00000014 0.0000255 0.7000 + 1 -204.7051217418 -0.000000004681 0.00000450 0.00000012 0.0000201 0.7000 + ***Turning on DIIS*** + 2 -204.7051217458 -0.000000003967 0.00001164 0.00000031 0.0000156 0.0000 + 3 -204.7051301766 -0.000008430864 0.00000459 0.00000013 0.0000043 0.0000 + 4 -204.7051199921 0.000010184484 0.00000137 0.00000004 0.0000012 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70511891 Eh -5570.30947 eV + +Components: +Nuclear Repulsion : 68.35776686 Eh 1860.10940 eV +Electronic Energy : -273.06288576 Eh -7430.41888 eV +One Electron Energy: -416.41286954 Eh -11331.17025 eV +Two Electron Energy: 143.34998378 Eh 3900.75137 eV + +Virial components: +Potential Energy : -408.93200669 Eh -11127.60562 eV +Kinetic Energy : 204.22688778 Eh 5557.29614 eV +Virial Ratio : 2.00234167 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.0865e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.0448e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.4895e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.7070e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.692581 -563.0737 + 1 1.0000 -20.616632 -561.0071 + 2 1.0000 -15.805929 -430.1012 + 3 1.0000 -1.618287 -44.0358 + 4 1.0000 -1.371599 -37.3231 + 5 1.0000 -0.956218 -26.0200 + 6 1.0000 -0.767529 -20.8855 + 7 1.0000 -0.734109 -19.9761 + 8 1.0000 -0.699782 -19.0420 + 9 1.0000 -0.604915 -16.4606 + 10 1.0000 -0.529519 -14.4089 + 11 1.0000 -0.459353 -12.4996 + 12 0.0000 0.031008 0.8438 + 13 0.0000 0.065972 1.7952 + 14 0.0000 0.091806 2.4982 + 15 0.0000 0.104271 2.8374 + 16 0.0000 0.113057 3.0764 + 17 0.0000 0.155512 4.2317 + 18 0.0000 0.157298 4.2803 + 19 0.0000 0.174476 4.7477 + 20 0.0000 0.178956 4.8696 + 21 0.0000 0.189860 5.1664 + 22 0.0000 0.201093 5.4720 + 23 0.0000 0.235280 6.4023 + 24 0.0000 0.269087 7.3222 + 25 0.0000 0.290478 7.9043 + 26 0.0000 0.301645 8.2082 + 27 0.0000 0.331823 9.0294 + 28 0.0000 0.334097 9.0912 + 29 0.0000 0.352097 9.5811 + 30 0.0000 0.424771 11.5586 + 31 0.0000 0.506481 13.7820 + 32 0.0000 0.529995 14.4219 + 33 0.0000 0.543529 14.7902 + 34 0.0000 0.565803 15.3963 + 35 0.0000 0.599591 16.3157 + 36 0.0000 0.630970 17.1696 + 37 0.0000 0.646412 17.5898 + 38 0.0000 0.709180 19.2978 + 39 0.0000 0.716604 19.4998 + 40 0.0000 0.736243 20.0342 + 41 0.0000 0.755511 20.5585 + 42 0.0000 0.761244 20.7145 + 43 0.0000 0.788959 21.4687 + 44 0.0000 0.807280 21.9672 + 45 0.0000 0.817479 22.2447 + 46 0.0000 0.860241 23.4083 + 47 0.0000 0.873203 23.7611 + 48 0.0000 0.893045 24.3010 + 49 0.0000 0.953738 25.9525 + 50 0.0000 0.961946 26.1759 + 51 0.0000 0.975830 26.5537 + 52 0.0000 0.991169 26.9711 + 53 0.0000 1.028556 27.9884 + 54 0.0000 1.044133 28.4123 + 55 0.0000 1.099835 29.9280 + 56 0.0000 1.154534 31.4165 + 57 0.0000 1.221491 33.2385 + 58 0.0000 1.246858 33.9287 + 59 0.0000 1.264137 34.3989 + 60 0.0000 1.315148 35.7870 + 61 0.0000 1.409195 38.3461 + 62 0.0000 1.459999 39.7286 + 63 0.0000 1.515790 41.2467 + 64 0.0000 1.530515 41.6474 + 65 0.0000 1.572478 42.7893 + 66 0.0000 1.589213 43.2447 + 67 0.0000 1.631034 44.3827 + 68 0.0000 1.649876 44.8954 + 69 0.0000 1.723366 46.8952 + 70 0.0000 1.761393 47.9299 + 71 0.0000 1.779733 48.4290 + 72 0.0000 1.902311 51.7645 + 73 0.0000 1.924372 52.3648 + 74 0.0000 1.979955 53.8773 + 75 0.0000 2.010153 54.6991 + 76 0.0000 2.042186 55.5707 + 77 0.0000 2.095513 57.0218 + 78 0.0000 2.135623 58.1133 + 79 0.0000 2.195478 59.7420 + 80 0.0000 2.273903 61.8761 + 81 0.0000 2.290468 62.3268 + 82 0.0000 2.332662 63.4750 + 83 0.0000 2.352860 64.0246 + 84 0.0000 2.406339 65.4798 + 85 0.0000 2.452485 66.7355 + 86 0.0000 2.465587 67.0920 + 87 0.0000 2.476696 67.3943 + 88 0.0000 2.509776 68.2945 + 89 0.0000 2.563604 69.7592 + 90 0.0000 2.584788 70.3357 + 91 0.0000 2.600662 70.7676 + 92 0.0000 2.664769 72.5121 + 93 0.0000 2.721378 74.0525 + 94 0.0000 2.749841 74.8270 + 95 0.0000 2.764312 75.2207 + 96 0.0000 2.842362 77.3446 + 97 0.0000 2.908257 79.1377 + 98 0.0000 2.958022 80.4919 + 99 0.0000 2.982381 81.1547 + 100 0.0000 3.066326 83.4390 + 101 0.0000 3.167406 86.1895 + 102 0.0000 3.223076 87.7044 + 103 0.0000 3.485767 94.8526 + 104 0.0000 3.718659 101.1899 + 105 0.0000 3.815136 103.8151 + 106 0.0000 4.045004 110.0702 + 107 0.0000 4.170784 113.4928 + 108 0.0000 4.202077 114.3443 + 109 0.0000 4.282807 116.5411 + 110 0.0000 4.365001 118.7777 + 111 0.0000 4.392961 119.5385 + 112 0.0000 4.523786 123.0985 + 113 0.0000 4.611058 125.4733 + 114 0.0000 4.662288 126.8673 + 115 0.0000 4.718667 128.4015 + 116 0.0000 4.838614 131.6654 + 117 0.0000 4.895220 133.2057 + 118 0.0000 4.928662 134.1157 + 119 0.0000 4.953726 134.7977 + 120 0.0000 5.048739 137.3832 + 121 0.0000 5.105325 138.9230 + 122 0.0000 5.184374 141.0740 + 123 0.0000 5.194942 141.3616 + 124 0.0000 5.232651 142.3877 + 125 0.0000 5.309355 144.4749 + 126 0.0000 5.387228 146.5939 + 127 0.0000 5.487146 149.3128 + 128 0.0000 5.548463 150.9814 + 129 0.0000 5.696055 154.9975 + 130 0.0000 5.740193 156.1986 + 131 0.0000 5.935903 161.5241 + 132 0.0000 6.173557 167.9910 + 133 0.0000 6.418210 174.6484 + 134 0.0000 6.479241 176.3091 + 135 0.0000 6.506109 177.0402 + 136 0.0000 6.696212 182.2132 + 137 0.0000 6.720456 182.8729 + 138 0.0000 6.772773 184.2965 + 139 0.0000 6.817135 185.5037 + 140 0.0000 6.830083 185.8560 + 141 0.0000 7.069365 192.3672 + 142 0.0000 7.102275 193.2627 + 143 0.0000 7.117315 193.6720 + 144 0.0000 7.200407 195.9330 + 145 0.0000 7.255887 197.4427 + 146 0.0000 7.281533 198.1406 + 147 0.0000 7.338811 199.6992 + 148 0.0000 7.383813 200.9238 + 149 0.0000 7.454441 202.8457 + 150 0.0000 7.464964 203.1320 + 151 0.0000 7.567172 205.9132 + 152 0.0000 7.570528 206.0045 + 153 0.0000 7.635410 207.7701 + 154 0.0000 7.700045 209.5289 + 155 0.0000 7.893653 214.7972 + 156 0.0000 7.930832 215.8089 + 157 0.0000 8.395729 228.4594 + 158 0.0000 14.051575 382.3628 + 159 0.0000 14.867986 404.5785 + 160 0.0000 16.079051 437.5332 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.692581 -563.0737 + 1 1.0000 -20.616632 -561.0071 + 2 1.0000 -15.805929 -430.1012 + 3 1.0000 -1.618287 -44.0358 + 4 1.0000 -1.371599 -37.3231 + 5 1.0000 -0.956218 -26.0200 + 6 1.0000 -0.767529 -20.8855 + 7 1.0000 -0.734109 -19.9761 + 8 1.0000 -0.699782 -19.0420 + 9 1.0000 -0.604915 -16.4606 + 10 1.0000 -0.529519 -14.4089 + 11 1.0000 -0.459353 -12.4996 + 12 0.0000 0.031008 0.8438 + 13 0.0000 0.065972 1.7952 + 14 0.0000 0.091806 2.4982 + 15 0.0000 0.104271 2.8374 + 16 0.0000 0.113057 3.0764 + 17 0.0000 0.155512 4.2317 + 18 0.0000 0.157298 4.2803 + 19 0.0000 0.174476 4.7477 + 20 0.0000 0.178956 4.8696 + 21 0.0000 0.189860 5.1664 + 22 0.0000 0.201093 5.4720 + 23 0.0000 0.235280 6.4023 + 24 0.0000 0.269087 7.3222 + 25 0.0000 0.290478 7.9043 + 26 0.0000 0.301645 8.2082 + 27 0.0000 0.331823 9.0294 + 28 0.0000 0.334097 9.0912 + 29 0.0000 0.352097 9.5811 + 30 0.0000 0.424771 11.5586 + 31 0.0000 0.506481 13.7820 + 32 0.0000 0.529995 14.4219 + 33 0.0000 0.543529 14.7902 + 34 0.0000 0.565803 15.3963 + 35 0.0000 0.599591 16.3157 + 36 0.0000 0.630970 17.1696 + 37 0.0000 0.646412 17.5898 + 38 0.0000 0.709180 19.2978 + 39 0.0000 0.716604 19.4998 + 40 0.0000 0.736243 20.0342 + 41 0.0000 0.755511 20.5585 + 42 0.0000 0.761244 20.7145 + 43 0.0000 0.788959 21.4687 + 44 0.0000 0.807280 21.9672 + 45 0.0000 0.817479 22.2447 + 46 0.0000 0.860241 23.4083 + 47 0.0000 0.873203 23.7611 + 48 0.0000 0.893045 24.3010 + 49 0.0000 0.953738 25.9525 + 50 0.0000 0.961946 26.1759 + 51 0.0000 0.975830 26.5537 + 52 0.0000 0.991169 26.9711 + 53 0.0000 1.028556 27.9884 + 54 0.0000 1.044133 28.4123 + 55 0.0000 1.099835 29.9280 + 56 0.0000 1.154534 31.4165 + 57 0.0000 1.221491 33.2385 + 58 0.0000 1.246858 33.9287 + 59 0.0000 1.264137 34.3989 + 60 0.0000 1.315148 35.7870 + 61 0.0000 1.409195 38.3461 + 62 0.0000 1.459999 39.7286 + 63 0.0000 1.515790 41.2467 + 64 0.0000 1.530515 41.6474 + 65 0.0000 1.572478 42.7893 + 66 0.0000 1.589213 43.2447 + 67 0.0000 1.631034 44.3827 + 68 0.0000 1.649876 44.8954 + 69 0.0000 1.723366 46.8952 + 70 0.0000 1.761393 47.9299 + 71 0.0000 1.779733 48.4290 + 72 0.0000 1.902311 51.7645 + 73 0.0000 1.924372 52.3648 + 74 0.0000 1.979955 53.8773 + 75 0.0000 2.010153 54.6991 + 76 0.0000 2.042186 55.5707 + 77 0.0000 2.095513 57.0218 + 78 0.0000 2.135623 58.1133 + 79 0.0000 2.195478 59.7420 + 80 0.0000 2.273903 61.8761 + 81 0.0000 2.290468 62.3268 + 82 0.0000 2.332662 63.4750 + 83 0.0000 2.352860 64.0246 + 84 0.0000 2.406339 65.4798 + 85 0.0000 2.452485 66.7355 + 86 0.0000 2.465587 67.0920 + 87 0.0000 2.476696 67.3943 + 88 0.0000 2.509776 68.2945 + 89 0.0000 2.563604 69.7592 + 90 0.0000 2.584788 70.3357 + 91 0.0000 2.600662 70.7676 + 92 0.0000 2.664769 72.5121 + 93 0.0000 2.721378 74.0525 + 94 0.0000 2.749841 74.8270 + 95 0.0000 2.764312 75.2207 + 96 0.0000 2.842362 77.3446 + 97 0.0000 2.908257 79.1377 + 98 0.0000 2.958022 80.4919 + 99 0.0000 2.982381 81.1547 + 100 0.0000 3.066326 83.4390 + 101 0.0000 3.167406 86.1895 + 102 0.0000 3.223076 87.7044 + 103 0.0000 3.485767 94.8526 + 104 0.0000 3.718659 101.1899 + 105 0.0000 3.815136 103.8151 + 106 0.0000 4.045004 110.0702 + 107 0.0000 4.170784 113.4928 + 108 0.0000 4.202077 114.3443 + 109 0.0000 4.282807 116.5411 + 110 0.0000 4.365001 118.7777 + 111 0.0000 4.392961 119.5385 + 112 0.0000 4.523786 123.0985 + 113 0.0000 4.611058 125.4733 + 114 0.0000 4.662288 126.8673 + 115 0.0000 4.718667 128.4015 + 116 0.0000 4.838614 131.6654 + 117 0.0000 4.895220 133.2057 + 118 0.0000 4.928662 134.1157 + 119 0.0000 4.953726 134.7977 + 120 0.0000 5.048739 137.3832 + 121 0.0000 5.105325 138.9230 + 122 0.0000 5.184374 141.0740 + 123 0.0000 5.194942 141.3616 + 124 0.0000 5.232651 142.3877 + 125 0.0000 5.309355 144.4749 + 126 0.0000 5.387228 146.5939 + 127 0.0000 5.487146 149.3128 + 128 0.0000 5.548463 150.9814 + 129 0.0000 5.696055 154.9975 + 130 0.0000 5.740193 156.1986 + 131 0.0000 5.935903 161.5241 + 132 0.0000 6.173557 167.9910 + 133 0.0000 6.418210 174.6484 + 134 0.0000 6.479241 176.3091 + 135 0.0000 6.506109 177.0402 + 136 0.0000 6.696212 182.2132 + 137 0.0000 6.720456 182.8729 + 138 0.0000 6.772773 184.2965 + 139 0.0000 6.817135 185.5037 + 140 0.0000 6.830083 185.8560 + 141 0.0000 7.069365 192.3672 + 142 0.0000 7.102275 193.2627 + 143 0.0000 7.117315 193.6720 + 144 0.0000 7.200407 195.9330 + 145 0.0000 7.255887 197.4427 + 146 0.0000 7.281533 198.1406 + 147 0.0000 7.338811 199.6992 + 148 0.0000 7.383813 200.9238 + 149 0.0000 7.454441 202.8457 + 150 0.0000 7.464964 203.1320 + 151 0.0000 7.567172 205.9132 + 152 0.0000 7.570528 206.0045 + 153 0.0000 7.635410 207.7701 + 154 0.0000 7.700045 209.5289 + 155 0.0000 7.893653 214.7972 + 156 0.0000 7.930832 215.8089 + 157 0.0000 8.395729 228.4594 + 158 0.0000 14.051575 382.3628 + 159 0.0000 14.867986 404.5785 + 160 0.0000 16.079051 437.5332 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.375273 0.000000 + 1 N : 0.353462 0.000000 + 2 O : -0.225967 0.000000 + 3 H : 0.247777 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.861059 s : 3.861059 + pz : 1.317124 p : 4.483762 + px : 1.576851 + py : 1.589787 + dz2 : 0.009744 d : 0.026246 + dxz : 0.007926 + dyz : 0.004815 + dx2y2 : 0.001862 + dxy : 0.001899 + f0 : 0.001346 f : 0.004205 + f+1 : 0.000880 + f-1 : 0.000710 + f+2 : 0.000280 + f-2 : 0.000333 + f+3 : 0.000347 + f-3 : 0.000308 + 1 N s : 3.823306 s : 3.823306 + pz : 0.821709 p : 2.654024 + px : 0.825918 + py : 1.006397 + dz2 : 0.027099 d : 0.138291 + dxz : 0.038475 + dyz : 0.019201 + dx2y2 : 0.034593 + dxy : 0.018924 + f0 : 0.007966 f : 0.030917 + f+1 : 0.002909 + f-1 : 0.005213 + f+2 : 0.002389 + f-2 : 0.005596 + f+3 : 0.003559 + f-3 : 0.003286 + 2 O s : 3.875330 s : 3.875330 + pz : 1.723948 p : 4.280560 + px : 1.217452 + py : 1.339159 + dz2 : 0.004573 d : 0.062595 + dxz : 0.008553 + dyz : 0.010895 + dx2y2 : 0.027194 + dxy : 0.011380 + f0 : 0.001168 f : 0.007482 + f+1 : 0.000608 + f-1 : 0.000637 + f+2 : -0.000039 + f-2 : 0.001336 + f+3 : 0.002218 + f-3 : 0.001555 + 3 H s : 0.643802 s : 0.643802 + pz : 0.021813 p : 0.088230 + px : 0.036250 + py : 0.030168 + dz2 : 0.001561 d : 0.020190 + dxz : 0.003124 + dyz : 0.004773 + dx2y2 : 0.009865 + dxy : 0.000867 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.574118 0.000000 + 1 N : -0.232418 0.000000 + 2 O : 0.249837 0.000000 + 3 H : -0.591537 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.136661 s : 3.136661 + pz : 1.228362 p : 3.960154 + px : 1.340640 + py : 1.391152 + dz2 : 0.081481 d : 0.255029 + dxz : 0.070593 + dyz : 0.051077 + dx2y2 : 0.015095 + dxy : 0.036783 + f0 : 0.016311 f : 0.074038 + f+1 : 0.016837 + f-1 : 0.014851 + f+2 : 0.009791 + f-2 : 0.010118 + f+3 : 0.004317 + f-3 : 0.001813 + 1 N s : 3.038661 s : 3.038661 + pz : 0.857204 p : 2.837846 + px : 0.923494 + py : 1.057148 + dz2 : 0.197093 d : 0.918085 + dxz : 0.243828 + dyz : 0.133531 + dx2y2 : 0.152940 + dxy : 0.190693 + f0 : 0.095268 f : 0.437826 + f+1 : 0.055016 + f-1 : 0.055659 + f+2 : 0.027030 + f-2 : 0.083677 + f+3 : 0.064006 + f-3 : 0.057169 + 2 O s : 3.314037 s : 3.314037 + pz : 1.416847 p : 3.987577 + px : 1.256163 + py : 1.314567 + dz2 : 0.050583 d : 0.330910 + dxz : 0.070304 + dyz : 0.032547 + dx2y2 : 0.061784 + dxy : 0.115691 + f0 : 0.012560 f : 0.117639 + f+1 : 0.013898 + f-1 : 0.013008 + f+2 : 0.005090 + f-2 : 0.021050 + f+3 : 0.029256 + f-3 : 0.022776 + 3 H s : 0.627147 s : 0.627147 + pz : 0.148429 p : 0.574493 + px : 0.198936 + py : 0.227127 + dz2 : 0.032040 d : 0.389898 + dxz : 0.068810 + dyz : 0.074514 + dx2y2 : 0.121459 + dxy : 0.093075 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3753 8.0000 -0.3753 1.8166 1.8166 0.0000 + 1 N 6.6465 7.0000 0.3535 2.5943 2.5943 -0.0000 + 2 O 8.2260 8.0000 -0.2260 1.8099 1.8099 0.0000 + 3 H 0.7522 1.0000 0.2478 0.9971 0.9971 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8027 B( 0-O , 3-H ) : 0.9565 B( 1-N , 2-O ) : 1.7517 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 3 sec + +Total time .... 3.953 sec +Sum of individual times .... 3.270 sec ( 82.7%) + +Fock matrix formation .... 1.888 sec ( 47.8%) +Diagonalization .... 0.613 sec ( 15.5%) +Density matrix formation .... 0.010 sec ( 0.3%) +Population analysis .... 0.166 sec ( 4.2%) +Initial guess .... 0.020 sec ( 0.5%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.011 sec ( 0.3%) +DIIS solution .... 0.573 sec ( 14.5%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.758 sec +Reference energy ... -204.705121757 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 12.471 sec +AO-integral generation ... 0.373 sec +Half transformation ... 0.186 sec +K-integral sorting ... 9.436 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.066 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.065 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.081 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.104 s ( 0.001 ms/b) +: 159120 b 0 skpd 0.054 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.100 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.090 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.066 s ( 0.001 ms/b) + 87516 b 0 skpd 0.118 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.064 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.947 sec +AO-integral generation ... 0.714 sec +Half transformation ... 0.101 sec +J-integral sorting ... 0.102 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.338 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.412 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090012215 +EMP2(bb)= -0.090012215 +EMP2(ab)= -0.517387454 + +Initial guess performed in 0.200 sec +E(0) ... -204.705121757 +E(MP2) ... -0.697411884 +Initial E(tot) ... -205.402533641 + ... 0.189543951 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.402533641 -0.697411884 -0.000000000 0.019036241 8.15 0.000001568 + *** Turning on DIIS *** + 1 -205.374212796 -0.669091039 0.028320845 0.010715279 6.26 0.055525105 + 2 -205.393754101 -0.688632344 -0.019541305 0.003786172 6.84 0.058242257 + 3 -205.397578021 -0.692456264 -0.003823920 0.002049287 7.21 0.071151275 + 4 -205.399114320 -0.693992563 -0.001536299 0.000942018 6.50 0.076869183 + 5 -205.399597051 -0.694475294 -0.000482731 0.000444429 6.19 0.081099759 + 6 -205.399673141 -0.694551384 -0.000076090 0.000332639 7.58 0.083015292 + 7 -205.399703392 -0.694581635 -0.000030250 0.000247621 7.03 0.083854759 + 8 -205.399710069 -0.694588312 -0.000006678 0.000176837 6.82 0.084227693 + 9 -205.399707068 -0.694585311 0.000003002 0.000116346 8.61 0.084384910 + 10 -205.399711799 -0.694590042 -0.000004731 0.000058828 7.70 0.084472394 + 11 -205.399708286 -0.694586529 0.000003513 0.000025529 5.98 0.084502343 + 12 -205.399710850 -0.694589093 -0.000002564 0.000012795 6.34 0.084519158 + 13 -205.399710960 -0.694589203 -0.000000110 0.000008923 7.17 0.084522598 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.705121757 +E(CORR) ... -0.694589203 +E(TOT) ... -205.399710960 +Singles norm **1/2 ... 0.084522598 ( 0.042261299, 0.042261299) +T1 diagnostic ... 0.019922167 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.060803 + 8a-> 13a 8b-> 13b 0.055967 + 9a-> 13a 8b-> 13b 0.046493 + 8a-> 13a 9b-> 13b 0.046493 + 5a-> 13a 5b-> 13b 0.030076 + 11a-> 13a 11b-> 13b 0.028360 + 8b-> 13b -1b-> -1b 0.028033 + 8a-> 13a -1a-> -1a 0.028033 + 11a-> 24a 11b-> 24b 0.024167 + 9a-> 22a 9b-> 13b 0.023471 + 9a-> 13a 9b-> 22b 0.023471 + 11a-> 25a 11b-> 25b 0.022648 + 11a-> 24a 11b-> 25b 0.022223 + 11a-> 25a 11b-> 24b 0.022223 + 11a-> 24a -1a-> -1a 0.020274 + 11b-> 24b -1b-> -1b 0.020274 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034498729 + alpha-alpha-alpha ... -0.000861008 ( 2.5%) + alpha-alpha-beta ... -0.016388357 ( 47.5%) + alpha-beta -beta ... -0.016388357 ( 47.5%) + beta -beta -beta ... -0.000861008 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034498729 + +Final correlation energy ... -0.729087933 +E(CCSD) ... -205.399710960 +E(CCSD(T)) ... -205.434209690 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210216093 sqrt= 1.100098220 +W(HF) = 0.826298713 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.318336 -0.000000 + 1 N : 0.181780 0.000000 + 2 O : -0.099542 -0.000000 + 3 H : 0.236098 -0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.840152 s : 3.840152 + pz : 1.295488 p : 4.413185 + px : 1.556992 + py : 1.560705 + dz2 : 0.014767 d : 0.057060 + dxz : 0.013056 + dyz : 0.011840 + dx2y2 : 0.009050 + dxy : 0.008348 + f0 : 0.001780 f : 0.007938 + f+1 : 0.001150 + f-1 : 0.001256 + f+2 : 0.000850 + f-2 : 0.000950 + f+3 : 0.000991 + f-3 : 0.000961 + 1 N s : 3.877546 s : 3.877546 + pz : 0.868568 p : 2.743458 + px : 0.865653 + py : 1.009237 + dz2 : 0.034588 d : 0.167381 + dxz : 0.046430 + dyz : 0.026357 + dx2y2 : 0.036147 + dxy : 0.023860 + f0 : 0.007528 f : 0.029835 + f+1 : 0.002735 + f-1 : 0.005312 + f+2 : 0.002847 + f-2 : 0.005310 + f+3 : 0.003232 + f-3 : 0.002869 + 2 O s : 3.862299 s : 3.862299 + pz : 1.641296 p : 4.143871 + px : 1.194600 + py : 1.307975 + dz2 : 0.009974 d : 0.083532 + dxz : 0.015264 + dyz : 0.016050 + dx2y2 : 0.027982 + dxy : 0.014261 + f0 : 0.001597 f : 0.009840 + f+1 : 0.001073 + f-1 : 0.001084 + f+2 : 0.000587 + f-2 : 0.001662 + f+3 : 0.002171 + f-3 : 0.001665 + 3 H s : 0.651116 s : 0.651116 + pz : 0.025550 p : 0.095503 + px : 0.038248 + py : 0.031705 + dz2 : 0.001347 d : 0.017283 + dxz : 0.002870 + dyz : 0.004124 + dx2y2 : 0.008641 + dxy : 0.000301 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.579007 0.000000 + 1 N : -0.275831 -0.000000 + 2 O : 0.293228 0.000000 + 3 H : -0.596405 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.140905 s : 3.140905 + pz : 1.219852 p : 3.913173 + px : 1.326332 + py : 1.366989 + dz2 : 0.087311 d : 0.285956 + dxz : 0.077293 + dyz : 0.056377 + dx2y2 : 0.021013 + dxy : 0.043961 + f0 : 0.017764 f : 0.080959 + f+1 : 0.018662 + f-1 : 0.015242 + f+2 : 0.010460 + f-2 : 0.011104 + f+3 : 0.005121 + f-3 : 0.002606 + 1 N s : 3.043588 s : 3.043588 + pz : 0.878636 p : 2.878399 + px : 0.945462 + py : 1.054302 + dz2 : 0.203290 d : 0.925309 + dxz : 0.244972 + dyz : 0.130903 + dx2y2 : 0.148572 + dxy : 0.197573 + f0 : 0.091792 f : 0.428534 + f+1 : 0.055884 + f-1 : 0.054941 + f+2 : 0.026625 + f-2 : 0.079755 + f+3 : 0.062509 + f-3 : 0.057028 + 2 O s : 3.316837 s : 3.316837 + pz : 1.364852 p : 3.904983 + px : 1.243137 + py : 1.296994 + dz2 : 0.056429 d : 0.358961 + dxz : 0.073975 + dyz : 0.038144 + dx2y2 : 0.070037 + dxy : 0.120375 + f0 : 0.013466 f : 0.125991 + f+1 : 0.014720 + f-1 : 0.013281 + f+2 : 0.005734 + f-2 : 0.022203 + f+3 : 0.031602 + f-3 : 0.024986 + 3 H s : 0.627464 s : 0.627464 + pz : 0.149078 p : 0.589189 + px : 0.205146 + py : 0.234965 + dz2 : 0.032622 d : 0.379752 + dxz : 0.066238 + dyz : 0.072201 + dx2y2 : 0.116542 + dxy : 0.092149 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3183 8.0000 -0.3183 2.1589 1.6962 0.4627 + 1 N 6.8182 7.0000 0.1818 2.8558 2.3612 0.4946 + 2 O 8.0995 8.0000 -0.0995 2.1937 1.6956 0.4982 + 3 H 0.7639 1.0000 0.2361 1.0176 0.9430 0.0747 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7142 B( 0-O , 3-H ) : 0.8939 B( 1-N , 2-O ) : 1.6027 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 134.968 sec + +Fock Matrix Formation ... 0.758 sec ( 0.6%) +Initial Guess ... 0.200 sec ( 0.1%) +DIIS Solver ... 5.651 sec ( 4.2%) +State Vector Update ... 0.241 sec ( 0.2%) +Sigma-vector construction ... 92.485 sec ( 68.5%) + <0|H|D> ... 0.010 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.053 sec ( 0.1% of sigma) + (0-ext) ... 0.180 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.061 sec ( 0.1% of sigma) + (2-ext) ... 2.210 sec ( 2.4% of sigma) + (4-ext) ... 55.069 sec ( 59.5% of sigma) + ... 4.734 sec ( 5.1% of sigma) + ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.023 sec ( 0.0% of sigma) + (1-ext) ... 0.231 sec ( 0.2% of sigma) + Fock-dressing ... 5.859 sec ( 6.3% of sigma) + (ik|jl)-dressing ... 0.198 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 19.429 sec ( 21.0% of sigma) + Pair energies ... 0.025 sec ( 0.0% of sigma) +Total Time for computing (T) ... 18.747 sec ( 13.9% of ALL) + I/O of integral and amplitudes ... 1.722 sec ( 9.2% of (T)) + External N**7 contributions ... 9.178 sec ( 49.0% of (T)) + Internal N**7 contributions ... 0.912 sec ( 4.9% of (T)) + N**6 triples energy contributions ... 3.325 sec ( 17.7% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.434209689695 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.033.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.033.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.590999, -0.245287 -0.291395) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.82200 -0.16604 -0.91298 +Nuclear contribution : -1.24655 0.56671 0.67182 + ----------------------------------------- +Total Dipole Moment : -0.42455 0.40067 -0.24116 + ----------------------------------------- +Magnitude (a.u.) : 0.63161 +Magnitude (Debye) : 1.60543 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.710753 0.399827 0.360324 +Rotational constants in MHz : 81266.319429 11986.514187 10802.236342 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.059367 0.062113 0.625741 +x,y,z [Debye]: 0.150899 0.157880 1.590507 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.590999, -0.245287 -0.291395) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.98101 -0.10508 -0.94036 +Nuclear contribution : -1.24655 0.56671 0.67182 + ----------------------------------------- +Total Dipole Moment : -0.26555 0.46163 -0.26854 + ----------------------------------------- +Magnitude (a.u.) : 0.59643 +Magnitude (Debye) : 1.51601 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.710753 0.399827 0.360324 +Rotational constants in MHz : 81266.319429 11986.514187 10802.236342 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.081487 0.146194 0.572468 +x,y,z [Debye]: -0.207124 0.371596 1.455097 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 34 * + * * + * Dihedral ( 2, 1, 0, 3) : 90.00000000 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0385364455 RMS(Int)= 0.0000625079 + Iter 1: RMS(Cart)= 0.0000168686 RMS(Int)= 0.0000000756 + Iter 2: RMS(Cart)= 0.0000000204 RMS(Int)= 0.0000000117 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.5043 0.000000 + 2. B(O 2,N 1) 1.1675 0.000000 + 3. B(H 3,O 0) 0.9725 0.000000 + 4. A(N 1,O 0,H 3) 103.1889 0.000000 + 5. A(O 0,N 1,O 2) 111.1907 0.000000 + 6. D(O 2,N 1,O 0,H 3) 90.0000 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.383110 -0.231826 0.757039 + N 0.261247 -0.464572 -0.582236 + O 1.172749 0.247417 -0.741467 + H -1.050886 0.448981 0.566664 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.723972 -0.438087 1.430596 + 1 N 7.0000 0 14.007 0.493686 -0.877914 -1.100266 + 2 O 8.0000 0 15.999 2.216175 0.467549 -1.401170 + 3 H 1.0000 0 1.008 -1.985887 0.848451 1.070840 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.503783052853 0.00000000 0.00000000 + O 2 1 0 1.165683324312 111.29966187 0.00000000 + H 1 2 3 0.969900905627 103.30356844 81.81818178 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.841738134724 0.00000000 0.00000000 + O 2 1 0 2.202822241830 111.29966187 0.00000000 + H 1 2 3 1.832847088677 103.30356844 81.81818178 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.1 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2229 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2696 + la=0 lb=0: 549 shell pairs + la=1 lb=0: 535 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.257687755186 Eh + +SHARK setup successfully completed in 0.5 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.2576877552 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.871e-04 +Time for diagonalization ... 0.013 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.004 sec +Total time needed ... 0.018 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7001209244 0.000000000000 0.00152656 0.00005027 0.0185314 0.7000 + 1 -204.7009853088 -0.000864384464 0.00145651 0.00004631 0.0153618 0.7000 + ***Turning on DIIS*** + 2 -204.7017298950 -0.000744586137 0.00411268 0.00012775 0.0125085 0.0000 + 3 -204.7049054528 -0.003175557873 0.00197806 0.00005901 0.0048610 0.0000 + 4 -204.7034895104 0.001415942396 0.00093107 0.00003150 0.0018600 0.0000 + 5 -204.7052870856 -0.001797575150 0.00093245 0.00002688 0.0011090 0.0000 + 6 -204.7045289577 0.000758127901 0.00091985 0.00003210 0.0008074 0.0000 + 7 -204.7040793213 0.000449636419 0.00048819 0.00001604 0.0003538 0.0000 + 8 -204.7049184411 -0.000839119855 0.00025942 0.00000926 0.0002032 0.0000 + 9 -204.7044639073 0.000454533798 0.00018308 0.00000606 0.0001268 0.0000 + 10 -204.7045590110 -0.000095103717 0.00007381 0.00000261 0.0000634 0.0000 + 11 -204.7047137280 -0.000154717012 0.00003710 0.00000101 0.0000301 0.0000 + 12 -204.7046104734 0.000103254640 0.00000910 0.00000028 0.0000103 0.0000 + 13 -204.7046352397 -0.000024766303 0.00000273 0.00000010 0.0000042 0.0000 + 14 -204.7046282315 0.000007008173 0.00000120 0.00000005 0.0000029 0.0000 + 15 -204.7046287500 -0.000000518489 0.00000122 0.00000003 0.0000025 0.0000 + 16 -204.7046310941 -0.000002344043 0.00000091 0.00000003 0.0000012 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 17 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70462981 Eh -5570.29617 eV + +Components: +Nuclear Repulsion : 68.25768776 Eh 1857.38611 eV +Electronic Energy : -272.96231756 Eh -7427.68228 eV +One Electron Energy: -416.22841258 Eh -11326.15092 eV +Two Electron Energy: 143.26609502 Eh 3898.46864 eV + +Virial components: +Potential Energy : -408.91592934 Eh -11127.16813 eV +Kinetic Energy : 204.21129954 Eh 5556.87197 eV +Virial Ratio : 2.00241578 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.2875e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.3283e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.8251e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.0709e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.692443 -563.0700 + 1 1.0000 -20.616841 -561.0128 + 2 1.0000 -15.805630 -430.0931 + 3 1.0000 -1.615845 -43.9694 + 4 1.0000 -1.370931 -37.3049 + 5 1.0000 -0.955482 -26.0000 + 6 1.0000 -0.767031 -20.8720 + 7 1.0000 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0.0000 0.030746 0.8366 + 13 0.0000 0.065847 1.7918 + 14 0.0000 0.091747 2.4965 + 15 0.0000 0.103376 2.8130 + 16 0.0000 0.113138 3.0786 + 17 0.0000 0.155312 4.2263 + 18 0.0000 0.157090 4.2746 + 19 0.0000 0.174244 4.7414 + 20 0.0000 0.180136 4.9018 + 21 0.0000 0.189770 5.1639 + 22 0.0000 0.200912 5.4671 + 23 0.0000 0.235828 6.4172 + 24 0.0000 0.268848 7.3157 + 25 0.0000 0.292841 7.9686 + 26 0.0000 0.299087 8.1386 + 27 0.0000 0.331451 9.0192 + 28 0.0000 0.332209 9.0399 + 29 0.0000 0.352165 9.5829 + 30 0.0000 0.424279 11.5452 + 31 0.0000 0.505432 13.7535 + 32 0.0000 0.528897 14.3920 + 33 0.0000 0.543980 14.8025 + 34 0.0000 0.569467 15.4960 + 35 0.0000 0.599782 16.3209 + 36 0.0000 0.629841 17.1388 + 37 0.0000 0.646567 17.5940 + 38 0.0000 0.706690 19.2300 + 39 0.0000 0.717387 19.5211 + 40 0.0000 0.738459 20.0945 + 41 0.0000 0.756661 20.5898 + 42 0.0000 0.760724 20.7004 + 43 0.0000 0.790114 21.5001 + 44 0.0000 0.808657 22.0047 + 45 0.0000 0.814854 22.1733 + 46 0.0000 0.862604 23.4726 + 47 0.0000 0.868548 23.6344 + 48 0.0000 0.892559 24.2878 + 49 0.0000 0.945361 25.7246 + 50 0.0000 0.960191 26.1281 + 51 0.0000 0.980247 26.6739 + 52 0.0000 0.993064 27.0226 + 53 0.0000 1.028235 27.9797 + 54 0.0000 1.044609 28.4253 + 55 0.0000 1.105727 30.0884 + 56 0.0000 1.151242 31.3269 + 57 0.0000 1.225639 33.3513 + 58 0.0000 1.254014 34.1235 + 59 0.0000 1.260791 34.3079 + 60 0.0000 1.313244 35.7352 + 61 0.0000 1.408983 38.3404 + 62 0.0000 1.450856 39.4798 + 63 0.0000 1.518833 41.3295 + 64 0.0000 1.527247 41.5585 + 65 0.0000 1.568553 42.6825 + 66 0.0000 1.585832 43.1527 + 67 0.0000 1.631338 44.3910 + 68 0.0000 1.648511 44.8583 + 69 0.0000 1.716772 46.7157 + 70 0.0000 1.770064 48.1659 + 71 0.0000 1.784836 48.5679 + 72 0.0000 1.893160 51.5155 + 73 0.0000 1.923197 52.3329 + 74 0.0000 1.984535 54.0019 + 75 0.0000 2.014683 54.8223 + 76 0.0000 2.046172 55.6792 + 77 0.0000 2.090220 56.8778 + 78 0.0000 2.137420 58.1621 + 79 0.0000 2.202585 59.9354 + 80 0.0000 2.261630 61.5421 + 81 0.0000 2.291990 62.3682 + 82 0.0000 2.323701 63.2311 + 83 0.0000 2.357471 64.1501 + 84 0.0000 2.404694 65.4350 + 85 0.0000 2.452111 66.7253 + 86 0.0000 2.462826 67.0169 + 87 0.0000 2.477753 67.4231 + 88 0.0000 2.506316 68.2003 + 89 0.0000 2.567119 69.8549 + 90 0.0000 2.570441 69.9453 + 91 0.0000 2.598404 70.7062 + 92 0.0000 2.669570 72.6427 + 93 0.0000 2.730713 74.3065 + 94 0.0000 2.744551 74.6830 + 95 0.0000 2.779631 75.6376 + 96 0.0000 2.847595 77.4870 + 97 0.0000 2.891513 78.6821 + 98 0.0000 2.955903 80.4342 + 99 0.0000 2.986134 81.2568 + 100 0.0000 3.058235 83.2188 + 101 0.0000 3.165777 86.1452 + 102 0.0000 3.222275 87.6826 + 103 0.0000 3.486311 94.8674 + 104 0.0000 3.722490 101.2941 + 105 0.0000 3.808828 103.6435 + 106 0.0000 4.048215 110.1575 + 107 0.0000 4.171161 113.5031 + 108 0.0000 4.188682 113.9798 + 109 0.0000 4.287417 116.6666 + 110 0.0000 4.357170 118.5646 + 111 0.0000 4.391766 119.5060 + 112 0.0000 4.517751 122.9342 + 113 0.0000 4.602583 125.2427 + 114 0.0000 4.661856 126.8556 + 115 0.0000 4.714470 128.2873 + 116 0.0000 4.830813 131.4531 + 117 0.0000 4.900531 133.3502 + 118 0.0000 4.931497 134.1929 + 119 0.0000 4.947472 134.6276 + 120 0.0000 5.049353 137.3999 + 121 0.0000 5.101685 138.8239 + 122 0.0000 5.180826 140.9774 + 123 0.0000 5.194494 141.3494 + 124 0.0000 5.220730 142.0633 + 125 0.0000 5.314871 144.6250 + 126 0.0000 5.378047 146.3441 + 127 0.0000 5.483388 149.2106 + 128 0.0000 5.552633 151.0948 + 129 0.0000 5.701166 155.1366 + 130 0.0000 5.734234 156.0364 + 131 0.0000 5.931087 161.3931 + 132 0.0000 6.175609 168.0469 + 133 0.0000 6.420422 174.7086 + 134 0.0000 6.480884 176.3538 + 135 0.0000 6.503234 176.9620 + 136 0.0000 6.698004 182.2620 + 137 0.0000 6.725175 183.0013 + 138 0.0000 6.768921 184.1917 + 139 0.0000 6.814045 185.4196 + 140 0.0000 6.821700 185.6279 + 141 0.0000 7.068286 192.3378 + 142 0.0000 7.098803 193.1683 + 143 0.0000 7.116896 193.6606 + 144 0.0000 7.191327 195.6860 + 145 0.0000 7.254620 197.4082 + 146 0.0000 7.278790 198.0659 + 147 0.0000 7.336198 199.6281 + 148 0.0000 7.381819 200.8695 + 149 0.0000 7.450547 202.7397 + 150 0.0000 7.460062 202.9986 + 151 0.0000 7.560245 205.7247 + 152 0.0000 7.574388 206.1096 + 153 0.0000 7.621902 207.4025 + 154 0.0000 7.716200 209.9685 + 155 0.0000 7.892142 214.7561 + 156 0.0000 7.921703 215.5605 + 157 0.0000 8.392291 228.3659 + 158 0.0000 14.038063 381.9951 + 159 0.0000 14.814326 403.1183 + 160 0.0000 16.001161 435.4137 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.377792 0.000000 + 1 N : 0.353374 0.000000 + 2 O : -0.226264 0.000000 + 3 H : 0.250682 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.864122 s : 3.864122 + pz : 1.304889 p : 4.483915 + px : 1.553193 + py : 1.625833 + dz2 : 0.010156 d : 0.025478 + dxz : 0.007745 + dyz : 0.004530 + dx2y2 : 0.001136 + dxy : 0.001911 + f0 : 0.001451 f : 0.004277 + f+1 : 0.000834 + f-1 : 0.000741 + f+2 : 0.000216 + f-2 : 0.000321 + f+3 : 0.000291 + f-3 : 0.000422 + 1 N s : 3.821570 s : 3.821570 + pz : 0.834772 p : 2.657348 + px : 0.846885 + py : 0.975692 + dz2 : 0.027151 d : 0.136978 + dxz : 0.039121 + dyz : 0.019061 + dx2y2 : 0.033131 + dxy : 0.018514 + f0 : 0.008184 f : 0.030729 + f+1 : 0.003171 + f-1 : 0.005300 + f+2 : 0.002290 + f-2 : 0.005345 + f+3 : 0.003790 + f-3 : 0.002648 + 2 O s : 3.875930 s : 3.875930 + pz : 1.743818 p : 4.280225 + px : 1.209045 + py : 1.327363 + dz2 : 0.004571 d : 0.062629 + dxz : 0.009452 + dyz : 0.009322 + dx2y2 : 0.027467 + dxy : 0.011817 + f0 : 0.001182 f : 0.007479 + f+1 : 0.000660 + f-1 : 0.000595 + f+2 : -0.000033 + f-2 : 0.001294 + f+3 : 0.002434 + f-3 : 0.001347 + 3 H s : 0.642031 s : 0.642031 + pz : 0.020663 p : 0.087239 + px : 0.034849 + py : 0.031727 + dz2 : 0.001470 d : 0.020048 + dxz : 0.003756 + dyz : 0.004132 + dx2y2 : 0.010186 + dxy : 0.000504 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.570663 0.000000 + 1 N : -0.232771 0.000000 + 2 O : 0.248281 0.000000 + 3 H : -0.586173 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.138125 s : 3.138125 + pz : 1.222998 p : 3.962059 + px : 1.334827 + py : 1.404234 + dz2 : 0.086338 d : 0.255103 + dxz : 0.068790 + dyz : 0.050543 + dx2y2 : 0.014008 + dxy : 0.035424 + f0 : 0.018070 f : 0.074050 + f+1 : 0.016673 + f-1 : 0.014949 + f+2 : 0.009360 + f-2 : 0.009145 + f+3 : 0.003418 + f-3 : 0.002434 + 1 N s : 3.039393 s : 3.039393 + pz : 0.868849 p : 2.839315 + px : 0.956138 + py : 1.014328 + dz2 : 0.199221 d : 0.917331 + dxz : 0.252732 + dyz : 0.129266 + dx2y2 : 0.146396 + dxy : 0.189716 + f0 : 0.098563 f : 0.436732 + f+1 : 0.056754 + f-1 : 0.055544 + f+2 : 0.028221 + f-2 : 0.079594 + f+3 : 0.063343 + f-3 : 0.054713 + 2 O s : 3.316681 s : 3.316681 + pz : 1.431477 p : 3.987566 + px : 1.271763 + py : 1.284326 + dz2 : 0.050288 d : 0.330094 + dxz : 0.075452 + dyz : 0.029146 + dx2y2 : 0.059427 + dxy : 0.115781 + f0 : 0.012995 f : 0.117379 + f+1 : 0.015103 + f-1 : 0.011570 + f+2 : 0.006333 + f-2 : 0.020042 + f+3 : 0.027825 + f-3 : 0.023511 + 3 H s : 0.626431 s : 0.626431 + pz : 0.146402 p : 0.571190 + px : 0.206022 + py : 0.218766 + dz2 : 0.031946 d : 0.388552 + dxz : 0.076370 + dyz : 0.066336 + dx2y2 : 0.121226 + dxy : 0.092674 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3778 8.0000 -0.3778 1.8176 1.8176 0.0000 + 1 N 6.6466 7.0000 0.3534 2.5978 2.5978 0.0000 + 2 O 8.2263 8.0000 -0.2263 1.8132 1.8132 0.0000 + 3 H 0.7493 1.0000 0.2507 0.9922 0.9922 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8057 B( 0-O , 3-H ) : 0.9557 B( 1-N , 2-O ) : 1.7563 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 13 sec + +Total time .... 13.243 sec +Sum of individual times .... 12.479 sec ( 94.2%) + +Fock matrix formation .... 6.692 sec ( 50.5%) +Diagonalization .... 1.831 sec ( 13.8%) +Density matrix formation .... 0.052 sec ( 0.4%) +Population analysis .... 0.177 sec ( 1.3%) +Initial guess .... 0.021 sec ( 0.2%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.012 sec ( 0.1%) +DIIS solution .... 3.707 sec ( 28.0%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.662 sec +Reference energy ... -204.704630351 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 12.222 sec +AO-integral generation ... 0.376 sec +Half transformation ... 0.184 sec +K-integral sorting ... 9.573 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.068 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.088 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.089 s ( 0.000 ms/b) + 151164 b 0 skpd 0.117 s ( 0.001 ms/b) +: : 159120 b 0 skpd 0.054 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.095 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.079 s ( 0.001 ms/b) + 87516 b 0 skpd 0.063 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.118 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.062 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 1.064 sec +AO-integral generation ... 0.734 sec +Half transformation ... 0.104 sec +J-integral sorting ... 0.158 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.408 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.484 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090051338 +EMP2(bb)= -0.090051338 +EMP2(ab)= -0.517743064 + +Initial guess performed in 0.203 sec +E(0) ... -204.704630351 +E(MP2) ... -0.697845741 +Initial E(tot) ... -205.402476092 + ... 0.189965940 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.402476092 -0.697845741 -0.000000000 0.018870673 6.60 0.000002062 + *** Turning on DIIS *** + 1 -205.374007194 -0.669376842 0.028468899 0.011055768 6.61 0.055539280 + 2 -205.393607126 -0.688976775 -0.019599933 0.003726389 6.73 0.058217271 + 3 -205.397445490 -0.692815139 -0.003838364 0.002128491 6.63 0.071078149 + 4 -205.398986733 -0.694356382 -0.001541243 0.000969158 5.72 0.076732368 + 5 -205.399467985 -0.694837634 -0.000481252 0.000405400 6.64 0.080866718 + 6 -205.399541223 -0.694910872 -0.000073237 0.000307129 5.98 0.082678199 + 7 -205.399569293 -0.694938942 -0.000028071 0.000234465 5.89 0.083438573 + 8 -205.399575060 -0.694944709 -0.000005766 0.000173097 8.13 0.083759941 + 9 -205.399572072 -0.694941721 0.000002988 0.000119231 6.62 0.083891894 + 10 -205.399576358 -0.694946007 -0.000004286 0.000061101 6.07 0.083973199 + 11 -205.399572826 -0.694942475 0.000003532 0.000022543 7.74 0.084006918 + 12 -205.399575469 -0.694945118 -0.000002643 0.000011502 6.88 0.084025492 + 13 -205.399575688 -0.694945337 -0.000000218 0.000003928 8.34 0.084028567 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.704630351 +E(CORR) ... -0.694945337 +E(TOT) ... -205.399575688 +Singles norm **1/2 ... 0.084028567 ( 0.042014284, 0.042014284) +T1 diagnostic ... 0.019805723 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.062980 + 8a-> 13a 8b-> 13b 0.054781 + 8a-> 13a 9b-> 13b 0.047529 + 9a-> 13a 8b-> 13b 0.047529 + 5a-> 13a 5b-> 13b 0.030224 + 11a-> 25a 11b-> 25b 0.029258 + 11a-> 13a 11b-> 13b 0.028231 + 8a-> 13a -1a-> -1a 0.027561 + 8b-> 13b -1b-> -1b 0.027561 + 11a-> 25a 11b-> 24b 0.025464 + 11a-> 24a 11b-> 25b 0.025464 + 11a-> 24a 11b-> 24b 0.024667 + 9a-> 13a 9b-> 22b 0.024072 + 9a-> 22a 9b-> 13b 0.024072 + 11b-> 25b -1b-> -1b 0.021355 + 11a-> 25a -1a-> -1a 0.021355 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034544751 + alpha-alpha-alpha ... -0.000860163 ( 2.5%) + alpha-alpha-beta ... -0.016412213 ( 47.5%) + alpha-beta -beta ... -0.016412213 ( 47.5%) + beta -beta -beta ... -0.000860163 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034544751 + +Final correlation energy ... -0.729490088 +E(CCSD) ... -205.399575688 +E(CCSD(T)) ... -205.434120439 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210490791 sqrt= 1.100223064 +W(HF) = 0.826111200 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.320894 -0.000000 + 1 N : 0.181971 0.000000 + 2 O : -0.099467 -0.000000 + 3 H : 0.238389 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.841797 s : 3.841797 + pz : 1.284915 p : 4.414757 + px : 1.535659 + py : 1.594183 + dz2 : 0.014972 d : 0.056336 + dxz : 0.012929 + dyz : 0.011630 + dx2y2 : 0.008463 + dxy : 0.008343 + f0 : 0.001838 f : 0.008003 + f+1 : 0.001128 + f-1 : 0.001282 + f+2 : 0.000804 + f-2 : 0.000948 + f+3 : 0.000931 + f-3 : 0.001072 + 1 N s : 3.876254 s : 3.876254 + pz : 0.880714 p : 2.745761 + px : 0.877892 + py : 0.987156 + dz2 : 0.034429 d : 0.166333 + dxz : 0.047497 + dyz : 0.026628 + dx2y2 : 0.034284 + dxy : 0.023495 + f0 : 0.007755 f : 0.029680 + f+1 : 0.002972 + f-1 : 0.005388 + f+2 : 0.002782 + f-2 : 0.005104 + f+3 : 0.003265 + f-3 : 0.002414 + 2 O s : 3.862978 s : 3.862978 + pz : 1.659012 p : 4.143193 + px : 1.188385 + py : 1.295797 + dz2 : 0.009937 d : 0.083462 + dxz : 0.016259 + dyz : 0.014767 + dx2y2 : 0.027794 + dxy : 0.014706 + f0 : 0.001620 f : 0.009833 + f+1 : 0.001125 + f-1 : 0.001045 + f+2 : 0.000595 + f-2 : 0.001638 + f+3 : 0.002292 + f-3 : 0.001517 + 3 H s : 0.649621 s : 0.649621 + pz : 0.024318 p : 0.094832 + px : 0.036049 + py : 0.034465 + dz2 : 0.001311 d : 0.017158 + dxz : 0.003395 + dyz : 0.003571 + dx2y2 : 0.008944 + dxy : -0.000064 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.575168 -0.000000 + 1 N : -0.276106 0.000000 + 2 O : 0.292185 -0.000000 + 3 H : -0.591247 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.142217 s : 3.142217 + pz : 1.216071 p : 3.915721 + px : 1.322137 + py : 1.377512 + dz2 : 0.092243 d : 0.285941 + dxz : 0.075406 + dyz : 0.055818 + dx2y2 : 0.019932 + dxy : 0.042542 + f0 : 0.019486 f : 0.080953 + f+1 : 0.018519 + f-1 : 0.015388 + f+2 : 0.009982 + f-2 : 0.010135 + f+3 : 0.004171 + f-3 : 0.003272 + 1 N s : 3.044354 s : 3.044354 + pz : 0.889652 p : 2.879333 + px : 0.972340 + py : 1.017341 + dz2 : 0.205648 d : 0.925022 + dxz : 0.253430 + dyz : 0.127864 + dx2y2 : 0.142012 + dxy : 0.196069 + f0 : 0.095253 f : 0.427396 + f+1 : 0.057454 + f-1 : 0.054732 + f+2 : 0.027609 + f-2 : 0.075598 + f+3 : 0.061826 + f-3 : 0.054925 + 2 O s : 3.319544 s : 3.319544 + pz : 1.377600 p : 3.904693 + px : 1.260228 + py : 1.266865 + dz2 : 0.056101 d : 0.357879 + dxz : 0.078822 + dyz : 0.034794 + dx2y2 : 0.067588 + dxy : 0.120575 + f0 : 0.013872 f : 0.125699 + f+1 : 0.015856 + f-1 : 0.011901 + f+2 : 0.006851 + f-2 : 0.021242 + f+3 : 0.030802 + f-3 : 0.025174 + 3 H s : 0.626664 s : 0.626664 + pz : 0.147025 p : 0.586018 + px : 0.212197 + py : 0.226797 + dz2 : 0.032727 d : 0.378565 + dxz : 0.073525 + dyz : 0.064259 + dx2y2 : 0.116179 + dxy : 0.091875 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3209 8.0000 -0.3209 2.1579 1.6948 0.4631 + 1 N 6.8180 7.0000 0.1820 2.8594 2.3632 0.4962 + 2 O 8.0995 8.0000 -0.0995 2.1976 1.6981 0.4995 + 3 H 0.7616 1.0000 0.2384 1.0139 0.9393 0.0747 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7148 B( 0-O , 3-H ) : 0.8937 B( 1-N , 2-O ) : 1.6073 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 130.506 sec + +Fock Matrix Formation ... 0.662 sec ( 0.5%) +Initial Guess ... 0.203 sec ( 0.2%) +DIIS Solver ... 5.413 sec ( 4.1%) +State Vector Update ... 0.238 sec ( 0.2%) +Sigma-vector construction ... 88.943 sec ( 68.2%) + <0|H|D> ... 0.009 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.052 sec ( 0.1% of sigma) + (0-ext) ... 0.182 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.064 sec ( 0.1% of sigma) + (2-ext) ... 2.286 sec ( 2.6% of sigma) + (4-ext) ... 50.736 sec ( 57.0% of sigma) + ... 5.237 sec ( 5.9% of sigma) + ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.023 sec ( 0.0% of sigma) + (1-ext) ... 0.223 sec ( 0.3% of sigma) + Fock-dressing ... 5.892 sec ( 6.6% of sigma) + (ik|jl)-dressing ... 0.193 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 19.711 sec ( 22.2% of sigma) + Pair energies ... 0.019 sec ( 0.0% of sigma) +Total Time for computing (T) ... 18.375 sec ( 14.1% of ALL) + I/O of integral and amplitudes ... 2.991 sec ( 16.3% of (T)) + External N**7 contributions ... 9.971 sec ( 54.3% of (T)) + Internal N**7 contributions ... 1.334 sec ( 7.3% of (T)) + N**6 triples energy contributions ... 3.868 sec ( 21.1% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.434120439029 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.000385361 -0.002781955 -0.000239306 + 2 N : -0.001991715 -0.002572887 0.001895436 + 3 O : 0.002795039 0.002801489 -0.001629338 + 4 H : -0.001188685 0.002553353 -0.000026791 + +Norm of the cartesian gradient ... 0.006955072 +RMS gradient ... 0.002007756 +MAX gradient ... 0.002801489 + +------- +TIMINGS +------- + +Total numerical gradient time ... 921.654 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: -552.23 cm**-1 ***imaginary mode*** + 7: 540.16 cm**-1 + 8: 780.38 cm**-1 + 9: 1113.80 cm**-1 + 10: 1697.37 cm**-1 + 11: 3719.21 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 -0.053161 -0.452438 -0.115358 -0.010210 0.023186 -0.043512 + 1 -0.041074 -0.073517 -0.219330 0.033691 -0.023884 0.043562 + 2 -0.022551 0.531103 -0.217751 -0.056725 -0.071723 -0.011387 + 3 0.047389 0.282702 -0.097156 0.034765 0.555262 -0.000539 + 4 -0.051720 0.105257 0.331415 -0.037988 0.495684 -0.000227 + 5 0.036087 -0.244423 0.657509 -0.008517 0.002445 -0.000051 + 6 -0.029922 0.227189 0.216535 0.000086 -0.512300 0.000497 + 7 0.040997 -0.016055 -0.054711 0.000121 -0.409286 0.000506 + 8 -0.020256 -0.333488 -0.367599 0.004784 0.072469 -0.000328 + 9 0.660177 -0.353216 -0.255827 -0.322398 0.047398 0.690227 + 10 0.719903 -0.040947 -0.255709 -0.008791 -0.012674 -0.696295 + 11 0.177978 0.259920 0.154055 0.942750 -0.045810 0.186651 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 7: 540.16 0.025574 129.24 0.014775 ( 0.083336 0.007533 -0.088164) + 8: 780.38 0.026890 135.89 0.010753 (-0.061848 0.008605 0.082788) + 9: 1113.80 0.010264 51.87 0.002876 (-0.029014 0.015308 0.042421) + 10: 1697.37 0.033788 170.75 0.006212 ( 0.058310 0.013524 -0.051274) + 11: 3719.21 0.011586 58.55 0.000972 ( 0.025295 -0.016374 -0.008013) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 7 +The total number of vibrations considered is 5 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 540.16 E(vib) ... 0.12 +freq. 780.38 E(vib) ... 0.05 +freq. 1113.80 E(vib) ... 0.01 +freq. 1697.37 E(vib) ... 0.00 +freq. 3719.21 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.43412044 Eh +Zero point energy ... 0.01788573 Eh 11.22 kcal/mol +Thermal vibrational correction ... 0.00030610 Eh 0.19 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.41309607 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00313864 Eh 1.97 kcal/mol +Non-thermal (ZPE) correction 0.01788573 Eh 11.22 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02102436 Eh 13.19 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.41309607 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.41215186 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.724048 0.397881 0.359466 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00040565 Eh 0.25 kcal/mol +Rotational entropy ... 0.00995581 Eh 6.25 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02816378 Eh 17.67 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00995581 Eh 6.25 kcal/mol| +| sn= 2 | S(rot)= 0.00930136 Eh 5.84 kcal/mol| +| sn= 3 | S(rot)= 0.00891852 Eh 5.60 kcal/mol| +| sn= 4 | S(rot)= 0.00864690 Eh 5.43 kcal/mol| +| sn= 5 | S(rot)= 0.00843621 Eh 5.29 kcal/mol| +| sn= 6 | S(rot)= 0.00826407 Eh 5.19 kcal/mol| +| sn= 7 | S(rot)= 0.00811852 Eh 5.09 kcal/mol| +| sn= 8 | S(rot)= 0.00799244 Eh 5.02 kcal/mol| +| sn= 9 | S(rot)= 0.00788123 Eh 4.95 kcal/mol| +| sn=10 | S(rot)= 0.00778175 Eh 4.88 kcal/mol| +| sn=11 | S(rot)= 0.00769176 Eh 4.83 kcal/mol| +| sn=12 | S(rot)= 0.00760961 Eh 4.78 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.41215186 Eh +Total entropy correction ... -0.02816378 Eh -17.67 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44031564 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00619521 Eh -3.89 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.434120438 Eh +Current gradient norm .... 0.006955068 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + -0.031856326 0.094068197 0.158604337 0.466568432 0.497592668 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999936172 +Lowest eigenvalues of augmented Hessian: + -0.000043990 0.093945448 0.158518974 0.466096942 0.497604668 +Length of the computed step .... 0.011299030 +The final length of the internal step .... 0.011299030 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0046128095 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0028046751 RMS(Int)= 0.0046105867 + Iter 1: RMS(Cart)= 0.0000056572 RMS(Int)= 0.0000090074 + Iter 2: RMS(Cart)= 0.0000000208 RMS(Int)= 0.0000000297 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000049 RMS(Int)= 0.0000000032 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0021204628 0.0001000000 NO + MAX gradient 0.0041129187 0.0003000000 NO + RMS step 0.0046128095 0.0020000000 NO + MAX step 0.0063761214 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0034 Max(Angles) 0.24 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.5043 0.000072 0.0034 1.5077 + 2. B(O 2,N 1) 1.1675 0.004113 -0.0029 1.1646 + 3. B(H 3,O 0) 0.9725 0.002609 -0.0028 0.9697 + 4. A(N 1,O 0,H 3) 103.19 0.000539 -0.24 102.95 + 5. A(O 0,N 1,O 2) 111.19 0.001720 -0.20 110.99 + 6. D(O 2,N 1,O 0,H 3) 90.00 -0.001827 -0.00 90.00 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.383559 -0.230912 0.758563 + N 0.261607 -0.464416 -0.583981 + O 1.170238 0.247268 -0.739642 + H -1.048284 0.448060 0.565060 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.724822 -0.436361 1.433476 + 1 N 7.0000 0 14.007 0.494365 -0.877619 -1.103564 + 2 O 8.0000 0 15.999 2.211429 0.467268 -1.397721 + 3 H 1.0000 0 1.008 -1.980970 0.846711 1.067809 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.507709284055 0.00000000 0.00000000 + O 2 1 0 1.164617674545 110.99159298 0.00000000 + H 1 2 3 0.969693889972 102.94901503 89.99999985 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.849157636435 0.00000000 0.00000000 + O 2 1 0 2.200808455614 110.99159298 0.00000000 + H 1 2 3 1.832455885784 102.94901503 89.99999985 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2229 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2696 + la=0 lb=0: 549 shell pairs + la=1 lb=0: 535 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.308171367524 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.867e-04 +Time for diagonalization ... 0.004 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.007 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7048959174 0.000000000000 0.00017032 0.00000509 0.0009836 0.7000 + 1 -204.7049021367 -0.000006219273 0.00014764 0.00000422 0.0007882 0.7000 + ***Turning on DIIS*** + 2 -204.7049071454 -0.000005008762 0.00038407 0.00001104 0.0006161 0.0000 + 3 -204.7044332561 0.000473889299 0.00009263 0.00000395 0.0001682 0.0000 + 4 -204.7049363845 -0.000503128361 0.00002747 0.00000139 0.0000470 0.0000 + 5 -204.7051044636 -0.000168079090 0.00001405 0.00000065 0.0000448 0.0000 + 6 -204.7048401136 0.000264350004 0.00000834 0.00000041 0.0000132 0.0000 + 7 -204.7049500144 -0.000109900812 0.00000532 0.00000026 0.0000076 0.0000 + 8 -204.7049278338 0.000022180525 0.00000485 0.00000018 0.0000054 0.0000 + 9 -204.7049120000 0.000015833833 0.00000355 0.00000012 0.0000033 0.0000 + 10 -204.7049303623 -0.000018362330 0.00000275 0.00000010 0.0000025 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + +Total Energy : -204.70492081 Eh -5570.30408 eV + Last Energy change ... 9.5571e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.2145e-06 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 2 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.270 sec +Reference energy ... -204.704922862 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 7.264 sec +AO-integral generation ... 0.176 sec +Half transformation ... 0.099 sec +K-integral sorting ... 6.062 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.041 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.035 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.036 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.044 s ( 0.000 ms/b) + 159120 b 0 skpd 0.023 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.045 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.041 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.030 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.048 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.030 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.450 sec +AO-integral generation ... 0.321 sec +Half transformation ... 0.053 sec +J-integral sorting ... 0.057 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.171 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.281 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090016118 +EMP2(bb)= -0.090016118 +EMP2(ab)= -0.517550405 + +Initial guess performed in 0.154 sec +E(0) ... -204.704922862 +E(MP2) ... -0.697582641 +Initial E(tot) ... -205.402505503 + ... 0.189723762 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.402505503 -0.697582641 -0.000000000 0.018766396 4.62 0.000001119 + *** Turning on DIIS *** + 1 -205.374138291 -0.669215429 0.028367211 0.010815397 4.00 0.055443349 + 2 -205.393694424 -0.688771563 -0.019556133 0.003689310 4.84 0.058116496 + 3 -205.397521738 -0.692598876 -0.003827314 0.002076131 4.78 0.070935284 + 4 -205.399055624 -0.694132762 -0.001533886 0.000958543 3.99 0.076564209 + 5 -205.399532823 -0.694609961 -0.000477199 0.000403911 3.51 0.080676874 + 6 -205.399605622 -0.694682760 -0.000072799 0.000305728 3.43 0.082487239 + 7 -205.399633674 -0.694710812 -0.000028052 0.000232614 3.58 0.083252087 + 8 -205.399639427 -0.694716565 -0.000005752 0.000171484 3.57 0.083574778 + 9 -205.399636429 -0.694713567 0.000002998 0.000118090 3.58 0.083705290 + 10 -205.399640655 -0.694717793 -0.000004226 0.000060485 3.90 0.083785519 + 11 -205.399637139 -0.694714278 0.000003515 0.000022266 4.40 0.083818471 + 12 -205.399639789 -0.694716927 -0.000002650 0.000011248 4.82 0.083836695 + 13 -205.399640002 -0.694717140 -0.000000213 0.000003785 4.79 0.083839719 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.704922862 +E(CORR) ... -0.694717140 +E(TOT) ... -205.399640002 +Singles norm **1/2 ... 0.083839719 ( 0.041919859, 0.041919859) +T1 diagnostic ... 0.019761211 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.061305 + 8a-> 13a 8b-> 13b 0.055538 + 9a-> 13a 8b-> 13b 0.047227 + 8a-> 13a 9b-> 13b 0.047227 + 5a-> 13a 5b-> 13b 0.030234 + 11a-> 25a 11b-> 25b 0.028139 + 11a-> 13a 11b-> 13b 0.027915 + 8a-> 13a -1a-> -1a 0.027250 + 8b-> 13b -1b-> -1b 0.027250 + 11a-> 24a 11b-> 24b 0.026292 + 11a-> 25a 11b-> 24b 0.025805 + 11a-> 24a 11b-> 25b 0.025805 + 9a-> 22a 9b-> 13b 0.023621 + 9a-> 13a 9b-> 22b 0.023621 + 11b-> 24b -1b-> -1b 0.020659 + 11a-> 24a -1a-> -1a 0.020659 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034502389 + alpha-alpha-alpha ... -0.000859098 ( 2.5%) + alpha-alpha-beta ... -0.016392096 ( 47.5%) + alpha-beta -beta ... -0.016392096 ( 47.5%) + beta -beta -beta ... -0.000859098 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034502389 + +Final correlation energy ... -0.729219529 +E(CCSD) ... -205.399640002 +E(CCSD(T)) ... -205.434142391 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210170205 sqrt= 1.100077363 +W(HF) = 0.826330045 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 75.861 sec + +Fock Matrix Formation ... 0.270 sec ( 0.4%) +Initial Guess ... 0.154 sec ( 0.2%) +DIIS Solver ... 3.185 sec ( 4.2%) +State Vector Update ... 0.147 sec ( 0.2%) +Sigma-vector construction ... 54.489 sec ( 71.8%) + <0|H|D> ... 0.006 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.036 sec ( 0.1% of sigma) + (0-ext) ... 0.095 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.033 sec ( 0.1% of sigma) + (2-ext) ... 1.219 sec ( 2.2% of sigma) + (4-ext) ... 32.112 sec ( 58.9% of sigma) + ... 2.207 sec ( 4.0% of sigma) + ... 0.004 sec ( 0.0% of sigma) + (1-ext) ... 0.011 sec ( 0.0% of sigma) + (1-ext) ... 0.155 sec ( 0.3% of sigma) + Fock-dressing ... 2.655 sec ( 4.9% of sigma) + (ik|jl)-dressing ... 0.118 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 12.723 sec ( 23.4% of sigma) + Pair energies ... 0.010 sec ( 0.0% of sigma) +Total Time for computing (T) ... 8.278 sec ( 10.9% of ALL) + I/O of integral and amplitudes ... 0.894 sec ( 10.8% of (T)) + External N**7 contributions ... 4.766 sec ( 57.6% of (T)) + Internal N**7 contributions ... 0.379 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.896 sec ( 22.9% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.434142390510 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.001007713 -0.000698354 -0.000380472 + 2 N : 0.000884985 -0.000669688 0.000542042 + 3 O : -0.000623429 0.000606405 -0.000386180 + 4 H : 0.000746157 0.000761637 0.000224610 + +Norm of the cartesian gradient ... 0.002294831 +RMS gradient ... 0.000662461 +MAX gradient ... 0.001007713 + +------- +TIMINGS +------- + +Total numerical gradient time ... 496.558 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.434142391 Eh +Current gradient norm .... 0.002294831 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999987 +Lowest eigenvalues of augmented Hessian: + -0.000000008 0.093435899 0.158530936 0.464699292 0.499565197 +Length of the computed step .... 0.000162870 +The final length of the internal step .... 0.000162870 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0000664913 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0000344811 RMS(Int)= 0.0000664914 + Iter 1: RMS(Cart)= 0.0000000050 RMS(Int)= 0.0000000064 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000050 RMS(Int)= 0.0000000032 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000219523 0.0000050000 NO + RMS gradient 0.0000293410 0.0001000000 YES + MAX gradient 0.0000640553 0.0003000000 YES + RMS step 0.0000664913 0.0020000000 YES + MAX step 0.0001042216 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.5077 -0.000017 0.0001 1.5078 + 2. B(O 2,N 1) 1.1646 -0.000064 0.0000 1.1647 + 3. B(H 3,O 0) 0.9697 -0.000023 0.0000 0.9697 + 4. A(N 1,O 0,H 3) 102.95 0.000008 -0.00 102.94 + 5. A(O 0,N 1,O 2) 110.99 0.000013 -0.00 110.99 + 6. D(O 2,N 1,O 0,H 3) 90.00 -0.001948 0.00 90.00 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.383562 -0.230926 0.758606 + N 0.261595 -0.464432 -0.584004 + O 1.170247 0.247286 -0.739640 + H -1.048279 0.448072 0.565039 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.724826 -0.436387 1.433557 + 1 N 7.0000 0 14.007 0.494343 -0.877649 -1.103608 + 2 O 8.0000 0 15.999 2.211446 0.467303 -1.397718 + 3 H 1.0000 0 1.008 -1.980960 0.846733 1.067769 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.507764435739 0.00000000 0.00000000 + O 2 1 0 1.164651702095 110.98913083 0.00000000 + H 1 2 3 0.969719079259 102.94408058 89.99999994 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.849261858013 0.00000000 0.00000000 + O 2 1 0 2.200872758366 110.98913083 0.00000000 + H 1 2 3 1.832503486637 102.94408058 89.99999994 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2229 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2696 + la=0 lb=0: 549 shell pairs + la=1 lb=0: 535 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.306304946135 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.3063049461 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.867e-04 +Time for diagonalization ... 0.005 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.004 sec +Total time needed ... 0.009 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7049109467 0.000000000000 0.00000222 0.00000007 0.0000100 0.7000 + 1 -204.7049109479 -0.000000001190 0.00000154 0.00000006 0.0000073 0.7000 + ***Turning on DIIS*** + 2 -204.7049109491 -0.000000001205 0.00000385 0.00000014 0.0000053 0.0000 + 3 -204.7049166306 -0.000005681534 0.00000170 0.00000005 0.0000017 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 4 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70491177 Eh -5570.30384 eV + +Components: +Nuclear Repulsion : 68.30630495 Eh 1858.70905 eV +Electronic Energy : -273.01121672 Eh -7429.01289 eV +One Electron Energy: -416.31786543 Eh -11328.58505 eV +Two Electron Energy: 143.30664871 Eh 3899.57216 eV + +Virial components: +Potential Energy : -408.93164452 Eh -11127.59576 eV +Kinetic Energy : 204.22673275 Eh 5557.29193 eV +Virial Ratio : 2.00234141 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 4.8600e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.1379e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.9982e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.6948e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.693153 -563.0893 + 1 1.0000 -20.615497 -560.9762 + 2 1.0000 -15.805830 -430.0985 + 3 1.0000 -1.618794 -44.0496 + 4 1.0000 -1.370230 -37.2859 + 5 1.0000 -0.955365 -25.9968 + 6 1.0000 -0.767545 -20.8860 + 7 1.0000 -0.733168 -19.9505 + 8 1.0000 -0.699936 -19.0462 + 9 1.0000 -0.605610 -16.4795 + 10 1.0000 -0.528777 -14.3888 + 11 1.0000 -0.458372 -12.4729 + 12 0.0000 0.030942 0.8420 + 13 0.0000 0.066318 1.8046 + 14 0.0000 0.091592 2.4923 + 15 0.0000 0.103238 2.8092 + 16 0.0000 0.113144 3.0788 + 17 0.0000 0.155430 4.2295 + 18 0.0000 0.157323 4.2810 + 19 0.0000 0.174183 4.7398 + 20 0.0000 0.180069 4.8999 + 21 0.0000 0.189711 5.1623 + 22 0.0000 0.200851 5.4654 + 23 0.0000 0.235660 6.4126 + 24 0.0000 0.268336 7.3018 + 25 0.0000 0.292246 7.9524 + 26 0.0000 0.299494 8.1496 + 27 0.0000 0.331631 9.0241 + 28 0.0000 0.332134 9.0378 + 29 0.0000 0.352155 9.5826 + 30 0.0000 0.425163 11.5693 + 31 0.0000 0.505368 13.7518 + 32 0.0000 0.528680 14.3861 + 33 0.0000 0.543859 14.7991 + 34 0.0000 0.569057 15.4848 + 35 0.0000 0.599659 16.3175 + 36 0.0000 0.630358 17.1529 + 37 0.0000 0.647833 17.6284 + 38 0.0000 0.706541 19.2260 + 39 0.0000 0.717419 19.5220 + 40 0.0000 0.738229 20.0882 + 41 0.0000 0.756891 20.5961 + 42 0.0000 0.760832 20.7033 + 43 0.0000 0.790744 21.5172 + 44 0.0000 0.808828 22.0093 + 45 0.0000 0.815359 22.1870 + 46 0.0000 0.862814 23.4784 + 47 0.0000 0.869018 23.6472 + 48 0.0000 0.892742 24.2927 + 49 0.0000 0.945965 25.7410 + 50 0.0000 0.960457 26.1354 + 51 0.0000 0.980825 26.6896 + 52 0.0000 0.993454 27.0332 + 53 0.0000 1.029157 28.0048 + 54 0.0000 1.045468 28.4486 + 55 0.0000 1.106605 30.1123 + 56 0.0000 1.151447 31.3325 + 57 0.0000 1.225723 33.3536 + 58 0.0000 1.254487 34.1363 + 59 0.0000 1.259933 34.2845 + 60 0.0000 1.314370 35.7658 + 61 0.0000 1.409975 38.3674 + 62 0.0000 1.452103 39.5137 + 63 0.0000 1.517998 41.3068 + 64 0.0000 1.528073 41.5810 + 65 0.0000 1.568806 42.6894 + 66 0.0000 1.585516 43.1441 + 67 0.0000 1.631254 44.3887 + 68 0.0000 1.648844 44.8673 + 69 0.0000 1.716423 46.7062 + 70 0.0000 1.768882 48.1337 + 71 0.0000 1.784308 48.5535 + 72 0.0000 1.891886 51.4808 + 73 0.0000 1.923794 52.3491 + 74 0.0000 1.986045 54.0430 + 75 0.0000 2.012606 54.7658 + 76 0.0000 2.047190 55.7069 + 77 0.0000 2.091751 56.9194 + 78 0.0000 2.136511 58.1374 + 79 0.0000 2.202640 59.9369 + 80 0.0000 2.262046 61.5534 + 81 0.0000 2.292606 62.3850 + 82 0.0000 2.324209 63.2450 + 83 0.0000 2.358003 64.1645 + 84 0.0000 2.405067 65.4452 + 85 0.0000 2.451868 66.7187 + 86 0.0000 2.463257 67.0286 + 87 0.0000 2.477768 67.4235 + 88 0.0000 2.506373 68.2019 + 89 0.0000 2.568813 69.9010 + 90 0.0000 2.571108 69.9634 + 91 0.0000 2.600201 70.7551 + 92 0.0000 2.672294 72.7168 + 93 0.0000 2.727829 74.2280 + 94 0.0000 2.743786 74.6622 + 95 0.0000 2.779023 75.6211 + 96 0.0000 2.847233 77.4772 + 97 0.0000 2.889961 78.6398 + 98 0.0000 2.956976 80.4634 + 99 0.0000 2.985328 81.2349 + 100 0.0000 3.054855 83.1268 + 101 0.0000 3.165696 86.1430 + 102 0.0000 3.224289 87.7374 + 103 0.0000 3.485430 94.8434 + 104 0.0000 3.725831 101.3850 + 105 0.0000 3.809062 103.6499 + 106 0.0000 4.050354 110.2157 + 107 0.0000 4.173595 113.5693 + 108 0.0000 4.193418 114.1087 + 109 0.0000 4.290429 116.7485 + 110 0.0000 4.357450 118.5722 + 111 0.0000 4.393453 119.5519 + 112 0.0000 4.519947 122.9940 + 113 0.0000 4.604878 125.3051 + 114 0.0000 4.661584 126.8481 + 115 0.0000 4.718774 128.4044 + 116 0.0000 4.832004 131.4855 + 117 0.0000 4.900103 133.3386 + 118 0.0000 4.930973 134.1786 + 119 0.0000 4.947982 134.6414 + 120 0.0000 5.048914 137.3879 + 121 0.0000 5.102552 138.8475 + 122 0.0000 5.185727 141.1108 + 123 0.0000 5.194779 141.3571 + 124 0.0000 5.221616 142.0874 + 125 0.0000 5.321943 144.8174 + 126 0.0000 5.380201 146.4027 + 127 0.0000 5.482207 149.1784 + 128 0.0000 5.553682 151.1234 + 129 0.0000 5.706471 155.2810 + 130 0.0000 5.738436 156.1508 + 131 0.0000 5.929370 161.3463 + 132 0.0000 6.178179 168.1168 + 133 0.0000 6.417963 174.6417 + 134 0.0000 6.480552 176.3448 + 135 0.0000 6.503338 176.9648 + 136 0.0000 6.699527 182.3034 + 137 0.0000 6.726671 183.0420 + 138 0.0000 6.769113 184.1969 + 139 0.0000 6.816817 185.4950 + 140 0.0000 6.823928 185.6885 + 141 0.0000 7.066113 192.2787 + 142 0.0000 7.099096 193.1762 + 143 0.0000 7.117675 193.6818 + 144 0.0000 7.197502 195.8540 + 145 0.0000 7.256805 197.4677 + 146 0.0000 7.282670 198.1715 + 147 0.0000 7.342978 199.8126 + 148 0.0000 7.385453 200.9684 + 149 0.0000 7.453616 202.8232 + 150 0.0000 7.460475 203.0098 + 151 0.0000 7.561429 205.7569 + 152 0.0000 7.577490 206.1940 + 153 0.0000 7.624472 207.4724 + 154 0.0000 7.715319 209.9445 + 155 0.0000 7.896397 214.8719 + 156 0.0000 7.917537 215.4471 + 157 0.0000 8.397665 228.5121 + 158 0.0000 14.058083 382.5399 + 159 0.0000 14.845593 403.9691 + 160 0.0000 16.088801 437.7985 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.693153 -563.0893 + 1 1.0000 -20.615497 -560.9762 + 2 1.0000 -15.805830 -430.0985 + 3 1.0000 -1.618794 -44.0496 + 4 1.0000 -1.370230 -37.2859 + 5 1.0000 -0.955365 -25.9968 + 6 1.0000 -0.767545 -20.8860 + 7 1.0000 -0.733168 -19.9505 + 8 1.0000 -0.699936 -19.0462 + 9 1.0000 -0.605610 -16.4795 + 10 1.0000 -0.528777 -14.3888 + 11 1.0000 -0.458372 -12.4729 + 12 0.0000 0.030942 0.8420 + 13 0.0000 0.066318 1.8046 + 14 0.0000 0.091592 2.4923 + 15 0.0000 0.103238 2.8092 + 16 0.0000 0.113144 3.0788 + 17 0.0000 0.155430 4.2295 + 18 0.0000 0.157323 4.2810 + 19 0.0000 0.174183 4.7398 + 20 0.0000 0.180069 4.8999 + 21 0.0000 0.189711 5.1623 + 22 0.0000 0.200851 5.4654 + 23 0.0000 0.235660 6.4126 + 24 0.0000 0.268336 7.3018 + 25 0.0000 0.292246 7.9524 + 26 0.0000 0.299494 8.1496 + 27 0.0000 0.331631 9.0241 + 28 0.0000 0.332134 9.0378 + 29 0.0000 0.352155 9.5826 + 30 0.0000 0.425163 11.5693 + 31 0.0000 0.505368 13.7518 + 32 0.0000 0.528680 14.3861 + 33 0.0000 0.543859 14.7991 + 34 0.0000 0.569057 15.4848 + 35 0.0000 0.599659 16.3175 + 36 0.0000 0.630358 17.1529 + 37 0.0000 0.647833 17.6284 + 38 0.0000 0.706541 19.2260 + 39 0.0000 0.717419 19.5220 + 40 0.0000 0.738229 20.0882 + 41 0.0000 0.756891 20.5961 + 42 0.0000 0.760832 20.7033 + 43 0.0000 0.790744 21.5172 + 44 0.0000 0.808828 22.0093 + 45 0.0000 0.815359 22.1870 + 46 0.0000 0.862814 23.4784 + 47 0.0000 0.869018 23.6472 + 48 0.0000 0.892742 24.2927 + 49 0.0000 0.945965 25.7410 + 50 0.0000 0.960457 26.1354 + 51 0.0000 0.980825 26.6896 + 52 0.0000 0.993454 27.0332 + 53 0.0000 1.029157 28.0048 + 54 0.0000 1.045468 28.4486 + 55 0.0000 1.106605 30.1123 + 56 0.0000 1.151447 31.3325 + 57 0.0000 1.225723 33.3536 + 58 0.0000 1.254487 34.1363 + 59 0.0000 1.259933 34.2845 + 60 0.0000 1.314370 35.7658 + 61 0.0000 1.409975 38.3674 + 62 0.0000 1.452103 39.5137 + 63 0.0000 1.517998 41.3068 + 64 0.0000 1.528073 41.5810 + 65 0.0000 1.568806 42.6894 + 66 0.0000 1.585516 43.1441 + 67 0.0000 1.631254 44.3887 + 68 0.0000 1.648844 44.8673 + 69 0.0000 1.716423 46.7062 + 70 0.0000 1.768882 48.1337 + 71 0.0000 1.784308 48.5535 + 72 0.0000 1.891886 51.4808 + 73 0.0000 1.923794 52.3491 + 74 0.0000 1.986045 54.0430 + 75 0.0000 2.012606 54.7658 + 76 0.0000 2.047190 55.7069 + 77 0.0000 2.091751 56.9194 + 78 0.0000 2.136511 58.1374 + 79 0.0000 2.202640 59.9369 + 80 0.0000 2.262046 61.5534 + 81 0.0000 2.292606 62.3850 + 82 0.0000 2.324209 63.2450 + 83 0.0000 2.358003 64.1645 + 84 0.0000 2.405067 65.4452 + 85 0.0000 2.451868 66.7187 + 86 0.0000 2.463257 67.0286 + 87 0.0000 2.477768 67.4235 + 88 0.0000 2.506373 68.2019 + 89 0.0000 2.568813 69.9010 + 90 0.0000 2.571108 69.9634 + 91 0.0000 2.600201 70.7551 + 92 0.0000 2.672294 72.7168 + 93 0.0000 2.727829 74.2280 + 94 0.0000 2.743786 74.6622 + 95 0.0000 2.779023 75.6211 + 96 0.0000 2.847233 77.4772 + 97 0.0000 2.889961 78.6398 + 98 0.0000 2.956976 80.4634 + 99 0.0000 2.985328 81.2349 + 100 0.0000 3.054855 83.1268 + 101 0.0000 3.165696 86.1430 + 102 0.0000 3.224289 87.7374 + 103 0.0000 3.485430 94.8434 + 104 0.0000 3.725831 101.3850 + 105 0.0000 3.809062 103.6499 + 106 0.0000 4.050354 110.2157 + 107 0.0000 4.173595 113.5693 + 108 0.0000 4.193418 114.1087 + 109 0.0000 4.290429 116.7485 + 110 0.0000 4.357450 118.5722 + 111 0.0000 4.393453 119.5519 + 112 0.0000 4.519947 122.9940 + 113 0.0000 4.604878 125.3051 + 114 0.0000 4.661584 126.8481 + 115 0.0000 4.718774 128.4044 + 116 0.0000 4.832004 131.4855 + 117 0.0000 4.900103 133.3386 + 118 0.0000 4.930973 134.1786 + 119 0.0000 4.947982 134.6414 + 120 0.0000 5.048914 137.3879 + 121 0.0000 5.102552 138.8475 + 122 0.0000 5.185727 141.1108 + 123 0.0000 5.194779 141.3571 + 124 0.0000 5.221616 142.0874 + 125 0.0000 5.321943 144.8174 + 126 0.0000 5.380201 146.4027 + 127 0.0000 5.482207 149.1784 + 128 0.0000 5.553682 151.1234 + 129 0.0000 5.706471 155.2810 + 130 0.0000 5.738436 156.1508 + 131 0.0000 5.929370 161.3463 + 132 0.0000 6.178179 168.1168 + 133 0.0000 6.417963 174.6417 + 134 0.0000 6.480552 176.3448 + 135 0.0000 6.503338 176.9648 + 136 0.0000 6.699527 182.3034 + 137 0.0000 6.726671 183.0420 + 138 0.0000 6.769113 184.1969 + 139 0.0000 6.816817 185.4950 + 140 0.0000 6.823928 185.6885 + 141 0.0000 7.066113 192.2787 + 142 0.0000 7.099096 193.1762 + 143 0.0000 7.117675 193.6818 + 144 0.0000 7.197502 195.8540 + 145 0.0000 7.256805 197.4677 + 146 0.0000 7.282670 198.1715 + 147 0.0000 7.342978 199.8126 + 148 0.0000 7.385453 200.9684 + 149 0.0000 7.453616 202.8232 + 150 0.0000 7.460475 203.0098 + 151 0.0000 7.561429 205.7569 + 152 0.0000 7.577490 206.1940 + 153 0.0000 7.624472 207.4724 + 154 0.0000 7.715319 209.9445 + 155 0.0000 7.896397 214.8719 + 156 0.0000 7.917537 215.4471 + 157 0.0000 8.397665 228.5121 + 158 0.0000 14.058083 382.5399 + 159 0.0000 14.845593 403.9691 + 160 0.0000 16.088801 437.7985 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.378206 0.000000 + 1 N : 0.353954 0.000000 + 2 O : -0.223853 0.000000 + 3 H : 0.248105 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.864915 s : 3.864915 + pz : 1.305249 p : 4.483883 + px : 1.554005 + py : 1.624628 + dz2 : 0.010061 d : 0.025177 + dxz : 0.007695 + dyz : 0.004485 + dx2y2 : 0.001109 + dxy : 0.001827 + f0 : 0.001441 f : 0.004230 + f+1 : 0.000826 + f-1 : 0.000733 + f+2 : 0.000210 + f-2 : 0.000318 + f+3 : 0.000286 + f-3 : 0.000417 + 1 N s : 3.822083 s : 3.822083 + pz : 0.834362 p : 2.656094 + px : 0.847419 + py : 0.974313 + dz2 : 0.027111 d : 0.137173 + dxz : 0.039364 + dyz : 0.019060 + dx2y2 : 0.033223 + dxy : 0.018416 + f0 : 0.008179 f : 0.030696 + f+1 : 0.003187 + f-1 : 0.005277 + f+2 : 0.002261 + f-2 : 0.005350 + f+3 : 0.003770 + f-3 : 0.002672 + 2 O s : 3.875060 s : 3.875060 + pz : 1.743258 p : 4.278323 + px : 1.209617 + py : 1.325448 + dz2 : 0.004564 d : 0.062968 + dxz : 0.009472 + dyz : 0.009384 + dx2y2 : 0.027658 + dxy : 0.011889 + f0 : 0.001191 f : 0.007502 + f+1 : 0.000657 + f-1 : 0.000596 + f+2 : -0.000039 + f-2 : 0.001301 + f+3 : 0.002445 + f-3 : 0.001350 + 3 H s : 0.644016 s : 0.644016 + pz : 0.020875 p : 0.087715 + px : 0.034974 + py : 0.031867 + dz2 : 0.001506 d : 0.020163 + dxz : 0.003761 + dyz : 0.004150 + dx2y2 : 0.010219 + dxy : 0.000528 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.573204 0.000000 + 1 N : -0.230264 0.000000 + 2 O : 0.250195 0.000000 + 3 H : -0.593135 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.137970 s : 3.137970 + pz : 1.222192 p : 3.961657 + px : 1.335506 + py : 1.403959 + dz2 : 0.085767 d : 0.253634 + dxz : 0.068576 + dyz : 0.050187 + dx2y2 : 0.013889 + dxy : 0.035215 + f0 : 0.017955 f : 0.073534 + f+1 : 0.016591 + f-1 : 0.014802 + f+2 : 0.009281 + f-2 : 0.009094 + f+3 : 0.003405 + f-3 : 0.002405 + 1 N s : 3.039567 s : 3.039567 + pz : 0.866969 p : 2.838401 + px : 0.956997 + py : 1.014435 + dz2 : 0.198445 d : 0.916033 + dxz : 0.252486 + dyz : 0.128979 + dx2y2 : 0.146397 + dxy : 0.189727 + f0 : 0.098579 f : 0.436263 + f+1 : 0.056491 + f-1 : 0.055291 + f+2 : 0.027816 + f-2 : 0.079823 + f+3 : 0.063407 + f-3 : 0.054855 + 2 O s : 3.314800 s : 3.314800 + pz : 1.429816 p : 3.985637 + px : 1.272409 + py : 1.283411 + dz2 : 0.050346 d : 0.331510 + dxz : 0.075911 + dyz : 0.029457 + dx2y2 : 0.059759 + dxy : 0.116037 + f0 : 0.013119 f : 0.117858 + f+1 : 0.015070 + f-1 : 0.011594 + f+2 : 0.006264 + f-2 : 0.020208 + f+3 : 0.027970 + f-3 : 0.023632 + 3 H s : 0.627886 s : 0.627886 + pz : 0.148141 p : 0.575174 + px : 0.207068 + py : 0.219965 + dz2 : 0.032117 d : 0.390076 + dxz : 0.076768 + dyz : 0.066924 + dx2y2 : 0.121555 + dxy : 0.092712 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3782 8.0000 -0.3782 1.8187 1.8187 0.0000 + 1 N 6.6460 7.0000 0.3540 2.5979 2.5979 -0.0000 + 2 O 8.2239 8.0000 -0.2239 1.8150 1.8150 0.0000 + 3 H 0.7519 1.0000 0.2481 0.9936 0.9936 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8045 B( 0-O , 3-H ) : 0.9577 B( 1-N , 2-O ) : 1.7581 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.388 sec +Sum of individual times .... 0.895 sec ( 64.5%) + +Fock matrix formation .... 0.655 sec ( 47.2%) +Diagonalization .... 0.068 sec ( 4.9%) +Density matrix formation .... 0.007 sec ( 0.5%) +Population analysis .... 0.103 sec ( 7.4%) +Initial guess .... 0.016 sec ( 1.1%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.009 sec ( 0.7%) +DIIS solution .... 0.046 sec ( 3.3%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.276 sec +Reference energy ... -204.704910950 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.963 sec +AO-integral generation ... 0.195 sec +Half transformation ... 0.112 sec +K-integral sorting ... 5.842 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.030 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.033 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.032 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.041 s ( 0.000 ms/b) + 159120 b 0 skpd 0.021 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.042 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.035 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.026 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.045 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.026 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.401 sec +AO-integral generation ... 0.284 sec +Half transformation ... 0.049 sec +J-integral sorting ... 0.052 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.156 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.271 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090017590 +EMP2(bb)= -0.090017590 +EMP2(ab)= -0.517559890 + +Initial guess performed in 0.141 sec +E(0) ... -204.704910950 +E(MP2) ... -0.697595070 +Initial E(tot) ... -205.402506021 + ... 0.189735107 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.402506021 -0.697595070 -0.000000000 0.018767463 3.24 0.000002427 + *** Turning on DIIS *** + 1 -205.374133437 -0.669222487 0.028372584 0.010817247 3.22 0.055447106 + 2 -205.393691456 -0.688780505 -0.019558019 0.003689552 3.32 0.058119532 + 3 -205.397519122 -0.692608172 -0.003827666 0.002076513 3.70 0.070939346 + 4 -205.399053216 -0.694142266 -0.001534094 0.000959078 3.59 0.076568701 + 5 -205.399530513 -0.694619563 -0.000477297 0.000403719 3.53 0.080681807 + 6 -205.399603319 -0.694692369 -0.000072806 0.000305592 3.96 0.082492263 + 7 -205.399631373 -0.694720423 -0.000028054 0.000232523 5.26 0.083257154 + 8 -205.399637126 -0.694726176 -0.000005753 0.000171427 4.34 0.083579829 + 9 -205.399634127 -0.694723177 0.000002999 0.000118070 3.63 0.083710275 + 10 -205.399638352 -0.694727402 -0.000004225 0.000060500 3.46 0.083790440 + 11 -205.399634836 -0.694723886 0.000003516 0.000022283 3.48 0.083823365 + 12 -205.399637485 -0.694726535 -0.000002649 0.000011251 3.47 0.083841591 + 13 -205.399637698 -0.694726748 -0.000000213 0.000003786 3.50 0.083844614 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.704910950 +E(CORR) ... -0.694726748 +E(TOT) ... -205.399637698 +Singles norm **1/2 ... 0.083844614 ( 0.041922307, 0.041922307) +T1 diagnostic ... 0.019762365 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.061317 + 8a-> 13a 8b-> 13b 0.055538 + 9a-> 13a 8b-> 13b 0.047234 + 8a-> 13a 9b-> 13b 0.047234 + 5a-> 13a 5b-> 13b 0.030237 + 11a-> 25a 11b-> 25b 0.028115 + 11a-> 13a 11b-> 13b 0.027913 + 8b-> 13b -1b-> -1b 0.027252 + 8a-> 13a -1a-> -1a 0.027252 + 11a-> 24a 11b-> 24b 0.026319 + 11a-> 25a 11b-> 24b 0.025808 + 11a-> 24a 11b-> 25b 0.025808 + 9a-> 22a 9b-> 13b 0.023622 + 9a-> 13a 9b-> 22b 0.023622 + 11a-> 24a -1a-> -1a 0.020671 + 11b-> 24b -1b-> -1b 0.020671 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034504697 + alpha-alpha-alpha ... -0.000859125 ( 2.5%) + alpha-alpha-beta ... -0.016393224 ( 47.5%) + alpha-beta -beta ... -0.016393224 ( 47.5%) + beta -beta -beta ... -0.000859125 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034504697 + +Final correlation energy ... -0.729231444 +E(CCSD) ... -205.399637698 +E(CCSD(T)) ... -205.434142395 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210182565 sqrt= 1.100082981 +W(HF) = 0.826321605 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.321801 0.000000 + 1 N : 0.182925 -0.000000 + 2 O : -0.097373 -0.000000 + 3 H : 0.236249 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.842999 s : 3.842999 + pz : 1.284993 p : 4.414736 + px : 1.536566 + py : 1.593176 + dz2 : 0.014906 d : 0.056100 + dxz : 0.012904 + dyz : 0.011583 + dx2y2 : 0.008438 + dxy : 0.008269 + f0 : 0.001830 f : 0.007966 + f+1 : 0.001120 + f-1 : 0.001277 + f+2 : 0.000799 + f-2 : 0.000946 + f+3 : 0.000927 + f-3 : 0.001066 + 1 N s : 3.876360 s : 3.876360 + pz : 0.880964 p : 2.744720 + px : 0.878213 + py : 0.985543 + dz2 : 0.034353 d : 0.166350 + dxz : 0.047635 + dyz : 0.026631 + dx2y2 : 0.034357 + dxy : 0.023373 + f0 : 0.007751 f : 0.029645 + f+1 : 0.002990 + f-1 : 0.005365 + f+2 : 0.002755 + f-2 : 0.005106 + f+3 : 0.003243 + f-3 : 0.002434 + 2 O s : 3.862232 s : 3.862232 + pz : 1.658248 p : 4.141485 + px : 1.189078 + py : 1.294159 + dz2 : 0.009934 d : 0.083804 + dxz : 0.016306 + dyz : 0.014849 + dx2y2 : 0.027960 + dxy : 0.014756 + f0 : 0.001627 f : 0.009852 + f+1 : 0.001125 + f-1 : 0.001045 + f+2 : 0.000592 + f-2 : 0.001645 + f+3 : 0.002299 + f-3 : 0.001519 + 3 H s : 0.651213 s : 0.651213 + pz : 0.024494 p : 0.095308 + px : 0.036203 + py : 0.034611 + dz2 : 0.001342 d : 0.017230 + dxz : 0.003391 + dyz : 0.003576 + dx2y2 : 0.008966 + dxy : -0.000045 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.577741 0.000000 + 1 N : -0.273608 -0.000000 + 2 O : 0.293785 -0.000000 + 3 H : -0.597918 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.141993 s : 3.141993 + pz : 1.215180 p : 3.915350 + px : 1.322865 + py : 1.377305 + dz2 : 0.091692 d : 0.284498 + dxz : 0.075211 + dyz : 0.055471 + dx2y2 : 0.019819 + dxy : 0.042305 + f0 : 0.019354 f : 0.080418 + f+1 : 0.018439 + f-1 : 0.015244 + f+2 : 0.009908 + f-2 : 0.010077 + f+3 : 0.004158 + f-3 : 0.003239 + 1 N s : 3.044403 s : 3.044403 + pz : 0.888341 p : 2.878672 + px : 0.973085 + py : 1.017246 + dz2 : 0.204863 d : 0.923545 + dxz : 0.252951 + dyz : 0.127600 + dx2y2 : 0.142046 + dxy : 0.196087 + f0 : 0.095257 f : 0.426988 + f+1 : 0.057233 + f-1 : 0.054493 + f+2 : 0.027236 + f-2 : 0.075782 + f+3 : 0.061924 + f-3 : 0.055064 + 2 O s : 3.317646 s : 3.317646 + pz : 1.375943 p : 3.903108 + px : 1.260988 + py : 1.266177 + dz2 : 0.056162 d : 0.359259 + dxz : 0.079275 + dyz : 0.035112 + dx2y2 : 0.067896 + dxy : 0.120813 + f0 : 0.014006 f : 0.126202 + f+1 : 0.015825 + f-1 : 0.011928 + f+2 : 0.006782 + f-2 : 0.021421 + f+3 : 0.030940 + f-3 : 0.025300 + 3 H s : 0.627984 s : 0.627984 + pz : 0.148659 p : 0.589946 + px : 0.213285 + py : 0.228002 + dz2 : 0.032888 d : 0.379988 + dxz : 0.073906 + dyz : 0.064822 + dx2y2 : 0.116470 + dxy : 0.091902 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3218 8.0000 -0.3218 2.1588 1.6952 0.4636 + 1 N 6.8171 7.0000 0.1829 2.8586 2.3632 0.4953 + 2 O 8.0974 8.0000 -0.0974 2.1989 1.7007 0.4982 + 3 H 0.7638 1.0000 0.2362 1.0150 0.9404 0.0746 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7130 B( 0-O , 3-H ) : 0.8955 B( 1-N , 2-O ) : 1.6096 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 69.782 sec + +Fock Matrix Formation ... 0.276 sec ( 0.4%) +Initial Guess ... 0.141 sec ( 0.2%) +DIIS Solver ... 2.891 sec ( 4.1%) +State Vector Update ... 0.123 sec ( 0.2%) +Sigma-vector construction ... 48.677 sec ( 69.8%) + <0|H|D> ... 0.005 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.031 sec ( 0.1% of sigma) + (0-ext) ... 0.092 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.032 sec ( 0.1% of sigma) + (2-ext) ... 1.181 sec ( 2.4% of sigma) + (4-ext) ... 28.372 sec ( 58.3% of sigma) + ... 1.911 sec ( 3.9% of sigma) + ... 0.003 sec ( 0.0% of sigma) + (1-ext) ... 0.010 sec ( 0.0% of sigma) + (1-ext) ... 0.136 sec ( 0.3% of sigma) + Fock-dressing ... 2.622 sec ( 5.4% of sigma) + (ik|jl)-dressing ... 0.099 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 11.350 sec ( 23.3% of sigma) + Pair energies ... 0.011 sec ( 0.0% of sigma) +Total Time for computing (T) ... 8.647 sec ( 12.4% of ALL) + I/O of integral and amplitudes ... 1.027 sec ( 11.9% of (T)) + External N**7 contributions ... 5.005 sec ( 57.9% of (T)) + Internal N**7 contributions ... 0.422 sec ( 4.9% of (T)) + N**6 triples energy contributions ... 2.096 sec ( 24.2% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.434142394582 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.034.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.034.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.610722, -0.232810 -0.293717) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.82822 -0.16372 -0.93337 +Nuclear contribution : -1.28493 0.53796 0.67844 + ----------------------------------------- +Total Dipole Moment : -0.45672 0.37423 -0.25493 + ----------------------------------------- +Magnitude (a.u.) : 0.64314 +Magnitude (Debye) : 1.63473 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.717896 0.398433 0.359770 +Rotational constants in MHz : 81480.465454 11944.709745 10785.622007 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.083661 0.035247 -0.636701 +x,y,z [Debye]: -0.212648 0.089591 -1.618366 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.610722, -0.232810 -0.293717) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.99472 -0.10795 -0.95993 +Nuclear contribution : -1.28493 0.53796 0.67844 + ----------------------------------------- +Total Dipole Moment : -0.29021 0.43001 -0.28149 + ----------------------------------------- +Magnitude (a.u.) : 0.59023 +Magnitude (Debye) : 1.50024 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.717896 0.398433 0.359770 +Rotational constants in MHz : 81480.465454 11944.709745 10785.622007 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.060170 -0.054953 -0.584576 +x,y,z [Debye]: 0.152939 -0.139681 -1.485873 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 35 * + * * + * Dihedral ( 2, 1, 0, 3) : 98.18181818 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0390815019 RMS(Int)= 0.0000088536 + Iter 1: RMS(Cart)= 0.0000024231 RMS(Int)= 0.0000000167 + Iter 2: RMS(Cart)= 0.0000000046 RMS(Int)= 0.0000000000 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.5082 0.000000 + 2. B(O 2,N 1) 1.1666 0.000000 + 3. B(H 3,O 0) 0.9723 0.000000 + 4. A(N 1,O 0,H 3) 102.8425 0.000000 + 5. A(O 0,N 1,O 2) 110.8894 0.000000 + 6. D(O 2,N 1,O 0,H 3) 98.1818 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.364564 -0.206755 0.763479 + N 0.247430 -0.438332 -0.595402 + O 1.197831 0.222149 -0.741599 + H -1.080696 0.422938 0.573522 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.688926 -0.390711 1.442767 + 1 N 7.0000 0 14.007 0.467575 -0.828327 -1.125146 + 2 O 8.0000 0 15.999 2.263573 0.419801 -1.401420 + 3 H 1.0000 0 1.008 -2.042220 0.799237 1.083799 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.507764435739 0.00000000 0.00000000 + O 2 1 0 1.164651702095 110.98913083 0.00000000 + H 1 2 3 0.969719079259 102.94408058 89.99999994 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.849261858013 0.00000000 0.00000000 + O 2 1 0 2.200872758366 110.98913083 0.00000000 + H 1 2 3 1.832503486637 102.94408058 89.99999994 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2228 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2695 + la=0 lb=0: 548 shell pairs + la=1 lb=0: 535 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.206729676442 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.2067296764 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.910e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.003 sec +Total time needed ... 0.006 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7002980709 0.000000000000 0.00153210 0.00005084 0.0190206 0.7000 + 1 -204.7011799173 -0.000881846327 0.00145890 0.00004672 0.0157589 0.7000 + ***Turning on DIIS*** + 2 -204.7019382417 -0.000758324450 0.00411408 0.00012859 0.0128241 0.0000 + 3 -204.7051356551 -0.003197413364 0.00196282 0.00005853 0.0048927 0.0000 + 4 -204.7037482231 0.001387432027 0.00092810 0.00003084 0.0018589 0.0000 + 5 -204.7055494594 -0.001801236379 0.00091893 0.00002615 0.0011267 0.0000 + 6 -204.7047336230 0.000815836401 0.00091339 0.00003117 0.0007797 0.0000 + 7 -204.7043381198 0.000395503184 0.00047101 0.00001536 0.0003273 0.0000 + 8 -204.7051624557 -0.000824335818 0.00025062 0.00000887 0.0002084 0.0000 + 9 -204.7046854383 0.000477017336 0.00017235 0.00000596 0.0001243 0.0000 + 10 -204.7048050104 -0.000119572035 0.00006814 0.00000260 0.0000651 0.0000 + 11 -204.7049422868 -0.000137276401 0.00003651 0.00000102 0.0000301 0.0000 + 12 -204.7048448500 0.000097436808 0.00000857 0.00000028 0.0000109 0.0000 + 13 -204.7048690332 -0.000024183282 0.00000260 0.00000009 0.0000041 0.0000 + 14 -204.7048628061 0.000006227161 0.00000122 0.00000004 0.0000029 0.0000 + 15 -204.7048635319 -0.000000725863 0.00000117 0.00000003 0.0000024 0.0000 + 16 -204.7048654673 -0.000001935349 0.00000088 0.00000002 0.0000012 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 17 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70486459 Eh -5570.30255 eV + +Components: +Nuclear Repulsion : 68.20672968 Eh 1855.99947 eV +Electronic Energy : -272.91159427 Eh -7426.30203 eV +One Electron Energy: -416.13317178 Eh -11323.55928 eV +Two Electron Energy: 143.22157751 Eh 3897.25726 eV + +Virial components: +Potential Energy : -408.91384669 Eh -11127.11146 eV +Kinetic Energy : 204.20898209 Eh 5556.80891 eV +Virial Ratio : 2.00242831 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 8.7303e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.5489e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.5543e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.8899e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.692694 -563.0768 + 1 1.0000 -20.616238 -560.9964 + 2 1.0000 -15.805788 -430.0973 + 3 1.0000 -1.616248 -43.9803 + 4 1.0000 -1.369798 -37.2741 + 5 1.0000 -0.954682 -25.9782 + 6 1.0000 -0.767191 -20.8763 + 7 1.0000 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0.0000 0.030712 0.8357 + 13 0.0000 0.066412 1.8072 + 14 0.0000 0.091550 2.4912 + 15 0.0000 0.102430 2.7873 + 16 0.0000 0.113583 3.0907 + 17 0.0000 0.155066 4.2196 + 18 0.0000 0.157198 4.2776 + 19 0.0000 0.173737 4.7276 + 20 0.0000 0.181421 4.9367 + 21 0.0000 0.189744 5.1632 + 22 0.0000 0.200785 5.4636 + 23 0.0000 0.236049 6.4232 + 24 0.0000 0.268113 7.2957 + 25 0.0000 0.289588 7.8801 + 26 0.0000 0.300917 8.1884 + 27 0.0000 0.330237 8.9862 + 28 0.0000 0.331971 9.0334 + 29 0.0000 0.353184 9.6106 + 30 0.0000 0.424605 11.5541 + 31 0.0000 0.505195 13.7471 + 32 0.0000 0.527216 14.3463 + 33 0.0000 0.543738 14.7959 + 34 0.0000 0.571738 15.5578 + 35 0.0000 0.600927 16.3521 + 36 0.0000 0.629596 17.1322 + 37 0.0000 0.648351 17.6425 + 38 0.0000 0.702289 19.1103 + 39 0.0000 0.719110 19.5680 + 40 0.0000 0.739486 20.1224 + 41 0.0000 0.753171 20.4948 + 42 0.0000 0.764883 20.8135 + 43 0.0000 0.791158 21.5285 + 44 0.0000 0.811527 22.0828 + 45 0.0000 0.813056 22.1244 + 46 0.0000 0.859930 23.3999 + 47 0.0000 0.869247 23.6534 + 48 0.0000 0.894578 24.3427 + 49 0.0000 0.939965 25.5777 + 50 0.0000 0.958612 26.0852 + 51 0.0000 0.985395 26.8140 + 52 0.0000 0.995514 27.0893 + 53 0.0000 1.026885 27.9430 + 54 0.0000 1.046466 28.4758 + 55 0.0000 1.112011 30.2594 + 56 0.0000 1.144634 31.1471 + 57 0.0000 1.230522 33.4842 + 58 0.0000 1.249420 33.9984 + 59 0.0000 1.270193 34.5637 + 60 0.0000 1.315798 35.8047 + 61 0.0000 1.412370 38.4325 + 62 0.0000 1.442889 39.2630 + 63 0.0000 1.518989 41.3338 + 64 0.0000 1.521835 41.4112 + 65 0.0000 1.566754 42.6335 + 66 0.0000 1.584158 43.1071 + 67 0.0000 1.632883 44.4330 + 68 0.0000 1.648202 44.8499 + 69 0.0000 1.709685 46.5229 + 70 0.0000 1.773060 48.2474 + 71 0.0000 1.790055 48.7099 + 72 0.0000 1.885088 51.2958 + 73 0.0000 1.925173 52.3866 + 74 0.0000 1.982116 53.9361 + 75 0.0000 2.020481 54.9801 + 76 0.0000 2.054284 55.8999 + 77 0.0000 2.079789 56.5939 + 78 0.0000 2.140221 58.2384 + 79 0.0000 2.210714 60.1566 + 80 0.0000 2.246332 61.1258 + 81 0.0000 2.295896 62.4745 + 82 0.0000 2.314259 62.9742 + 83 0.0000 2.365484 64.3681 + 84 0.0000 2.406802 65.4924 + 85 0.0000 2.452424 66.7339 + 86 0.0000 2.459298 66.9209 + 87 0.0000 2.476903 67.4000 + 88 0.0000 2.505361 68.1743 + 89 0.0000 2.559101 69.6367 + 90 0.0000 2.566784 69.8457 + 91 0.0000 2.596947 70.6665 + 92 0.0000 2.673908 72.7607 + 93 0.0000 2.721422 74.0537 + 94 0.0000 2.749855 74.8274 + 95 0.0000 2.799759 76.1853 + 96 0.0000 2.847137 77.4745 + 97 0.0000 2.877401 78.2981 + 98 0.0000 2.951782 80.3221 + 99 0.0000 2.986431 81.2649 + 100 0.0000 3.050784 83.0161 + 101 0.0000 3.163888 86.0938 + 102 0.0000 3.226382 87.7943 + 103 0.0000 3.485744 94.8519 + 104 0.0000 3.726924 101.4148 + 105 0.0000 3.808025 103.6216 + 106 0.0000 4.051923 110.2584 + 107 0.0000 4.174278 113.5879 + 108 0.0000 4.182671 113.8163 + 109 0.0000 4.294911 116.8705 + 110 0.0000 4.348418 118.3265 + 111 0.0000 4.390734 119.4780 + 112 0.0000 4.522893 123.0742 + 113 0.0000 4.601766 125.2204 + 114 0.0000 4.662606 126.8760 + 115 0.0000 4.715447 128.3138 + 116 0.0000 4.819095 131.1342 + 117 0.0000 4.900413 133.3470 + 118 0.0000 4.932814 134.2287 + 119 0.0000 4.947386 134.6252 + 120 0.0000 5.051221 137.4507 + 121 0.0000 5.098202 138.7291 + 122 0.0000 5.179876 140.9516 + 123 0.0000 5.195311 141.3716 + 124 0.0000 5.211169 141.8031 + 125 0.0000 5.327051 144.9564 + 126 0.0000 5.369683 146.1165 + 127 0.0000 5.476844 149.0325 + 128 0.0000 5.538152 150.7008 + 129 0.0000 5.720296 155.6572 + 130 0.0000 5.731303 155.9567 + 131 0.0000 5.924922 161.2253 + 132 0.0000 6.177529 168.0991 + 133 0.0000 6.415555 174.5761 + 134 0.0000 6.483135 176.4151 + 135 0.0000 6.500865 176.8975 + 136 0.0000 6.700098 182.3189 + 137 0.0000 6.727056 183.0525 + 138 0.0000 6.770675 184.2394 + 139 0.0000 6.808360 185.2649 + 140 0.0000 6.821512 185.6228 + 141 0.0000 7.061183 192.1446 + 142 0.0000 7.098569 193.1619 + 143 0.0000 7.117488 193.6767 + 144 0.0000 7.193288 195.7393 + 145 0.0000 7.255593 197.4347 + 146 0.0000 7.278148 198.0485 + 147 0.0000 7.341130 199.7623 + 148 0.0000 7.383791 200.9232 + 149 0.0000 7.444241 202.5681 + 150 0.0000 7.459495 202.9832 + 151 0.0000 7.551776 205.4943 + 152 0.0000 7.580911 206.2871 + 153 0.0000 7.606431 206.9815 + 154 0.0000 7.733645 210.4432 + 155 0.0000 7.897899 214.9128 + 156 0.0000 7.916447 215.4175 + 157 0.0000 8.389818 228.2986 + 158 0.0000 14.040462 382.0604 + 159 0.0000 14.784851 402.3162 + 160 0.0000 16.025727 436.0822 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.380695 0.000000 + 1 N : 0.355066 0.000000 + 2 O : -0.226138 0.000000 + 3 H : 0.251768 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.867697 s : 3.867697 + pz : 1.296488 p : 4.484202 + px : 1.527149 + py : 1.660565 + dz2 : 0.010354 d : 0.024491 + dxz : 0.007478 + dyz : 0.004270 + dx2y2 : 0.000677 + dxy : 0.001712 + f0 : 0.001534 f : 0.004305 + f+1 : 0.000780 + f-1 : 0.000762 + f+2 : 0.000163 + f-2 : 0.000312 + f+3 : 0.000222 + f-3 : 0.000532 + 1 N s : 3.821309 s : 3.821309 + pz : 0.845403 p : 2.657461 + px : 0.868889 + py : 0.943168 + dz2 : 0.027253 d : 0.135676 + dxz : 0.039880 + dyz : 0.018819 + dx2y2 : 0.031094 + dxy : 0.018630 + f0 : 0.008361 f : 0.030489 + f+1 : 0.003414 + f-1 : 0.005352 + f+2 : 0.002233 + f-2 : 0.005021 + f+3 : 0.003934 + f-3 : 0.002174 + 2 O s : 3.875865 s : 3.875865 + pz : 1.761355 p : 4.279671 + px : 1.203962 + py : 1.314355 + dz2 : 0.004616 d : 0.063089 + dxz : 0.010459 + dyz : 0.007840 + dx2y2 : 0.027326 + dxy : 0.012849 + f0 : 0.001200 f : 0.007513 + f+1 : 0.000714 + f-1 : 0.000561 + f+2 : 0.000011 + f-2 : 0.001222 + f+3 : 0.002624 + f-3 : 0.001181 + 3 H s : 0.641647 s : 0.641647 + pz : 0.019918 p : 0.086525 + px : 0.033219 + py : 0.033388 + dz2 : 0.001364 d : 0.020060 + dxz : 0.004405 + dyz : 0.003583 + dx2y2 : 0.010143 + dxy : 0.000565 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.570141 0.000000 + 1 N : -0.230274 0.000000 + 2 O : 0.248245 0.000000 + 3 H : -0.588112 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.139561 s : 3.139561 + pz : 1.218246 p : 3.962772 + px : 1.327970 + py : 1.416556 + dz2 : 0.090279 d : 0.253933 + dxz : 0.066947 + dyz : 0.049248 + dx2y2 : 0.014011 + dxy : 0.033448 + f0 : 0.019619 f : 0.073594 + f+1 : 0.016530 + f-1 : 0.014710 + f+2 : 0.008919 + f-2 : 0.008246 + f+3 : 0.002461 + f-3 : 0.003108 + 1 N s : 3.040305 s : 3.040305 + pz : 0.877193 p : 2.839156 + px : 0.990671 + py : 0.971292 + dz2 : 0.200271 d : 0.915617 + dxz : 0.261530 + dyz : 0.124139 + dx2y2 : 0.142329 + dxy : 0.187347 + f0 : 0.101430 f : 0.435196 + f+1 : 0.058139 + f-1 : 0.055176 + f+2 : 0.030511 + f-2 : 0.074434 + f+3 : 0.062244 + f-3 : 0.053263 + 2 O s : 3.317156 s : 3.317156 + pz : 1.443016 p : 3.986409 + px : 1.289974 + py : 1.253419 + dz2 : 0.050002 d : 0.330653 + dxz : 0.081105 + dyz : 0.025873 + dx2y2 : 0.059640 + dxy : 0.114035 + f0 : 0.013503 f : 0.117537 + f+1 : 0.016236 + f-1 : 0.010162 + f+2 : 0.007973 + f-2 : 0.018750 + f+3 : 0.026379 + f-3 : 0.024534 + 3 H s : 0.627209 s : 0.627209 + pz : 0.145972 p : 0.571658 + px : 0.214249 + py : 0.211437 + dz2 : 0.032189 d : 0.389246 + dxz : 0.084424 + dyz : 0.058596 + dx2y2 : 0.120392 + dxy : 0.093644 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3807 8.0000 -0.3807 1.8229 1.8229 -0.0000 + 1 N 6.6449 7.0000 0.3551 2.5985 2.5985 -0.0000 + 2 O 8.2261 8.0000 -0.2261 1.8152 1.8152 0.0000 + 3 H 0.7482 1.0000 0.2518 0.9879 0.9879 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8098 B( 0-O , 3-H ) : 0.9568 B( 1-N , 2-O ) : 1.7582 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 3 sec + +Total time .... 3.548 sec +Sum of individual times .... 3.126 sec ( 88.1%) + +Fock matrix formation .... 2.561 sec ( 72.2%) +Diagonalization .... 0.232 sec ( 6.5%) +Density matrix formation .... 0.020 sec ( 0.6%) +Population analysis .... 0.099 sec ( 2.8%) +Initial guess .... 0.012 sec ( 0.3%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.007 sec ( 0.2%) +DIIS solution .... 0.202 sec ( 5.7%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.267 sec +Reference energy ... -204.704864948 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 7.157 sec +AO-integral generation ... 0.169 sec +Half transformation ... 0.093 sec +K-integral sorting ... 6.041 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.031 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.037 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.062 s ( 0.000 ms/b) + 159120 b 0 skpd 0.021 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.051 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.036 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.035 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.055 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.030 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.470 sec +AO-integral generation ... 0.333 sec +Half transformation ... 0.060 sec +J-integral sorting ... 0.057 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.156 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.266 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090111678 +EMP2(bb)= -0.090111678 +EMP2(ab)= -0.518047209 + +Initial guess performed in 0.140 sec +E(0) ... -204.704864948 +E(MP2) ... -0.698270566 +Initial E(tot) ... -205.403135513 + ... 0.190316883 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.403135513 -0.698270566 -0.000000000 0.018905017 3.19 0.000002079 + *** Turning on DIIS *** + 1 -205.374455573 -0.669590625 0.028679940 0.010737632 3.19 0.055751775 + 2 -205.394113745 -0.689248797 -0.019658172 0.003711910 3.36 0.058399458 + 3 -205.397959979 -0.693095031 -0.003846234 0.002056554 3.39 0.071345467 + 4 -205.399507696 -0.694642748 -0.001547717 0.000962733 3.36 0.077048894 + 5 -205.399994452 -0.695129504 -0.000486756 0.000399752 3.80 0.081264245 + 6 -205.400069720 -0.695204772 -0.000075268 0.000266450 4.66 0.083139812 + 7 -205.400099183 -0.695234235 -0.000029463 0.000204278 4.82 0.083952019 + 8 -205.400105568 -0.695240620 -0.000006385 0.000151755 3.42 0.084299474 + 9 -205.400102401 -0.695237454 0.000003166 0.000105438 4.32 0.084439942 + 10 -205.400106895 -0.695241947 -0.000004493 0.000057287 4.83 0.084520673 + 11 -205.400103333 -0.695238385 0.000003562 0.000027250 3.82 0.084545741 + 12 -205.400106078 -0.695241131 -0.000002746 0.000012564 3.56 0.084564197 + 13 -205.400106166 -0.695241218 -0.000000087 0.000006402 3.73 0.084566292 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.704864948 +E(CORR) ... -0.695241218 +E(TOT) ... -205.400106166 +Singles norm **1/2 ... 0.084566292 ( 0.042283146, 0.042283146) +T1 diagnostic ... 0.019932466 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.061228 + 8a-> 13a 8b-> 13b 0.054918 + 8a-> 13a 9b-> 13b 0.047582 + 9a-> 13a 8b-> 13b 0.047582 + 5a-> 13a 5b-> 13b 0.030301 + 11a-> 13a 11b-> 13b 0.027736 + 8a-> 13a -1a-> -1a 0.027402 + 8b-> 13b -1b-> -1b 0.027402 + 11a-> 24a 11b-> 24b 0.026474 + 11a-> 25a 11b-> 25b 0.024263 + 11a-> 25a 11b-> 24b 0.023940 + 11a-> 24a 11b-> 25b 0.023940 + 9a-> 13a 9b-> 22b 0.023275 + 9a-> 22a 9b-> 13b 0.023275 + 11a-> 24a -1a-> -1a 0.020737 + 11b-> 24b -1b-> -1b 0.020737 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034631484 + alpha-alpha-alpha ... -0.000861689 ( 2.5%) + alpha-alpha-beta ... -0.016454053 ( 47.5%) + alpha-beta -beta ... -0.016454053 ( 47.5%) + beta -beta -beta ... -0.000861689 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034631484 + +Final correlation energy ... -0.729872702 +E(CCSD) ... -205.400106166 +E(CCSD(T)) ... -205.434737650 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210952473 sqrt= 1.100432857 +W(HF) = 0.825796241 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.322482 -0.000000 + 1 N : 0.182807 0.000000 + 2 O : -0.099563 0.000000 + 3 H : 0.239238 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.844654 s : 3.844654 + pz : 1.277933 p : 4.414283 + px : 1.511216 + py : 1.625135 + dz2 : 0.015058 d : 0.055504 + dxz : 0.012747 + dyz : 0.011452 + dx2y2 : 0.008071 + dxy : 0.008176 + f0 : 0.001882 f : 0.008040 + f+1 : 0.001099 + f-1 : 0.001306 + f+2 : 0.000768 + f-2 : 0.000948 + f+3 : 0.000860 + f-3 : 0.001177 + 1 N s : 3.875778 s : 3.875778 + pz : 0.891602 p : 2.746786 + px : 0.891688 + py : 0.963497 + dz2 : 0.034262 d : 0.165141 + dxz : 0.048548 + dyz : 0.026767 + dx2y2 : 0.032063 + dxy : 0.023501 + f0 : 0.007946 f : 0.029487 + f+1 : 0.003198 + f-1 : 0.005431 + f+2 : 0.002730 + f-2 : 0.004846 + f+3 : 0.003227 + f-3 : 0.002109 + 2 O s : 3.863067 s : 3.863067 + pz : 1.674561 p : 4.142774 + px : 1.185498 + py : 1.282716 + dz2 : 0.009942 d : 0.083858 + dxz : 0.017411 + dyz : 0.013554 + dx2y2 : 0.027352 + dxy : 0.015599 + f0 : 0.001644 f : 0.009864 + f+1 : 0.001180 + f-1 : 0.001011 + f+2 : 0.000636 + f-2 : 0.001593 + f+3 : 0.002399 + f-3 : 0.001401 + 3 H s : 0.649403 s : 0.649403 + pz : 0.023485 p : 0.094218 + px : 0.033530 + py : 0.037203 + dz2 : 0.001264 d : 0.017142 + dxz : 0.003936 + dyz : 0.003099 + dx2y2 : 0.008874 + dxy : -0.000030 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.575082 0.000000 + 1 N : -0.274165 0.000000 + 2 O : 0.291823 -0.000000 + 3 H : -0.592740 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.143601 s : 3.143601 + pz : 1.212916 p : 3.916030 + px : 1.316613 + py : 1.386501 + dz2 : 0.096329 d : 0.284807 + dxz : 0.073496 + dyz : 0.054506 + dx2y2 : 0.020008 + dxy : 0.040469 + f0 : 0.020988 f : 0.080479 + f+1 : 0.018387 + f-1 : 0.015220 + f+2 : 0.009518 + f-2 : 0.009213 + f+3 : 0.003159 + f-3 : 0.003994 + 1 N s : 3.045149 s : 3.045149 + pz : 0.898230 p : 2.879645 + px : 1.001322 + py : 0.980094 + dz2 : 0.206833 d : 0.923569 + dxz : 0.261535 + dyz : 0.123925 + dx2y2 : 0.138271 + dxy : 0.193004 + f0 : 0.098282 f : 0.425802 + f+1 : 0.058711 + f-1 : 0.054251 + f+2 : 0.029543 + f-2 : 0.070464 + f+3 : 0.060847 + f-3 : 0.053704 + 2 O s : 3.319994 s : 3.319994 + pz : 1.387595 p : 3.903928 + px : 1.279963 + py : 1.236370 + dz2 : 0.055790 d : 0.358362 + dxz : 0.084173 + dyz : 0.031660 + dx2y2 : 0.067730 + dxy : 0.119008 + f0 : 0.014363 f : 0.125893 + f+1 : 0.016937 + f-1 : 0.010552 + f+2 : 0.008380 + f-2 : 0.020012 + f+3 : 0.029916 + f-3 : 0.025733 + 3 H s : 0.627317 s : 0.627317 + pz : 0.146490 p : 0.586232 + px : 0.220239 + py : 0.219504 + dz2 : 0.033148 d : 0.379190 + dxz : 0.081288 + dyz : 0.056716 + dx2y2 : 0.115291 + dxy : 0.092748 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3225 8.0000 -0.3225 2.1646 1.6998 0.4649 + 1 N 6.8172 7.0000 0.1828 2.8610 2.3645 0.4965 + 2 O 8.0996 8.0000 -0.0996 2.2006 1.7011 0.4996 + 3 H 0.7608 1.0000 0.2392 1.0103 0.9357 0.0746 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7179 B( 0-O , 3-H ) : 0.8947 B( 1-N , 2-O ) : 1.6098 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 72.756 sec + +Fock Matrix Formation ... 0.267 sec ( 0.4%) +Initial Guess ... 0.140 sec ( 0.2%) +DIIS Solver ... 3.150 sec ( 4.3%) +State Vector Update ... 0.130 sec ( 0.2%) +Sigma-vector construction ... 50.143 sec ( 68.9%) + <0|H|D> ... 0.005 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.035 sec ( 0.1% of sigma) + (0-ext) ... 0.094 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.033 sec ( 0.1% of sigma) + (2-ext) ... 1.167 sec ( 2.3% of sigma) + (4-ext) ... 29.278 sec ( 58.4% of sigma) + ... 1.985 sec ( 4.0% of sigma) + ... 0.003 sec ( 0.0% of sigma) + (1-ext) ... 0.010 sec ( 0.0% of sigma) + (1-ext) ... 0.139 sec ( 0.3% of sigma) + Fock-dressing ... 2.596 sec ( 5.2% of sigma) + (ik|jl)-dressing ... 0.107 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 11.787 sec ( 23.5% of sigma) + Pair energies ... 0.010 sec ( 0.0% of sigma) +Total Time for computing (T) ... 9.648 sec ( 13.3% of ALL) + I/O of integral and amplitudes ... 1.312 sec ( 13.6% of (T)) + External N**7 contributions ... 4.961 sec ( 51.4% of (T)) + Internal N**7 contributions ... 0.398 sec ( 4.1% of (T)) + N**6 triples energy contributions ... 2.136 sec ( 22.1% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.434737649729 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.002037771 -0.004286894 -0.000128150 + 2 N : 0.000189014 -0.004501623 0.002084105 + 3 O : 0.001578053 0.004324928 -0.002352625 + 4 H : 0.000270703 0.004463589 0.000396671 + +Norm of the cartesian gradient ... 0.009699204 +RMS gradient ... 0.002799919 +MAX gradient ... 0.004501623 + +------- +TIMINGS +------- + +Total numerical gradient time ... 445.265 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: -521.59 cm**-1 ***imaginary mode*** + 7: 535.52 cm**-1 + 8: 778.43 cm**-1 + 9: 1111.65 cm**-1 + 10: 1703.15 cm**-1 + 11: 3723.35 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 -0.053663 -0.431751 0.144871 -0.019284 0.019931 -0.046646 + 1 -0.042379 -0.055493 0.232652 0.024923 -0.020903 0.040217 + 2 -0.008275 0.534020 0.212109 -0.059636 -0.076368 -0.011336 + 3 0.048322 0.271993 0.075886 0.030529 0.587161 -0.000620 + 4 -0.056535 0.101771 -0.336959 -0.031576 0.459810 -0.000432 + 5 0.021594 -0.250073 -0.706745 0.006796 0.011796 -0.000068 + 6 -0.027381 0.220068 -0.217066 0.010936 -0.535508 0.000508 + 7 0.043422 -0.024579 0.052812 0.002543 -0.380705 0.000632 + 8 -0.018792 -0.325402 0.397277 -0.006356 0.065010 -0.000306 + 9 0.614859 -0.419741 0.091378 -0.291726 0.024151 0.740925 + 10 0.769050 -0.143284 0.151436 0.002837 -0.015104 -0.642351 + 11 0.129544 0.163788 0.148623 0.952994 0.016375 0.185719 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 7: 535.52 0.026341 133.12 0.015350 ( 0.081914 0.001960 -0.092929) + 8: 778.43 0.022203 112.21 0.008901 ( 0.053900 -0.009396 -0.076861) + 9: 1111.65 0.013475 68.10 0.003783 (-0.032234 0.016018 0.049872) + 10: 1703.15 0.034053 172.09 0.006239 ( 0.058549 0.012249 -0.051588) + 11: 3723.35 0.011840 59.83 0.000992 ( 0.026013 -0.015618 -0.008467) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 7 +The total number of vibrations considered is 5 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 535.52 E(vib) ... 0.12 +freq. 778.43 E(vib) ... 0.05 +freq. 1111.65 E(vib) ... 0.01 +freq. 1703.15 E(vib) ... 0.00 +freq. 3723.35 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.43473765 Eh +Zero point energy ... 0.01788839 Eh 11.23 kcal/mol +Thermal vibrational correction ... 0.00030992 Eh 0.19 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.41370679 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00314247 Eh 1.97 kcal/mol +Non-thermal (ZPE) correction 0.01788839 Eh 11.23 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02103086 Eh 13.20 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.41370679 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.41276258 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.734506 0.396766 0.358602 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00041144 Eh 0.26 kcal/mol +Rotational entropy ... 0.00995646 Eh 6.25 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02817023 Eh 17.68 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00995646 Eh 6.25 kcal/mol| +| sn= 2 | S(rot)= 0.00930201 Eh 5.84 kcal/mol| +| sn= 3 | S(rot)= 0.00891918 Eh 5.60 kcal/mol| +| sn= 4 | S(rot)= 0.00864755 Eh 5.43 kcal/mol| +| sn= 5 | S(rot)= 0.00843686 Eh 5.29 kcal/mol| +| sn= 6 | S(rot)= 0.00826472 Eh 5.19 kcal/mol| +| sn= 7 | S(rot)= 0.00811917 Eh 5.09 kcal/mol| +| sn= 8 | S(rot)= 0.00799310 Eh 5.02 kcal/mol| +| sn= 9 | S(rot)= 0.00788189 Eh 4.95 kcal/mol| +| sn=10 | S(rot)= 0.00778241 Eh 4.88 kcal/mol| +| sn=11 | S(rot)= 0.00769242 Eh 4.83 kcal/mol| +| sn=12 | S(rot)= 0.00761026 Eh 4.78 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.41276258 Eh +Total entropy correction ... -0.02817023 Eh -17.68 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44093281 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00619516 Eh -3.89 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.434737649 Eh +Current gradient norm .... 0.009699204 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + -0.028957959 0.093483541 0.154805658 0.466527492 0.498057118 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999967014 +Lowest eigenvalues of augmented Hessian: + -0.000038852 0.093442908 0.154587839 0.466203945 0.498052145 +Length of the computed step .... 0.008122465 +The final length of the internal step .... 0.008122465 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0033159825 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0032391828 RMS(Int)= 0.0033152291 + Iter 1: RMS(Cart)= 0.0000035733 RMS(Int)= 0.0000047332 + Iter 2: RMS(Cart)= 0.0000000084 RMS(Int)= 0.0000000145 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0021172052 0.0001000000 NO + MAX gradient 0.0040292853 0.0003000000 NO + RMS step 0.0033159825 0.0020000000 NO + MAX step 0.0052164422 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0028 Max(Angles) 0.18 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.5082 0.000986 -0.0012 1.5070 + 2. B(O 2,N 1) 1.1666 0.004029 -0.0022 1.1643 + 3. B(H 3,O 0) 0.9723 0.002614 -0.0028 0.9696 + 4. A(N 1,O 0,H 3) 102.84 0.000664 -0.18 102.67 + 5. A(O 0,N 1,O 2) 110.89 0.001554 -0.14 110.75 + 6. D(O 2,N 1,O 0,H 3) 98.18 -0.006509 0.00 98.18 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.363908 -0.206171 0.763108 + N 0.246438 -0.437866 -0.595151 + O 1.194717 0.222162 -0.739268 + H -1.077247 0.421875 0.571311 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.687686 -0.389607 1.442066 + 1 N 7.0000 0 14.007 0.465701 -0.827447 -1.124673 + 2 O 8.0000 0 15.999 2.257689 0.419825 -1.397014 + 3 H 1.0000 0 1.008 -2.035702 0.797229 1.079621 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.507008359916 0.00000000 0.00000000 + O 2 1 0 1.164319474499 110.74820599 0.00000000 + H 1 2 3 0.969578291438 102.66612671 98.18181802 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.847833081771 0.00000000 0.00000000 + O 2 1 0 2.200244939193 110.74820599 0.00000000 + H 1 2 3 1.832237436214 102.66612671 98.18181802 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2228 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2695 + la=0 lb=0: 548 shell pairs + la=1 lb=0: 535 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.325684106097 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.899e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7054682297 0.000000000000 0.00018996 0.00000450 0.0007335 0.7000 + 1 -204.7054709021 -0.000002672382 0.00015869 0.00000364 0.0005589 0.7000 + ***Turning on DIIS*** + 2 -204.7054729809 -0.000002078733 0.00041035 0.00000920 0.0004165 0.0000 + 3 -204.7051721013 0.000300879556 0.00009601 0.00000260 0.0000967 0.0000 + 4 -204.7054043176 -0.000232216334 0.00002565 0.00000101 0.0000461 0.0000 + 5 -204.7056565589 -0.000252241298 0.00001188 0.00000058 0.0000294 0.0000 + 6 -204.7054262955 0.000230263404 0.00001028 0.00000041 0.0000131 0.0000 + 7 -204.7054924480 -0.000066152471 0.00000902 0.00000034 0.0000092 0.0000 + 8 -204.7054841233 0.000008324700 0.00000615 0.00000022 0.0000057 0.0000 + 9 -204.7054662891 0.000017834159 0.00000367 0.00000013 0.0000030 0.0000 + 10 -204.7054841731 -0.000017883939 0.00000232 0.00000008 0.0000021 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + +Total Energy : -204.70547771 Eh -5570.31924 eV + Last Energy change ... 6.4609e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.6411e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.204 sec +Reference energy ... -204.705479292 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.404 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.079 sec +K-integral sorting ... 5.414 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.025 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.029 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.045 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.038 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.359 sec +AO-integral generation ... 0.249 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.054 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.144 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.252 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090036317 +EMP2(bb)= -0.090036317 +EMP2(ab)= -0.517585675 + +Initial guess performed in 0.130 sec +E(0) ... -204.705479292 +E(MP2) ... -0.697658309 +Initial E(tot) ... -205.403137601 + ... 0.189742169 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.403137601 -0.697658309 -0.000000000 0.018790831 2.72 0.000000677 + *** Turning on DIIS *** + 1 -205.374731284 -0.669251992 0.028406317 0.010619498 2.72 0.055512880 + 2 -205.394290184 -0.688810892 -0.019558900 0.003682710 2.79 0.058192228 + 3 -205.398117327 -0.692638035 -0.003827143 0.002029945 2.82 0.071067064 + 4 -205.399652303 -0.694173011 -0.001534976 0.000946394 2.77 0.076734563 + 5 -205.400132700 -0.694653408 -0.000480397 0.000393660 2.90 0.080913065 + 6 -205.400207305 -0.694728013 -0.000074605 0.000265027 2.84 0.082775930 + 7 -205.400236463 -0.694757171 -0.000029158 0.000202628 3.21 0.083581557 + 8 -205.400242723 -0.694763431 -0.000006260 0.000150384 3.08 0.083924939 + 9 -205.400239595 -0.694760303 0.000003128 0.000104270 2.88 0.084063159 + 10 -205.400243982 -0.694764690 -0.000004387 0.000056391 2.97 0.084142662 + 11 -205.400240490 -0.694761197 0.000003492 0.000026720 2.95 0.084167077 + 12 -205.400243212 -0.694763919 -0.000002722 0.000012235 2.91 0.084185196 + 13 -205.400243291 -0.694763999 -0.000000080 0.000006301 2.89 0.084187188 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.705479292 +E(CORR) ... -0.694763999 +E(TOT) ... -205.400243291 +Singles norm **1/2 ... 0.084187188 ( 0.042093594, 0.042093594) +T1 diagnostic ... 0.019843110 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.060516 + 8a-> 13a 8b-> 13b 0.054821 + 9a-> 13a 8b-> 13b 0.047210 + 8a-> 13a 9b-> 13b 0.047210 + 5a-> 13a 5b-> 13b 0.030173 + 11a-> 13a 11b-> 13b 0.027651 + 8b-> 13b -1b-> -1b 0.027164 + 8a-> 13a -1a-> -1a 0.027164 + 11a-> 24a 11b-> 24b 0.025872 + 11a-> 25a 11b-> 25b 0.024726 + 11a-> 24a 11b-> 25b 0.023889 + 11a-> 25a 11b-> 24b 0.023889 + 9a-> 13a 9b-> 22b 0.023203 + 9a-> 22a 9b-> 13b 0.023203 + 11a-> 24a -1a-> -1a 0.020389 + 11b-> 24b -1b-> -1b 0.020389 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034513706 + alpha-alpha-alpha ... -0.000860019 ( 2.5%) + alpha-alpha-beta ... -0.016396834 ( 47.5%) + alpha-beta -beta ... -0.016396834 ( 47.5%) + beta -beta -beta ... -0.000860019 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034513706 + +Final correlation energy ... -0.729277705 +E(CCSD) ... -205.400243291 +E(CCSD(T)) ... -205.434756997 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210273640 sqrt= 1.100124375 +W(HF) = 0.826259423 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 55.646 sec + +Fock Matrix Formation ... 0.204 sec ( 0.4%) +Initial Guess ... 0.130 sec ( 0.2%) +DIIS Solver ... 1.747 sec ( 3.1%) +State Vector Update ... 0.083 sec ( 0.1%) +Sigma-vector construction ... 38.598 sec ( 69.4%) + <0|H|D> ... 0.005 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.025 sec ( 0.1% of sigma) + (0-ext) ... 0.073 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (2-ext) ... 0.940 sec ( 2.4% of sigma) + (4-ext) ... 21.536 sec ( 55.8% of sigma) + ... 1.547 sec ( 4.0% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.108 sec ( 0.3% of sigma) + Fock-dressing ... 2.142 sec ( 5.5% of sigma) + (ik|jl)-dressing ... 0.075 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.516 sec ( 24.7% of sigma) + Pair energies ... 0.006 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.881 sec ( 12.4% of ALL) + I/O of integral and amplitudes ... 0.680 sec ( 9.9% of (T)) + External N**7 contributions ... 3.901 sec ( 56.7% of (T)) + Internal N**7 contributions ... 0.311 sec ( 4.5% of (T)) + N**6 triples energy contributions ... 1.599 sec ( 23.2% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.434756997031 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.003162280 -0.002557948 -0.000999244 + 2 N : 0.002693266 -0.002560502 0.001640035 + 3 O : -0.001870578 0.002315350 -0.001212935 + 4 H : 0.002339592 0.002803100 0.000572144 + +Norm of the cartesian gradient ... 0.007617788 +RMS gradient ... 0.002199066 +MAX gradient ... 0.003162280 + +------- +TIMINGS +------- + +Total numerical gradient time ... 356.244 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.434756997 Eh +Current gradient norm .... 0.007617788 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999992 +Lowest eigenvalues of augmented Hessian: + -0.000000006 0.093439857 0.154413757 0.465444091 0.498966890 +Length of the computed step .... 0.000125113 +The final length of the internal step .... 0.000125113 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0000510774 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0000273348 RMS(Int)= 0.0000510774 + Iter 1: RMS(Cart)= 0.0000000010 RMS(Int)= 0.0000000013 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000193479 0.0000050000 NO + RMS gradient 0.0000267314 0.0001000000 YES + MAX gradient 0.0000606876 0.0003000000 YES + RMS step 0.0000510774 0.0020000000 YES + MAX step 0.0000710893 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0000 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.5070 -0.000014 0.0000 1.5070 + 2. B(O 2,N 1) 1.1643 -0.000061 0.0000 1.1644 + 3. B(H 3,O 0) 0.9696 -0.000019 0.0000 0.9696 + 4. A(N 1,O 0,H 3) 102.67 0.000007 -0.00 102.66 + 5. A(O 0,N 1,O 2) 110.75 0.000001 -0.00 110.75 + 6. D(O 2,N 1,O 0,H 3) 98.18 -0.006609 0.00 98.18 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.363911 -0.206184 0.763144 + N 0.246426 -0.437873 -0.595163 + O 1.194733 0.222174 -0.739276 + H -1.077247 0.421883 0.571295 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.687693 -0.389632 1.442132 + 1 N 7.0000 0 14.007 0.465679 -0.827460 -1.124694 + 2 O 8.0000 0 15.999 2.257719 0.419849 -1.397029 + 3 H 1.0000 0 1.008 -2.035702 0.797243 1.079591 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.507045978774 0.00000000 0.00000000 + O 2 1 0 1.164352626925 110.74741481 0.00000000 + H 1 2 3 0.969599126069 102.66210212 98.18181802 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.847904171109 0.00000000 0.00000000 + O 2 1 0 2.200307588199 110.74741481 0.00000000 + H 1 2 3 1.832276807960 102.66210212 98.18181802 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2228 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2695 + la=0 lb=0: 548 shell pairs + la=1 lb=0: 535 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 395 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.324039476971 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.3240394770 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.899e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7054692679 0.000000000000 0.00000170 0.00000006 0.0000098 0.7000 + 1 -204.7054692688 -0.000000000825 0.00000136 0.00000004 0.0000072 0.7000 + ***Turning on DIIS*** + 2 -204.7054692696 -0.000000000836 0.00000354 0.00000011 0.0000053 0.0000 + 3 -204.7054734989 -0.000004229328 0.00000145 0.00000004 0.0000012 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 4 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70547011 Eh -5570.31903 eV + +Components: +Nuclear Repulsion : 68.32403948 Eh 1859.19163 eV +Electronic Energy : -273.02950958 Eh -7429.51066 eV +One Electron Energy: -416.35944417 Eh -11329.71647 eV +Two Electron Energy: 143.32993459 Eh 3900.20580 eV + +Virial components: +Potential Energy : -408.93315505 Eh -11127.63687 eV +Kinetic Energy : 204.22768494 Eh 5557.31784 eV +Virial Ratio : 2.00233947 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.3922e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.2554e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.6589e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.9911e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.692537 -563.0726 + 1 1.0000 -20.615602 -560.9791 + 2 1.0000 -15.805380 -430.0862 + 3 1.0000 -1.618429 -44.0397 + 4 1.0000 -1.370584 -37.2955 + 5 1.0000 -0.954455 -25.9721 + 6 1.0000 -0.768174 -20.9031 + 7 1.0000 -0.732120 -19.9220 + 8 1.0000 -0.699667 -19.0389 + 9 1.0000 -0.606420 -16.5015 + 10 1.0000 -0.528476 -14.3806 + 11 1.0000 -0.457939 -12.4612 + 12 0.0000 0.030803 0.8382 + 13 0.0000 0.067121 1.8264 + 14 0.0000 0.091523 2.4905 + 15 0.0000 0.102397 2.7864 + 16 0.0000 0.113510 3.0888 + 17 0.0000 0.155219 4.2237 + 18 0.0000 0.157285 4.2799 + 19 0.0000 0.173742 4.7278 + 20 0.0000 0.181484 4.9384 + 21 0.0000 0.189678 5.1614 + 22 0.0000 0.200840 5.4651 + 23 0.0000 0.236143 6.4258 + 24 0.0000 0.268606 7.3091 + 25 0.0000 0.290067 7.8931 + 26 0.0000 0.301175 8.1954 + 27 0.0000 0.330333 8.9888 + 28 0.0000 0.332300 9.0423 + 29 0.0000 0.353200 9.6111 + 30 0.0000 0.425256 11.5718 + 31 0.0000 0.505184 13.7468 + 32 0.0000 0.527115 14.3435 + 33 0.0000 0.543869 14.7994 + 34 0.0000 0.571481 15.5508 + 35 0.0000 0.600959 16.3529 + 36 0.0000 0.630086 17.1455 + 37 0.0000 0.649407 17.6713 + 38 0.0000 0.702399 19.1132 + 39 0.0000 0.719090 19.5674 + 40 0.0000 0.739453 20.1216 + 41 0.0000 0.753438 20.5021 + 42 0.0000 0.764966 20.8158 + 43 0.0000 0.791772 21.5452 + 44 0.0000 0.811807 22.0904 + 45 0.0000 0.813382 22.1332 + 46 0.0000 0.860250 23.4086 + 47 0.0000 0.869850 23.6698 + 48 0.0000 0.894747 24.3473 + 49 0.0000 0.940654 25.5965 + 50 0.0000 0.958825 26.0910 + 51 0.0000 0.985974 26.8297 + 52 0.0000 0.995641 27.0928 + 53 0.0000 1.027709 27.9654 + 54 0.0000 1.047397 28.5011 + 55 0.0000 1.113118 30.2895 + 56 0.0000 1.145284 31.1647 + 57 0.0000 1.230886 33.4941 + 58 0.0000 1.250156 34.0185 + 59 0.0000 1.270007 34.5586 + 60 0.0000 1.316656 35.8280 + 61 0.0000 1.413192 38.4549 + 62 0.0000 1.443327 39.2749 + 63 0.0000 1.518884 41.3309 + 64 0.0000 1.522580 41.4315 + 65 0.0000 1.567332 42.6493 + 66 0.0000 1.584441 43.1148 + 67 0.0000 1.633286 44.4440 + 68 0.0000 1.648585 44.8603 + 69 0.0000 1.709897 46.5287 + 70 0.0000 1.772986 48.2454 + 71 0.0000 1.790145 48.7123 + 72 0.0000 1.885079 51.2956 + 73 0.0000 1.925997 52.4090 + 74 0.0000 1.984078 53.9895 + 75 0.0000 2.020024 54.9677 + 76 0.0000 2.056064 55.9483 + 77 0.0000 2.082425 56.6657 + 78 0.0000 2.139633 58.2224 + 79 0.0000 2.211511 60.1783 + 80 0.0000 2.247409 61.1551 + 81 0.0000 2.296565 62.4927 + 82 0.0000 2.315340 63.0036 + 83 0.0000 2.365799 64.3767 + 84 0.0000 2.407461 65.5103 + 85 0.0000 2.452668 66.7405 + 86 0.0000 2.461119 66.9705 + 87 0.0000 2.476998 67.4025 + 88 0.0000 2.506001 68.1917 + 89 0.0000 2.559365 69.6439 + 90 0.0000 2.568778 69.9000 + 91 0.0000 2.598442 70.7072 + 92 0.0000 2.676253 72.8245 + 93 0.0000 2.721036 74.0431 + 94 0.0000 2.750365 74.8412 + 95 0.0000 2.800760 76.2126 + 96 0.0000 2.847015 77.4712 + 97 0.0000 2.878251 78.3212 + 98 0.0000 2.954907 80.4071 + 99 0.0000 2.987659 81.2983 + 100 0.0000 3.050984 83.0215 + 101 0.0000 3.164086 86.0991 + 102 0.0000 3.227885 87.8352 + 103 0.0000 3.486187 94.8640 + 104 0.0000 3.730400 101.5094 + 105 0.0000 3.809818 103.6704 + 106 0.0000 4.053414 110.2990 + 107 0.0000 4.176553 113.6498 + 108 0.0000 4.187059 113.9357 + 109 0.0000 4.298244 116.9612 + 110 0.0000 4.350544 118.3843 + 111 0.0000 4.392996 119.5395 + 112 0.0000 4.524486 123.1175 + 113 0.0000 4.604808 125.3032 + 114 0.0000 4.665253 126.9480 + 115 0.0000 4.719842 128.4334 + 116 0.0000 4.820531 131.1733 + 117 0.0000 4.900479 133.3488 + 118 0.0000 4.932526 134.2209 + 119 0.0000 4.948425 134.6535 + 120 0.0000 5.051816 137.4669 + 121 0.0000 5.099376 138.7611 + 122 0.0000 5.186248 141.1250 + 123 0.0000 5.196260 141.3974 + 124 0.0000 5.212074 141.8277 + 125 0.0000 5.333795 145.1400 + 126 0.0000 5.373326 146.2156 + 127 0.0000 5.479723 149.1108 + 128 0.0000 5.541698 150.7973 + 129 0.0000 5.725817 155.8074 + 130 0.0000 5.737297 156.1198 + 131 0.0000 5.928238 161.3156 + 132 0.0000 6.179750 168.1595 + 133 0.0000 6.414756 174.5544 + 134 0.0000 6.483434 176.4232 + 135 0.0000 6.501786 176.9226 + 136 0.0000 6.701300 182.3516 + 137 0.0000 6.728361 183.0880 + 138 0.0000 6.769363 184.2037 + 139 0.0000 6.812725 185.3837 + 140 0.0000 6.824687 185.7092 + 141 0.0000 7.063210 192.1997 + 142 0.0000 7.099815 193.1958 + 143 0.0000 7.119240 193.7244 + 144 0.0000 7.198860 195.8909 + 145 0.0000 7.257681 197.4915 + 146 0.0000 7.282822 198.1757 + 147 0.0000 7.347076 199.9241 + 148 0.0000 7.388929 201.0630 + 149 0.0000 7.448759 202.6910 + 150 0.0000 7.460755 203.0175 + 151 0.0000 7.553268 205.5349 + 152 0.0000 7.586381 206.4359 + 153 0.0000 7.611108 207.1088 + 154 0.0000 7.735841 210.5029 + 155 0.0000 7.902340 215.0336 + 156 0.0000 7.919450 215.4992 + 157 0.0000 8.397531 228.5084 + 158 0.0000 14.065084 382.7304 + 159 0.0000 14.830285 403.5526 + 160 0.0000 16.099643 438.0936 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.692537 -563.0726 + 1 1.0000 -20.615602 -560.9791 + 2 1.0000 -15.805380 -430.0862 + 3 1.0000 -1.618429 -44.0397 + 4 1.0000 -1.370584 -37.2955 + 5 1.0000 -0.954455 -25.9721 + 6 1.0000 -0.768174 -20.9031 + 7 1.0000 -0.732120 -19.9220 + 8 1.0000 -0.699667 -19.0389 + 9 1.0000 -0.606420 -16.5015 + 10 1.0000 -0.528476 -14.3806 + 11 1.0000 -0.457939 -12.4612 + 12 0.0000 0.030803 0.8382 + 13 0.0000 0.067121 1.8264 + 14 0.0000 0.091523 2.4905 + 15 0.0000 0.102397 2.7864 + 16 0.0000 0.113510 3.0888 + 17 0.0000 0.155219 4.2237 + 18 0.0000 0.157285 4.2799 + 19 0.0000 0.173742 4.7278 + 20 0.0000 0.181484 4.9384 + 21 0.0000 0.189678 5.1614 + 22 0.0000 0.200840 5.4651 + 23 0.0000 0.236143 6.4258 + 24 0.0000 0.268606 7.3091 + 25 0.0000 0.290067 7.8931 + 26 0.0000 0.301175 8.1954 + 27 0.0000 0.330333 8.9888 + 28 0.0000 0.332300 9.0423 + 29 0.0000 0.353200 9.6111 + 30 0.0000 0.425256 11.5718 + 31 0.0000 0.505184 13.7468 + 32 0.0000 0.527115 14.3435 + 33 0.0000 0.543869 14.7994 + 34 0.0000 0.571481 15.5508 + 35 0.0000 0.600959 16.3529 + 36 0.0000 0.630086 17.1455 + 37 0.0000 0.649407 17.6713 + 38 0.0000 0.702399 19.1132 + 39 0.0000 0.719090 19.5674 + 40 0.0000 0.739453 20.1216 + 41 0.0000 0.753438 20.5021 + 42 0.0000 0.764966 20.8158 + 43 0.0000 0.791772 21.5452 + 44 0.0000 0.811807 22.0904 + 45 0.0000 0.813382 22.1332 + 46 0.0000 0.860250 23.4086 + 47 0.0000 0.869850 23.6698 + 48 0.0000 0.894747 24.3473 + 49 0.0000 0.940654 25.5965 + 50 0.0000 0.958825 26.0910 + 51 0.0000 0.985974 26.8297 + 52 0.0000 0.995641 27.0928 + 53 0.0000 1.027709 27.9654 + 54 0.0000 1.047397 28.5011 + 55 0.0000 1.113118 30.2895 + 56 0.0000 1.145284 31.1647 + 57 0.0000 1.230886 33.4941 + 58 0.0000 1.250156 34.0185 + 59 0.0000 1.270007 34.5586 + 60 0.0000 1.316656 35.8280 + 61 0.0000 1.413192 38.4549 + 62 0.0000 1.443327 39.2749 + 63 0.0000 1.518884 41.3309 + 64 0.0000 1.522580 41.4315 + 65 0.0000 1.567332 42.6493 + 66 0.0000 1.584441 43.1148 + 67 0.0000 1.633286 44.4440 + 68 0.0000 1.648585 44.8603 + 69 0.0000 1.709897 46.5287 + 70 0.0000 1.772986 48.2454 + 71 0.0000 1.790145 48.7123 + 72 0.0000 1.885079 51.2956 + 73 0.0000 1.925997 52.4090 + 74 0.0000 1.984078 53.9895 + 75 0.0000 2.020024 54.9677 + 76 0.0000 2.056064 55.9483 + 77 0.0000 2.082425 56.6657 + 78 0.0000 2.139633 58.2224 + 79 0.0000 2.211511 60.1783 + 80 0.0000 2.247409 61.1551 + 81 0.0000 2.296565 62.4927 + 82 0.0000 2.315340 63.0036 + 83 0.0000 2.365799 64.3767 + 84 0.0000 2.407461 65.5103 + 85 0.0000 2.452668 66.7405 + 86 0.0000 2.461119 66.9705 + 87 0.0000 2.476998 67.4025 + 88 0.0000 2.506001 68.1917 + 89 0.0000 2.559365 69.6439 + 90 0.0000 2.568778 69.9000 + 91 0.0000 2.598442 70.7072 + 92 0.0000 2.676253 72.8245 + 93 0.0000 2.721036 74.0431 + 94 0.0000 2.750365 74.8412 + 95 0.0000 2.800760 76.2126 + 96 0.0000 2.847015 77.4712 + 97 0.0000 2.878251 78.3212 + 98 0.0000 2.954907 80.4071 + 99 0.0000 2.987659 81.2983 + 100 0.0000 3.050984 83.0215 + 101 0.0000 3.164086 86.0991 + 102 0.0000 3.227885 87.8352 + 103 0.0000 3.486187 94.8640 + 104 0.0000 3.730400 101.5094 + 105 0.0000 3.809818 103.6704 + 106 0.0000 4.053414 110.2990 + 107 0.0000 4.176553 113.6498 + 108 0.0000 4.187059 113.9357 + 109 0.0000 4.298244 116.9612 + 110 0.0000 4.350544 118.3843 + 111 0.0000 4.392996 119.5395 + 112 0.0000 4.524486 123.1175 + 113 0.0000 4.604808 125.3032 + 114 0.0000 4.665253 126.9480 + 115 0.0000 4.719842 128.4334 + 116 0.0000 4.820531 131.1733 + 117 0.0000 4.900479 133.3488 + 118 0.0000 4.932526 134.2209 + 119 0.0000 4.948425 134.6535 + 120 0.0000 5.051816 137.4669 + 121 0.0000 5.099376 138.7611 + 122 0.0000 5.186248 141.1250 + 123 0.0000 5.196260 141.3974 + 124 0.0000 5.212074 141.8277 + 125 0.0000 5.333795 145.1400 + 126 0.0000 5.373326 146.2156 + 127 0.0000 5.479723 149.1108 + 128 0.0000 5.541698 150.7973 + 129 0.0000 5.725817 155.8074 + 130 0.0000 5.737297 156.1198 + 131 0.0000 5.928238 161.3156 + 132 0.0000 6.179750 168.1595 + 133 0.0000 6.414756 174.5544 + 134 0.0000 6.483434 176.4232 + 135 0.0000 6.501786 176.9226 + 136 0.0000 6.701300 182.3516 + 137 0.0000 6.728361 183.0880 + 138 0.0000 6.769363 184.2037 + 139 0.0000 6.812725 185.3837 + 140 0.0000 6.824687 185.7092 + 141 0.0000 7.063210 192.1997 + 142 0.0000 7.099815 193.1958 + 143 0.0000 7.119240 193.7244 + 144 0.0000 7.198860 195.8909 + 145 0.0000 7.257681 197.4915 + 146 0.0000 7.282822 198.1757 + 147 0.0000 7.347076 199.9241 + 148 0.0000 7.388929 201.0630 + 149 0.0000 7.448759 202.6910 + 150 0.0000 7.460755 203.0175 + 151 0.0000 7.553268 205.5349 + 152 0.0000 7.586381 206.4359 + 153 0.0000 7.611108 207.1088 + 154 0.0000 7.735841 210.5029 + 155 0.0000 7.902340 215.0336 + 156 0.0000 7.919450 215.4992 + 157 0.0000 8.397531 228.5084 + 158 0.0000 14.065084 382.7304 + 159 0.0000 14.830285 403.5526 + 160 0.0000 16.099643 438.0936 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.378566 0.000000 + 1 N : 0.354501 0.000000 + 2 O : -0.225319 0.000000 + 3 H : 0.249383 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.867615 s : 3.867615 + pz : 1.295931 p : 4.482393 + px : 1.527263 + py : 1.659198 + dz2 : 0.010297 d : 0.024269 + dxz : 0.007429 + dyz : 0.004279 + dx2y2 : 0.000656 + dxy : 0.001607 + f0 : 0.001539 f : 0.004288 + f+1 : 0.000773 + f-1 : 0.000764 + f+2 : 0.000158 + f-2 : 0.000312 + f+3 : 0.000218 + f-3 : 0.000525 + 1 N s : 3.821661 s : 3.821661 + pz : 0.845371 p : 2.657215 + px : 0.869216 + py : 0.942628 + dz2 : 0.027347 d : 0.136079 + dxz : 0.040063 + dyz : 0.018894 + dx2y2 : 0.031176 + dxy : 0.018599 + f0 : 0.008394 f : 0.030543 + f+1 : 0.003430 + f-1 : 0.005359 + f+2 : 0.002224 + f-2 : 0.005021 + f+3 : 0.003921 + f-3 : 0.002194 + 2 O s : 3.875181 s : 3.875181 + pz : 1.762046 p : 4.279330 + px : 1.204282 + py : 1.313002 + dz2 : 0.004617 d : 0.063283 + dxz : 0.010450 + dyz : 0.007862 + dx2y2 : 0.027460 + dxy : 0.012893 + f0 : 0.001203 f : 0.007525 + f+1 : 0.000714 + f-1 : 0.000562 + f+2 : 0.000008 + f-2 : 0.001224 + f+3 : 0.002635 + f-3 : 0.001179 + 3 H s : 0.643296 s : 0.643296 + pz : 0.020121 p : 0.087076 + px : 0.033381 + py : 0.033574 + dz2 : 0.001386 d : 0.020245 + dxz : 0.004442 + dyz : 0.003620 + dx2y2 : 0.010201 + dxy : 0.000594 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.573744 0.000000 + 1 N : -0.230684 0.000000 + 2 O : 0.250016 0.000000 + 3 H : -0.593076 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.137745 s : 3.137745 + pz : 1.217690 p : 3.960353 + px : 1.327626 + py : 1.415037 + dz2 : 0.090325 d : 0.254302 + dxz : 0.067064 + dyz : 0.049428 + dx2y2 : 0.014044 + dxy : 0.033440 + f0 : 0.019704 f : 0.073857 + f+1 : 0.016551 + f-1 : 0.014772 + f+2 : 0.008975 + f-2 : 0.008289 + f+3 : 0.002469 + f-3 : 0.003097 + 1 N s : 3.038614 s : 3.038614 + pz : 0.876918 p : 2.838866 + px : 0.990903 + py : 0.971046 + dz2 : 0.200511 d : 0.916995 + dxz : 0.261893 + dyz : 0.124527 + dx2y2 : 0.142478 + dxy : 0.187586 + f0 : 0.101873 f : 0.436209 + f+1 : 0.058144 + f-1 : 0.055308 + f+2 : 0.030412 + f-2 : 0.074745 + f+3 : 0.062347 + f-3 : 0.053379 + 2 O s : 3.315371 s : 3.315371 + pz : 1.442309 p : 3.984902 + px : 1.290239 + py : 1.252355 + dz2 : 0.050041 d : 0.331683 + dxz : 0.081588 + dyz : 0.026115 + dx2y2 : 0.059832 + dxy : 0.114107 + f0 : 0.013619 f : 0.118028 + f+1 : 0.016246 + f-1 : 0.010189 + f+2 : 0.007978 + f-2 : 0.018909 + f+3 : 0.026495 + f-3 : 0.024591 + 3 H s : 0.628039 s : 0.628039 + pz : 0.147258 p : 0.574569 + px : 0.214986 + py : 0.212326 + dz2 : 0.032330 d : 0.390467 + dxz : 0.084815 + dyz : 0.059095 + dx2y2 : 0.120623 + dxy : 0.093603 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3786 8.0000 -0.3786 1.8230 1.8230 0.0000 + 1 N 6.6455 7.0000 0.3545 2.5968 2.5968 -0.0000 + 2 O 8.2253 8.0000 -0.2253 1.8143 1.8143 0.0000 + 3 H 0.7506 1.0000 0.2494 0.9893 0.9893 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8086 B( 0-O , 3-H ) : 0.9585 B( 1-N , 2-O ) : 1.7578 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.016 sec +Sum of individual times .... 0.713 sec ( 70.2%) + +Fock matrix formation .... 0.517 sec ( 50.9%) +Diagonalization .... 0.056 sec ( 5.5%) +Density matrix formation .... 0.004 sec ( 0.4%) +Population analysis .... 0.087 sec ( 8.6%) +Initial guess .... 0.012 sec ( 1.2%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.007 sec ( 0.7%) +DIIS solution .... 0.036 sec ( 3.6%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.207 sec +Reference energy ... -204.705469270 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.354 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.364 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.025 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.029 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.045 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.039 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.357 sec +AO-integral generation ... 0.252 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.160 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.252 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090037588 +EMP2(bb)= -0.090037588 +EMP2(ab)= -0.517593667 + +Initial guess performed in 0.133 sec +E(0) ... -204.705469270 +E(MP2) ... -0.697668844 +Initial E(tot) ... -205.403138115 + ... 0.189751747 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.403138115 -0.697668844 -0.000000000 0.018792205 2.81 0.000001993 + *** Turning on DIIS *** + 1 -205.374727159 -0.669257889 0.028410955 0.010621613 2.77 0.055516054 + 2 -205.394287680 -0.688818410 -0.019560521 0.003683055 2.85 0.058194718 + 3 -205.398115113 -0.692645843 -0.003827433 0.002030371 2.86 0.071070408 + 4 -205.399650270 -0.694181000 -0.001535157 0.000946850 2.86 0.076738255 + 5 -205.400130752 -0.694661481 -0.000480482 0.000393838 2.89 0.080917097 + 6 -205.400205361 -0.694736091 -0.000074610 0.000264891 2.87 0.082779986 + 7 -205.400234520 -0.694765250 -0.000029159 0.000202537 2.92 0.083585608 + 8 -205.400240780 -0.694771510 -0.000006260 0.000150326 2.92 0.083928955 + 9 -205.400237651 -0.694768381 0.000003129 0.000104245 2.84 0.084067118 + 10 -205.400242037 -0.694772767 -0.000004387 0.000056395 2.81 0.084146568 + 11 -205.400238544 -0.694769274 0.000003493 0.000026729 2.96 0.084170963 + 12 -205.400241266 -0.694771996 -0.000002722 0.000012242 2.94 0.084189080 + 13 -205.400241346 -0.694772076 -0.000000080 0.000006300 2.83 0.084191069 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.705469270 +E(CORR) ... -0.694772076 +E(TOT) ... -205.400241346 +Singles norm **1/2 ... 0.084191069 ( 0.042095535, 0.042095535) +T1 diagnostic ... 0.019844025 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.060530 + 8a-> 13a 8b-> 13b 0.054819 + 8a-> 13a 9b-> 13b 0.047216 + 9a-> 13a 8b-> 13b 0.047216 + 5a-> 13a 5b-> 13b 0.030176 + 11a-> 13a 11b-> 13b 0.027650 + 8a-> 13a -1a-> -1a 0.027167 + 8b-> 13b -1b-> -1b 0.027167 + 11a-> 24a 11b-> 24b 0.025893 + 11a-> 25a 11b-> 25b 0.024716 + 11a-> 25a 11b-> 24b 0.023894 + 11a-> 24a 11b-> 25b 0.023894 + 9a-> 13a 9b-> 22b 0.023206 + 9a-> 22a 9b-> 13b 0.023206 + 11b-> 24b -1b-> -1b 0.020399 + 11a-> 24a -1a-> -1a 0.020399 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034515657 + alpha-alpha-alpha ... -0.000860043 ( 2.5%) + alpha-alpha-beta ... -0.016397786 ( 47.5%) + alpha-beta -beta ... -0.016397786 ( 47.5%) + beta -beta -beta ... -0.000860043 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034515657 + +Final correlation energy ... -0.729287733 +E(CCSD) ... -205.400241346 +E(CCSD(T)) ... -205.434757003 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210283944 sqrt= 1.100129058 +W(HF) = 0.826252389 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.320833 -0.000000 + 1 N : 0.182783 0.000000 + 2 O : -0.099298 0.000000 + 3 H : 0.237347 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.844832 s : 3.844832 + pz : 1.277338 p : 4.412652 + px : 1.511369 + py : 1.623946 + dz2 : 0.015011 d : 0.055322 + dxz : 0.012714 + dyz : 0.011460 + dx2y2 : 0.008054 + dxy : 0.008083 + f0 : 0.001887 f : 0.008027 + f+1 : 0.001094 + f-1 : 0.001307 + f+2 : 0.000764 + f-2 : 0.000949 + f+3 : 0.000856 + f-3 : 0.001170 + 1 N s : 3.875989 s : 3.875989 + pz : 0.891501 p : 2.746212 + px : 0.891887 + py : 0.962824 + dz2 : 0.034334 d : 0.165473 + dxz : 0.048701 + dyz : 0.026839 + dx2y2 : 0.032136 + dxy : 0.023464 + f0 : 0.007979 f : 0.029543 + f+1 : 0.003215 + f-1 : 0.005436 + f+2 : 0.002724 + f-2 : 0.004850 + f+3 : 0.003213 + f-3 : 0.002126 + 2 O s : 3.862449 s : 3.862449 + pz : 1.675475 p : 4.142887 + px : 1.185810 + py : 1.281602 + dz2 : 0.009950 d : 0.084083 + dxz : 0.017429 + dyz : 0.013596 + dx2y2 : 0.027475 + dxy : 0.015632 + f0 : 0.001648 f : 0.009879 + f+1 : 0.001184 + f-1 : 0.001012 + f+2 : 0.000634 + f-2 : 0.001596 + f+3 : 0.002407 + f-3 : 0.001400 + 3 H s : 0.650647 s : 0.650647 + pz : 0.023654 p : 0.094707 + px : 0.033692 + py : 0.037362 + dz2 : 0.001287 d : 0.017298 + dxz : 0.003965 + dyz : 0.003127 + dx2y2 : 0.008923 + dxy : -0.000004 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.578693 -0.000000 + 1 N : -0.274340 -0.000000 + 2 O : 0.293180 0.000000 + 3 H : -0.597532 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.141771 s : 3.141771 + pz : 1.212308 p : 3.913681 + px : 1.316262 + py : 1.385110 + dz2 : 0.096372 d : 0.285136 + dxz : 0.073610 + dyz : 0.054679 + dx2y2 : 0.020038 + dxy : 0.040438 + f0 : 0.021071 f : 0.080719 + f+1 : 0.018399 + f-1 : 0.015279 + f+2 : 0.009572 + f-2 : 0.009252 + f+3 : 0.003167 + f-3 : 0.003979 + 1 N s : 3.043412 s : 3.043412 + pz : 0.897935 p : 2.879169 + px : 1.001499 + py : 0.979735 + dz2 : 0.207078 d : 0.924921 + dxz : 0.261843 + dyz : 0.124306 + dx2y2 : 0.138452 + dxy : 0.193243 + f0 : 0.098717 f : 0.426839 + f+1 : 0.058730 + f-1 : 0.054381 + f+2 : 0.029459 + f-2 : 0.070757 + f+3 : 0.060978 + f-3 : 0.053816 + 2 O s : 3.318194 s : 3.318194 + pz : 1.387147 p : 3.902877 + px : 1.280234 + py : 1.235496 + dz2 : 0.055839 d : 0.359376 + dxz : 0.084656 + dyz : 0.031902 + dx2y2 : 0.067906 + dxy : 0.119072 + f0 : 0.014477 f : 0.126374 + f+1 : 0.016951 + f-1 : 0.010581 + f+2 : 0.008385 + f-2 : 0.020164 + f+3 : 0.030025 + f-3 : 0.025791 + 3 H s : 0.628069 s : 0.628069 + pz : 0.147744 p : 0.589073 + px : 0.220978 + py : 0.220351 + dz2 : 0.033286 d : 0.380391 + dxz : 0.081682 + dyz : 0.057208 + dx2y2 : 0.115505 + dxy : 0.092710 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3208 8.0000 -0.3208 2.1640 1.7001 0.4639 + 1 N 6.8172 7.0000 0.1828 2.8584 2.3635 0.4950 + 2 O 8.0993 8.0000 -0.0993 2.1990 1.7007 0.4983 + 3 H 0.7627 1.0000 0.2373 1.0113 0.9369 0.0744 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7171 B( 0-O , 3-H ) : 0.8962 B( 1-N , 2-O ) : 1.6098 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 55.335 sec + +Fock Matrix Formation ... 0.207 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 1.774 sec ( 3.2%) +State Vector Update ... 0.083 sec ( 0.2%) +Sigma-vector construction ... 38.274 sec ( 69.2%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.022 sec ( 0.1% of sigma) + (0-ext) ... 0.069 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (2-ext) ... 0.943 sec ( 2.5% of sigma) + (4-ext) ... 21.295 sec ( 55.6% of sigma) + ... 1.356 sec ( 3.5% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.106 sec ( 0.3% of sigma) + Fock-dressing ... 2.211 sec ( 5.8% of sigma) + (ik|jl)-dressing ... 0.075 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.592 sec ( 25.1% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.820 sec ( 12.3% of ALL) + I/O of integral and amplitudes ... 0.781 sec ( 11.5% of (T)) + External N**7 contributions ... 3.989 sec ( 58.5% of (T)) + Internal N**7 contributions ... 0.324 sec ( 4.7% of (T)) + N**6 triples energy contributions ... 1.601 sec ( 23.5% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.434757003179 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.035.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.035.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.629392, -0.219156 -0.296594) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.82419 -0.16224 -0.94093 +Nuclear contribution : -1.32116 0.50650 0.68581 + ----------------------------------------- +Total Dipole Moment : -0.49697 0.34426 -0.25513 + ----------------------------------------- +Magnitude (a.u.) : 0.65619 +Magnitude (Debye) : 1.66790 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.734970 0.398414 0.359906 +Rotational constants in MHz : 81992.333274 11944.147906 10789.702673 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.123428 -0.132640 0.630681 +x,y,z [Debye]: -0.313730 -0.337144 1.603062 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.629392, -0.219156 -0.296594) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.99510 -0.11203 -0.96326 +Nuclear contribution : -1.32116 0.50650 0.68581 + ----------------------------------------- +Total Dipole Moment : -0.32606 0.39447 -0.27746 + ----------------------------------------- +Magnitude (a.u.) : 0.58215 +Magnitude (Debye) : 1.47971 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.734970 0.398414 0.359906 +Rotational constants in MHz : 81992.333274 11944.147906 10789.702673 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.019072 -0.035524 0.580755 +x,y,z [Debye]: 0.048478 -0.090295 1.476161 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 36 * + * * + * Dihedral ( 2, 1, 0, 3) : 106.36363636 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0394799147 RMS(Int)= 0.0000438399 + Iter 1: RMS(Cart)= 0.0000121204 RMS(Int)= 0.0000001125 + Iter 2: RMS(Cart)= 0.0000000311 RMS(Int)= 0.0000000003 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.5074 0.000000 + 2. B(O 2,N 1) 1.1663 0.000000 + 3. B(H 3,O 0) 0.9723 0.000000 + 4. A(N 1,O 0,H 3) 102.5728 0.000000 + 5. A(O 0,N 1,O 2) 110.6565 0.000000 + 6. D(O 2,N 1,O 0,H 3) 106.3636 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.346585 -0.180260 0.766482 + N 0.233644 -0.409969 -0.605690 + O 1.221212 0.195497 -0.741439 + H -1.108270 0.394731 0.580647 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.654951 -0.340642 1.448441 + 1 N 7.0000 0 14.007 0.441524 -0.774729 -1.144589 + 2 O 8.0000 0 15.999 2.307757 0.369436 -1.401117 + 3 H 1.0000 0 1.008 -2.094327 0.745934 1.097265 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.507045978774 0.00000000 0.00000000 + O 2 1 0 1.164352626925 110.74741481 0.00000000 + H 1 2 3 0.969599126069 102.66210212 98.18181802 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.847904171109 0.00000000 0.00000000 + O 2 1 0 2.200307588199 110.74741481 0.00000000 + H 1 2 3 1.832276807960 102.66210212 98.18181802 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2693 + la=0 lb=0: 548 shell pairs + la=1 lb=0: 534 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 394 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.225609191549 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.2256091915 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.936e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7012266204 0.000000000000 0.00150054 0.00005136 0.0193887 0.7000 + 1 -204.7021220109 -0.000895390527 0.00142578 0.00004708 0.0160569 0.7000 + ***Turning on DIIS*** + 2 -204.7028908114 -0.000768800498 0.00401523 0.00012930 0.0130599 0.0000 + 3 -204.7060975302 -0.003206718826 0.00189970 0.00005800 0.0049512 0.0000 + 4 -204.7047449972 0.001352533013 0.00090412 0.00003008 0.0018773 0.0000 + 5 -204.7065312772 -0.001786280007 0.00088452 0.00002532 0.0011325 0.0000 + 6 -204.7056707469 0.000860530351 0.00088633 0.00003011 0.0007544 0.0000 + 7 -204.7053360213 0.000334725628 0.00044596 0.00001470 0.0003173 0.0000 + 8 -204.7061267219 -0.000790700627 0.00023669 0.00000850 0.0002130 0.0000 + 9 -204.7056421411 0.000484580781 0.00016018 0.00000585 0.0001292 0.0000 + 10 -204.7057924534 -0.000150312266 0.00006368 0.00000253 0.0000651 0.0000 + 11 -204.7059021384 -0.000109685039 0.00003485 0.00000102 0.0000322 0.0000 + 12 -204.7058119047 0.000090233690 0.00000789 0.00000028 0.0000113 0.0000 + 13 -204.7058352939 -0.000023389165 0.00000264 0.00000009 0.0000038 0.0000 + 14 -204.7058296795 0.000005614434 0.00000123 0.00000004 0.0000028 0.0000 + 15 -204.7058305645 -0.000000885018 0.00000107 0.00000003 0.0000023 0.0000 + 16 -204.7058322290 -0.000001664571 0.00000081 0.00000002 0.0000012 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 17 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70583157 Eh -5570.32887 eV + +Components: +Nuclear Repulsion : 68.22560919 Eh 1856.51321 eV +Electronic Energy : -272.93144076 Eh -7426.84208 eV +One Electron Energy: -416.17573342 Eh -11324.71744 eV +Two Electron Energy: 143.24429266 Eh 3897.87537 eV + +Virial components: +Potential Energy : -408.91384318 Eh -11127.11136 eV +Kinetic Energy : 204.20801161 Eh 5556.78250 eV +Virial Ratio : 2.00243781 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 6.6242e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.0657e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.3991e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.6220e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.691767 -563.0516 + 1 1.0000 -20.616845 -561.0129 + 2 1.0000 -15.805590 -430.0920 + 3 1.0000 -1.615803 -43.9682 + 4 1.0000 -1.370374 -37.2898 + 5 1.0000 -0.953816 -25.9547 + 6 1.0000 -0.767940 -20.8967 + 7 1.0000 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0.0000 0.869382 23.6571 + 48 0.0000 0.900590 24.5063 + 49 0.0000 0.937805 25.5190 + 50 0.0000 0.957664 26.0594 + 51 0.0000 0.990142 26.9431 + 52 0.0000 0.997881 27.1537 + 53 0.0000 1.025129 27.8952 + 54 0.0000 1.047482 28.5034 + 55 0.0000 1.114013 30.3138 + 56 0.0000 1.138165 30.9711 + 57 0.0000 1.234377 33.5891 + 58 0.0000 1.246453 33.9177 + 59 0.0000 1.279245 34.8100 + 60 0.0000 1.323364 36.0106 + 61 0.0000 1.417052 38.5599 + 62 0.0000 1.436149 39.0796 + 63 0.0000 1.513603 41.1872 + 64 0.0000 1.522817 41.4380 + 65 0.0000 1.563985 42.5582 + 66 0.0000 1.582948 43.0742 + 67 0.0000 1.636451 44.5301 + 68 0.0000 1.649392 44.8822 + 69 0.0000 1.703643 46.3585 + 70 0.0000 1.774787 48.2944 + 71 0.0000 1.792700 48.7818 + 72 0.0000 1.881333 51.1937 + 73 0.0000 1.929464 52.5034 + 74 0.0000 1.973677 53.7065 + 75 0.0000 2.028914 55.2096 + 76 0.0000 2.060026 56.0562 + 77 0.0000 2.071288 56.3626 + 78 0.0000 2.143466 58.3267 + 79 0.0000 2.215333 60.2823 + 80 0.0000 2.238032 60.8999 + 81 0.0000 2.299651 62.5767 + 82 0.0000 2.306325 62.7583 + 83 0.0000 2.373519 64.5867 + 84 0.0000 2.409251 65.5590 + 85 0.0000 2.452643 66.7398 + 86 0.0000 2.458303 66.8938 + 87 0.0000 2.476632 67.3926 + 88 0.0000 2.507362 68.2288 + 89 0.0000 2.552818 69.4657 + 90 0.0000 2.559457 69.6464 + 91 0.0000 2.598690 70.7140 + 92 0.0000 2.673506 72.7498 + 93 0.0000 2.711478 73.7831 + 94 0.0000 2.756555 75.0097 + 95 0.0000 2.805452 76.3402 + 96 0.0000 2.841141 77.3114 + 97 0.0000 2.879799 78.3633 + 98 0.0000 2.948241 80.2257 + 99 0.0000 2.992679 81.4349 + 100 0.0000 3.050280 83.0023 + 101 0.0000 3.162761 86.0631 + 102 0.0000 3.232750 87.9676 + 103 0.0000 3.485444 94.8437 + 104 0.0000 3.729009 101.4715 + 105 0.0000 3.813974 103.7835 + 106 0.0000 4.052716 110.2800 + 107 0.0000 4.171309 113.5071 + 108 0.0000 4.185301 113.8878 + 109 0.0000 4.302009 117.0636 + 110 0.0000 4.341389 118.1352 + 111 0.0000 4.389681 119.4493 + 112 0.0000 4.533403 123.3602 + 113 0.0000 4.608117 125.3932 + 114 0.0000 4.668789 127.0442 + 115 0.0000 4.716940 128.3545 + 116 0.0000 4.805625 130.7677 + 117 0.0000 4.895238 133.2062 + 118 0.0000 4.933007 134.2340 + 119 0.0000 4.953715 134.7974 + 120 0.0000 5.055123 137.5569 + 121 0.0000 5.094641 138.6322 + 122 0.0000 5.173059 140.7661 + 123 0.0000 5.196671 141.4086 + 124 0.0000 5.211650 141.8162 + 125 0.0000 5.334139 145.1493 + 126 0.0000 5.366014 146.0167 + 127 0.0000 5.465188 148.7153 + 128 0.0000 5.522977 150.2878 + 129 0.0000 5.723251 155.7376 + 130 0.0000 5.743760 156.2957 + 131 0.0000 5.925667 161.2456 + 132 0.0000 6.174969 168.0294 + 133 0.0000 6.409348 174.4072 + 134 0.0000 6.486299 176.5012 + 135 0.0000 6.499498 176.8603 + 136 0.0000 6.700719 182.3358 + 137 0.0000 6.723478 182.9551 + 138 0.0000 6.774764 184.3507 + 139 0.0000 6.804042 185.1474 + 140 0.0000 6.826350 185.7544 + 141 0.0000 7.055472 191.9892 + 142 0.0000 7.102331 193.2643 + 143 0.0000 7.118124 193.6940 + 144 0.0000 7.196672 195.8314 + 145 0.0000 7.255820 197.4409 + 146 0.0000 7.276812 198.0121 + 147 0.0000 7.345987 199.8945 + 148 0.0000 7.387542 201.0252 + 149 0.0000 7.440430 202.4644 + 150 0.0000 7.459281 202.9774 + 151 0.0000 7.543735 205.2755 + 152 0.0000 7.586773 206.4466 + 153 0.0000 7.594609 206.6598 + 154 0.0000 7.756533 211.0660 + 155 0.0000 7.898274 214.9229 + 156 0.0000 7.929392 215.7697 + 157 0.0000 8.385915 228.1923 + 158 0.0000 14.043808 382.1514 + 159 0.0000 14.763226 401.7278 + 160 0.0000 16.054178 436.8564 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.381174 0.000000 + 1 N : 0.356371 0.000000 + 2 O : -0.229077 0.000000 + 3 H : 0.253879 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.870154 s : 3.870154 + pz : 1.290304 p : 4.482970 + px : 1.498568 + py : 1.694098 + dz2 : 0.010446 d : 0.023704 + dxz : 0.007156 + dyz : 0.004208 + dx2y2 : 0.000501 + dxy : 0.001393 + f0 : 0.001617 f : 0.004346 + f+1 : 0.000723 + f-1 : 0.000797 + f+2 : 0.000127 + f-2 : 0.000301 + f+3 : 0.000162 + f-3 : 0.000620 + 1 N s : 3.821786 s : 3.821786 + pz : 0.854517 p : 2.656918 + px : 0.890703 + py : 0.911699 + dz2 : 0.027562 d : 0.134597 + dxz : 0.040549 + dyz : 0.018536 + dx2y2 : 0.028501 + dxy : 0.019449 + f0 : 0.008538 f : 0.030327 + f+1 : 0.003622 + f-1 : 0.005423 + f+2 : 0.002273 + f-2 : 0.004619 + f+3 : 0.003983 + f-3 : 0.001870 + 2 O s : 3.876359 s : 3.876359 + pz : 1.778257 p : 4.281728 + px : 1.200089 + py : 1.303382 + dz2 : 0.004688 d : 0.063443 + dxz : 0.011495 + dyz : 0.006383 + dx2y2 : 0.026500 + dxy : 0.014376 + f0 : 0.001207 f : 0.007546 + f+1 : 0.000772 + f-1 : 0.000530 + f+2 : 0.000105 + f-2 : 0.001106 + f+3 : 0.002743 + f-3 : 0.001084 + 3 H s : 0.640230 s : 0.640230 + pz : 0.019376 p : 0.085711 + px : 0.031280 + py : 0.035054 + dz2 : 0.001209 d : 0.020180 + dxz : 0.005097 + dyz : 0.003101 + dx2y2 : 0.009718 + dxy : 0.001055 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.571067 0.000000 + 1 N : -0.230356 0.000000 + 2 O : 0.247660 0.000000 + 3 H : -0.588370 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.139442 s : 3.139442 + pz : 1.215102 p : 3.960716 + px : 1.318841 + py : 1.426774 + dz2 : 0.094500 d : 0.254824 + dxz : 0.065624 + dyz : 0.048179 + dx2y2 : 0.015328 + dxy : 0.031192 + f0 : 0.021239 f : 0.073952 + f+1 : 0.016618 + f-1 : 0.014522 + f+2 : 0.008677 + f-2 : 0.007553 + f+3 : 0.001627 + f-3 : 0.003716 + 1 N s : 3.039342 s : 3.039342 + pz : 0.885725 p : 2.838894 + px : 1.024519 + py : 0.928650 + dz2 : 0.202050 d : 0.916910 + dxz : 0.270857 + dyz : 0.119299 + dx2y2 : 0.140911 + dxy : 0.183792 + f0 : 0.104331 f : 0.435210 + f+1 : 0.059691 + f-1 : 0.055188 + f+2 : 0.034556 + f-2 : 0.068133 + f+3 : 0.060819 + f-3 : 0.052492 + 2 O s : 3.317459 s : 3.317459 + pz : 1.454121 p : 3.986442 + px : 1.308542 + py : 1.223779 + dz2 : 0.049648 d : 0.330786 + dxz : 0.086670 + dyz : 0.022459 + dx2y2 : 0.061898 + dxy : 0.110111 + f0 : 0.013950 f : 0.117654 + f+1 : 0.017347 + f-1 : 0.008795 + f+2 : 0.010097 + f-2 : 0.017039 + f+3 : 0.024955 + f-3 : 0.025471 + 3 H s : 0.627393 s : 0.627393 + pz : 0.145028 p : 0.570937 + px : 0.222144 + py : 0.203765 + dz2 : 0.032556 d : 0.390040 + dxz : 0.092411 + dyz : 0.050735 + dx2y2 : 0.118506 + dxy : 0.095832 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3812 8.0000 -0.3812 1.8309 1.8309 0.0000 + 1 N 6.6436 7.0000 0.3564 2.5944 2.5944 -0.0000 + 2 O 8.2291 8.0000 -0.2291 1.8114 1.8114 0.0000 + 3 H 0.7461 1.0000 0.2539 0.9828 0.9828 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8164 B( 0-O , 3-H ) : 0.9576 B( 1-N , 2-O ) : 1.7537 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.675 sec +Sum of individual times .... 2.351 sec ( 87.9%) + +Fock matrix formation .... 1.878 sec ( 70.2%) +Diagonalization .... 0.196 sec ( 7.3%) +Density matrix formation .... 0.014 sec ( 0.5%) +Population analysis .... 0.086 sec ( 3.2%) +Initial guess .... 0.010 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.2%) +DIIS solution .... 0.167 sec ( 6.2%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.203 sec +Reference energy ... -204.705831893 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.372 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.077 sec +K-integral sorting ... 5.385 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.024 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.028 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.029 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.344 sec +AO-integral generation ... 0.241 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.049 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.155 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.251 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090183081 +EMP2(bb)= -0.090183081 +EMP2(ab)= -0.518204810 + +Initial guess performed in 0.133 sec +E(0) ... -204.705831893 +E(MP2) ... -0.698570972 +Initial E(tot) ... -205.404402865 + ... 0.190482323 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.404402865 -0.698570972 -0.000000000 0.019213970 2.70 0.000002000 + *** Turning on DIIS *** + 1 -205.375534379 -0.669702485 0.028868487 0.010143144 2.70 0.056086925 + 2 -205.395233726 -0.689401833 -0.019699347 0.003784552 2.78 0.058750981 + 3 -205.399082935 -0.693251042 -0.003849209 0.001916921 2.82 0.071909650 + 4 -205.400639494 -0.694807600 -0.001556558 0.000955624 2.79 0.077774402 + 5 -205.401139428 -0.695307535 -0.000499935 0.000581561 2.89 0.082234929 + 6 -205.401221315 -0.695389421 -0.000081886 0.000400404 2.82 0.084314193 + 7 -205.401255093 -0.695423200 -0.000033778 0.000239836 2.88 0.085280349 + 8 -205.401263347 -0.695431453 -0.000008254 0.000144275 2.89 0.085710848 + 9 -205.401259919 -0.695428025 0.000003428 0.000085675 2.80 0.085882355 + 10 -205.401265074 -0.695433181 -0.000005156 0.000050772 2.76 0.085967897 + 11 -205.401261462 -0.695429569 0.000003612 0.000031548 2.78 0.085979443 + 12 -205.401264212 -0.695432319 -0.000002750 0.000018364 2.93 0.085998909 + 13 -205.401264090 -0.695432197 0.000000122 0.000010724 3.04 0.085997785 + 14 -205.401264545 -0.695432651 -0.000000454 0.000005582 2.90 0.086004043 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.705831893 +E(CORR) ... -0.695432651 +E(TOT) ... -205.401264545 +Singles norm **1/2 ... 0.086004043 ( 0.043002022, 0.043002022) +T1 diagnostic ... 0.020271347 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.058237 + 8a-> 13a 8b-> 13b 0.054841 + 8a-> 13a 9b-> 13b 0.046853 + 9a-> 13a 8b-> 13b 0.046853 + 5a-> 13a 5b-> 13b 0.030153 + 8a-> 13a -1a-> -1a 0.027916 + 8b-> 13b -1b-> -1b 0.027916 + 11a-> 13a 11b-> 13b 0.027459 + 11a-> 24a 11b-> 24b 0.025746 + 11a-> 24a 11b-> 25b 0.022139 + 11a-> 25a 11b-> 24b 0.022139 + 9a-> 22a 9b-> 13b 0.021931 + 9a-> 13a 9b-> 22b 0.021931 + 11a-> 25a 11b-> 25b 0.021493 + 11b-> 24b -1b-> -1b 0.020537 + 11a-> 24a -1a-> -1a 0.020537 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034717652 + alpha-alpha-alpha ... -0.000865723 ( 2.5%) + alpha-alpha-beta ... -0.016493103 ( 47.5%) + alpha-beta -beta ... -0.016493103 ( 47.5%) + beta -beta -beta ... -0.000865723 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034717652 + +Final correlation energy ... -0.730150303 +E(CCSD) ... -205.401264545 +E(CCSD(T)) ... -205.435982196 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.211503609 sqrt= 1.100683247 +W(HF) = 0.825420570 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.319973 -0.000000 + 1 N : 0.182081 0.000000 + 2 O : -0.103223 -0.000000 + 3 H : 0.241116 -0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.846591 s : 3.846591 + pz : 1.273428 p : 4.410393 + px : 1.483551 + py : 1.653414 + dz2 : 0.015087 d : 0.054896 + dxz : 0.012512 + dyz : 0.011468 + dx2y2 : 0.007902 + dxy : 0.007927 + f0 : 0.001932 f : 0.008094 + f+1 : 0.001071 + f-1 : 0.001343 + f+2 : 0.000746 + f-2 : 0.000945 + f+3 : 0.000799 + f-3 : 0.001259 + 1 N s : 3.876033 s : 3.876033 + pz : 0.900320 p : 2.748221 + px : 0.906155 + py : 0.941746 + dz2 : 0.034314 d : 0.164280 + dxz : 0.049543 + dyz : 0.026808 + dx2y2 : 0.029521 + dxy : 0.024095 + f0 : 0.008138 f : 0.029385 + f+1 : 0.003391 + f-1 : 0.005490 + f+2 : 0.002753 + f-2 : 0.004534 + f+3 : 0.003143 + f-3 : 0.001935 + 2 O s : 3.863557 s : 3.863557 + pz : 1.690188 p : 4.145554 + px : 1.183521 + py : 1.271844 + dz2 : 0.009969 d : 0.084206 + dxz : 0.018611 + dyz : 0.012321 + dx2y2 : 0.026427 + dxy : 0.016879 + f0 : 0.001660 f : 0.009906 + f+1 : 0.001239 + f-1 : 0.000980 + f+2 : 0.000717 + f-2 : 0.001512 + f+3 : 0.002464 + f-3 : 0.001333 + 3 H s : 0.648401 s : 0.648401 + pz : 0.022898 p : 0.093244 + px : 0.030602 + py : 0.039744 + dz2 : 0.001178 d : 0.017238 + dxz : 0.004531 + dyz : 0.002697 + dx2y2 : 0.008426 + dxy : 0.000408 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.577164 -0.000000 + 1 N : -0.275123 0.000000 + 2 O : 0.290333 0.000000 + 3 H : -0.592373 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.143648 s : 3.143648 + pz : 1.211465 p : 3.912596 + px : 1.308468 + py : 1.392663 + dz2 : 0.100689 d : 0.285757 + dxz : 0.072077 + dyz : 0.053432 + dx2y2 : 0.021453 + dxy : 0.038105 + f0 : 0.022576 f : 0.080835 + f+1 : 0.018464 + f-1 : 0.015121 + f+2 : 0.009264 + f-2 : 0.008489 + f+3 : 0.002276 + f-3 : 0.004645 + 1 N s : 3.044127 s : 3.044127 + pz : 0.906401 p : 2.880121 + px : 1.030010 + py : 0.943710 + dz2 : 0.208700 d : 0.925217 + dxz : 0.270286 + dyz : 0.120071 + dx2y2 : 0.137554 + dxy : 0.188607 + f0 : 0.101348 f : 0.425658 + f+1 : 0.060128 + f-1 : 0.054098 + f+2 : 0.033045 + f-2 : 0.064372 + f+3 : 0.059628 + f-3 : 0.053039 + 2 O s : 3.320207 s : 3.320207 + pz : 1.397669 p : 3.904754 + px : 1.299738 + py : 1.207347 + dz2 : 0.055421 d : 0.358656 + dxz : 0.089455 + dyz : 0.028416 + dx2y2 : 0.069961 + dxy : 0.115402 + f0 : 0.014777 f : 0.126050 + f+1 : 0.018011 + f-1 : 0.009239 + f+2 : 0.010405 + f-2 : 0.018335 + f+3 : 0.028933 + f-3 : 0.026351 + 3 H s : 0.627524 s : 0.627524 + pz : 0.145554 p : 0.584969 + px : 0.227760 + py : 0.211655 + dz2 : 0.033676 d : 0.379880 + dxz : 0.089010 + dyz : 0.049056 + dx2y2 : 0.113513 + dxy : 0.094626 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3200 8.0000 -0.3200 2.1765 1.7105 0.4660 + 1 N 6.8179 7.0000 0.1821 2.8596 2.3638 0.4957 + 2 O 8.1032 8.0000 -0.1032 2.1987 1.6991 0.4996 + 3 H 0.7589 1.0000 0.2411 1.0057 0.9313 0.0744 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7265 B( 0-O , 3-H ) : 0.8950 B( 1-N , 2-O ) : 1.6056 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 58.015 sec + +Fock Matrix Formation ... 0.203 sec ( 0.3%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 1.933 sec ( 3.3%) +State Vector Update ... 0.091 sec ( 0.2%) +Sigma-vector construction ... 40.470 sec ( 69.8%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.025 sec ( 0.1% of sigma) + (0-ext) ... 0.074 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.031 sec ( 0.1% of sigma) + (2-ext) ... 1.000 sec ( 2.5% of sigma) + (4-ext) ... 22.591 sec ( 55.8% of sigma) + ... 1.427 sec ( 3.5% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.115 sec ( 0.3% of sigma) + Fock-dressing ... 2.233 sec ( 5.5% of sigma) + (ik|jl)-dressing ... 0.079 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.126 sec ( 25.0% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 7.074 sec ( 12.2% of ALL) + I/O of integral and amplitudes ... 0.757 sec ( 10.7% of (T)) + External N**7 contributions ... 4.033 sec ( 57.0% of (T)) + Internal N**7 contributions ... 0.311 sec ( 4.4% of (T)) + N**6 triples energy contributions ... 1.573 sec ( 22.2% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.435982196190 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.003735827 -0.005767879 0.000310154 + 2 N : 0.001781086 -0.006368187 0.001958672 + 3 O : 0.000669131 0.005805069 -0.002814926 + 4 H : 0.001285610 0.006330997 0.000546100 + +Norm of the cartesian gradient ... 0.013378581 +RMS gradient ... 0.003862064 +MAX gradient ... 0.006368187 + +------- +TIMINGS +------- + +Total numerical gradient time ... 371.768 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: -467.27 cm**-1 ***imaginary mode*** + 7: 537.16 cm**-1 + 8: 776.42 cm**-1 + 9: 1122.87 cm**-1 + 10: 1706.58 cm**-1 + 11: 3726.48 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 -0.053434 -0.404895 0.145390 -0.028606 0.015955 -0.049577 + 1 -0.043406 -0.038892 0.213938 0.017079 -0.018776 0.036634 + 2 0.005838 0.518115 0.188463 -0.062238 -0.081471 -0.011072 + 3 0.048580 0.255891 0.050811 0.027197 0.614399 -0.000722 + 4 -0.060999 0.101349 -0.297564 -0.026283 0.420009 -0.000631 + 5 0.007199 -0.237489 -0.669733 0.021079 0.021163 -0.000070 + 6 -0.024572 0.210270 -0.186857 0.021277 -0.554269 0.000540 + 7 0.045555 -0.033829 0.044846 0.004686 -0.348032 0.000749 + 8 -0.017517 -0.315368 0.371139 -0.016765 0.057874 -0.000283 + 9 0.563040 -0.466725 -0.047896 -0.261602 0.006561 0.788353 + 10 0.813519 -0.254094 0.027459 0.019749 -0.014395 -0.584582 + 11 0.085328 0.082104 0.424483 0.961020 0.080456 0.181215 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 7: 537.16 0.026067 131.73 0.015144 ( 0.078830 -0.003848 -0.094417) + 8: 776.42 0.018659 94.29 0.007499 ( 0.047910 -0.010389 -0.071387) + 9: 1122.87 0.016521 83.49 0.004591 (-0.034294 0.016573 0.056041) + 10: 1706.58 0.033892 171.28 0.006197 ( 0.058582 0.010949 -0.051437) + 11: 3726.48 0.012189 61.60 0.001021 ( 0.026867 -0.014836 -0.008877) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 7 +The total number of vibrations considered is 5 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 537.16 E(vib) ... 0.12 +freq. 776.42 E(vib) ... 0.05 +freq. 1122.87 E(vib) ... 0.01 +freq. 1706.58 E(vib) ... 0.00 +freq. 3726.48 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.43598220 Eh +Zero point energy ... 0.01792808 Eh 11.25 kcal/mol +Thermal vibrational correction ... 0.00030839 Eh 0.19 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.41491318 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00314093 Eh 1.97 kcal/mol +Non-thermal (ZPE) correction 0.01792808 Eh 11.25 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02106902 Eh 13.22 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.41491318 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.41396897 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.754579 0.397040 0.358443 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00040928 Eh 0.26 kcal/mol +Rotational entropy ... 0.00995289 Eh 6.25 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02816449 Eh 17.67 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00995289 Eh 6.25 kcal/mol| +| sn= 2 | S(rot)= 0.00929844 Eh 5.83 kcal/mol| +| sn= 3 | S(rot)= 0.00891561 Eh 5.59 kcal/mol| +| sn= 4 | S(rot)= 0.00864398 Eh 5.42 kcal/mol| +| sn= 5 | S(rot)= 0.00843329 Eh 5.29 kcal/mol| +| sn= 6 | S(rot)= 0.00826115 Eh 5.18 kcal/mol| +| sn= 7 | S(rot)= 0.00811560 Eh 5.09 kcal/mol| +| sn= 8 | S(rot)= 0.00798953 Eh 5.01 kcal/mol| +| sn= 9 | S(rot)= 0.00787832 Eh 4.94 kcal/mol| +| sn=10 | S(rot)= 0.00777884 Eh 4.88 kcal/mol| +| sn=11 | S(rot)= 0.00768885 Eh 4.82 kcal/mol| +| sn=12 | S(rot)= 0.00760669 Eh 4.77 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.41396897 Eh +Total entropy correction ... -0.02816449 Eh -17.67 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44213346 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00615127 Eh -3.86 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.435982195 Eh +Current gradient norm .... 0.013378585 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + -0.023950022 0.094713786 0.152778140 0.469532762 0.498721699 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999925033 +Lowest eigenvalues of augmented Hessian: + -0.000047700 0.094230641 0.152406389 0.469347441 0.498685836 +Length of the computed step .... 0.012245454 +The final length of the internal step .... 0.012245454 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0049991856 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0043555572 RMS(Int)= 0.0049988673 + Iter 1: RMS(Cart)= 0.0000029352 RMS(Int)= 0.0000033036 + Iter 2: RMS(Cart)= 0.0000000079 RMS(Int)= 0.0000000103 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0021501601 0.0001000000 NO + MAX gradient 0.0039078800 0.0003000000 NO + RMS step 0.0049991856 0.0020000000 NO + MAX step 0.0103512170 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0055 Max(Angles) 0.12 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.5074 0.001808 -0.0055 1.5019 + 2. B(O 2,N 1) 1.1663 0.003908 -0.0016 1.1647 + 3. B(H 3,O 0) 0.9723 0.002632 -0.0028 0.9695 + 4. A(N 1,O 0,H 3) 102.57 0.000743 -0.12 102.45 + 5. A(O 0,N 1,O 2) 110.66 0.001310 -0.07 110.58 + 6. D(O 2,N 1,O 0,H 3) 106.36 -0.010602 -0.00 106.36 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.345031 -0.180020 0.764333 + N 0.231489 -0.409165 -0.603484 + O 1.217631 0.195623 -0.738754 + H -1.104088 0.393562 0.577904 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.652015 -0.340188 1.444381 + 1 N 7.0000 0 14.007 0.437451 -0.773209 -1.140419 + 2 O 8.0000 0 15.999 2.300989 0.369673 -1.396042 + 3 H 1.0000 0 1.008 -2.086424 0.743724 1.092080 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.501934154823 0.00000000 0.00000000 + O 2 1 0 1.164706394120 110.58219654 0.00000000 + H 1 2 3 0.969493962917 102.45497224 106.36363642 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.838244223798 0.00000000 0.00000000 + O 2 1 0 2.200976111315 110.58219654 0.00000000 + H 1 2 3 1.832078078403 102.45497224 106.36363642 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2693 + la=0 lb=0: 548 shell pairs + la=1 lb=0: 534 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 394 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.407058179169 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.920e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7067355084 0.000000000000 0.00025053 0.00000557 0.0009374 0.7000 + 1 -204.7067391579 -0.000003649507 0.00019201 0.00000452 0.0007039 0.7000 + ***Turning on DIIS*** + 2 -204.7067420832 -0.000002925351 0.00045540 0.00001149 0.0005208 0.0000 + 3 -204.7063073478 0.000434735384 0.00016841 0.00000375 0.0001072 0.0000 + 4 -204.7067033129 -0.000395965112 0.00004213 0.00000140 0.0000630 0.0000 + 5 -204.7069438710 -0.000240558058 0.00002139 0.00000072 0.0000247 0.0000 + 6 -204.7066776236 0.000266247438 0.00001431 0.00000049 0.0000181 0.0000 + 7 -204.7067550076 -0.000077384035 0.00001092 0.00000038 0.0000118 0.0000 + 8 -204.7067511109 0.000003896670 0.00000774 0.00000027 0.0000060 0.0000 + 9 -204.7067377592 0.000013351714 0.00000430 0.00000018 0.0000036 0.0000 + 10 -204.7067589138 -0.000021154549 0.00000213 0.00000008 0.0000021 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + +Total Energy : -204.70675051 Eh -5570.35387 eV + Last Energy change ... 8.4025e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.1377e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.207 sec +Reference energy ... -204.706751455 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.376 sec +AO-integral generation ... 0.145 sec +Half transformation ... 0.079 sec +K-integral sorting ... 5.384 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.026 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.028 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.034 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.354 sec +AO-integral generation ... 0.248 sec +Half transformation ... 0.042 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.150 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.258 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090070359 +EMP2(bb)= -0.090070359 +EMP2(ab)= -0.517494906 + +Initial guess performed in 0.132 sec +E(0) ... -204.706751455 +E(MP2) ... -0.697635624 +Initial E(tot) ... -205.404387078 + ... 0.189599374 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.404387078 -0.697635624 -0.000000000 0.019097349 2.71 0.000000853 + *** Turning on DIIS *** + 1 -205.375952029 -0.669200574 0.028435050 0.010125069 2.70 0.055713951 + 2 -205.395500538 -0.688749083 -0.019548509 0.003763863 2.78 0.058442943 + 3 -205.399323152 -0.692571698 -0.003822614 0.001910577 2.83 0.071501493 + 4 -205.400861980 -0.694110526 -0.001538828 0.000912984 2.77 0.077318713 + 5 -205.401353266 -0.694601812 -0.000491286 0.000576156 2.90 0.081724938 + 6 -205.401434188 -0.694682733 -0.000080922 0.000395764 2.81 0.083777626 + 7 -205.401467292 -0.694715838 -0.000033104 0.000236594 2.84 0.084723071 + 8 -205.401475256 -0.694723801 -0.000007963 0.000142059 2.88 0.085142076 + 9 -205.401471915 -0.694720461 0.000003340 0.000084340 2.82 0.085308914 + 10 -205.401476878 -0.694725423 -0.000004963 0.000049916 2.79 0.085391808 + 11 -205.401473404 -0.694721950 0.000003474 0.000030992 2.83 0.085403030 + 12 -205.401476063 -0.694724608 -0.000002659 0.000018022 2.79 0.085421823 + 13 -205.401475956 -0.694724501 0.000000107 0.000010476 2.79 0.085420853 + 14 -205.401476393 -0.694724938 -0.000000437 0.000005431 2.80 0.085426899 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.706751455 +E(CORR) ... -0.694724938 +E(TOT) ... -205.401476393 +Singles norm **1/2 ... 0.085426899 ( 0.042713449, 0.042713449) +T1 diagnostic ... 0.020135313 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.058345 + 8a-> 13a 8b-> 13b 0.053940 + 8a-> 13a 9b-> 13b 0.046409 + 9a-> 13a 8b-> 13b 0.046409 + 5a-> 13a 5b-> 13b 0.029899 + 8a-> 13a -1a-> -1a 0.027751 + 8b-> 13b -1b-> -1b 0.027751 + 11a-> 13a 11b-> 13b 0.027579 + 11a-> 25a 11b-> 25b 0.022928 + 11a-> 24a 11b-> 24b 0.022480 + 9a-> 22a 9b-> 13b 0.022149 + 9a-> 13a 9b-> 22b 0.022149 + 11a-> 24a 11b-> 25b 0.021333 + 11a-> 25a 11b-> 24b 0.021333 + 11a-> 25a -1a-> -1a 0.019950 + 11b-> 25b -1b-> -1b 0.019950 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034529478 + alpha-alpha-alpha ... -0.000863457 ( 2.5%) + alpha-alpha-beta ... -0.016401282 ( 47.5%) + alpha-beta -beta ... -0.016401282 ( 47.5%) + beta -beta -beta ... -0.000863457 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034529478 + +Final correlation energy ... -0.729254416 +E(CCSD) ... -205.401476393 +E(CCSD(T)) ... -205.436005871 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210482261 sqrt= 1.100219188 +W(HF) = 0.826117021 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 57.148 sec + +Fock Matrix Formation ... 0.207 sec ( 0.4%) +Initial Guess ... 0.132 sec ( 0.2%) +DIIS Solver ... 1.836 sec ( 3.2%) +State Vector Update ... 0.090 sec ( 0.2%) +Sigma-vector construction ... 40.109 sec ( 70.2%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.024 sec ( 0.1% of sigma) + (0-ext) ... 0.076 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.028 sec ( 0.1% of sigma) + (2-ext) ... 1.016 sec ( 2.5% of sigma) + (4-ext) ... 22.148 sec ( 55.2% of sigma) + ... 1.358 sec ( 3.4% of sigma) + ... 0.003 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.116 sec ( 0.3% of sigma) + Fock-dressing ... 2.267 sec ( 5.7% of sigma) + (ik|jl)-dressing ... 0.080 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.135 sec ( 25.3% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.839 sec ( 12.0% of ALL) + I/O of integral and amplitudes ... 0.796 sec ( 11.6% of (T)) + External N**7 contributions ... 3.945 sec ( 57.7% of (T)) + Internal N**7 contributions ... 0.322 sec ( 4.7% of (T)) + N**6 triples energy contributions ... 1.601 sec ( 23.4% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.436005870611 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.004729536 -0.004418234 -0.001290329 + 2 N : 0.004014306 -0.004456198 0.002448490 + 3 O : -0.002797625 0.004027995 -0.001822908 + 4 H : 0.003512856 0.004846437 0.000664747 + +Norm of the cartesian gradient ... 0.012213359 +RMS gradient ... 0.003525693 +MAX gradient ... 0.004846437 + +------- +TIMINGS +------- + +Total numerical gradient time ... 361.234 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.436005871 Eh +Current gradient norm .... 0.012213359 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999964 +Lowest eigenvalues of augmented Hessian: + -0.000000013 0.094794433 0.152562606 0.469347590 0.497869627 +Length of the computed step .... 0.000268178 +The final length of the internal step .... 0.000268178 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0001094834 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0000680153 RMS(Int)= 0.0001094836 + Iter 1: RMS(Cart)= 0.0000000007 RMS(Int)= 0.0000000012 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000236751 0.0000050000 NO + RMS gradient 0.0000315664 0.0001000000 YES + MAX gradient 0.0000652825 0.0003000000 YES + RMS step 0.0001094834 0.0020000000 YES + MAX step 0.0002594764 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.5019 -0.000037 0.0001 1.5021 + 2. B(O 2,N 1) 1.1647 -0.000065 0.0000 1.1647 + 3. B(H 3,O 0) 0.9695 -0.000011 0.0000 0.9695 + 4. A(N 1,O 0,H 3) 102.45 -0.000001 -0.00 102.45 + 5. A(O 0,N 1,O 2) 110.58 -0.000014 0.00 110.58 + 6. D(O 2,N 1,O 0,H 3) 106.36 -0.010777 -0.00 106.36 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.345072 -0.180021 0.764404 + N 0.231517 -0.409173 -0.603534 + O 1.217679 0.195624 -0.738793 + H -1.104124 0.393570 0.577923 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.652091 -0.340190 1.444514 + 1 N 7.0000 0 14.007 0.437504 -0.773224 -1.140514 + 2 O 8.0000 0 15.999 2.301081 0.369676 -1.396116 + 3 H 1.0000 0 1.008 -2.086492 0.743739 1.092116 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.502071463809 0.00000000 0.00000000 + O 2 1 0 1.164727406705 110.58240067 0.00000000 + H 1 2 3 0.969506097968 102.45212100 106.36363642 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.838503700177 0.00000000 0.00000000 + O 2 1 0 2.201015819344 110.58240067 0.00000000 + H 1 2 3 1.832101010325 102.45212100 106.36363642 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2693 + la=0 lb=0: 548 shell pairs + la=1 lb=0: 534 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 394 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.403625715019 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.4036257150 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.920e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7067343667 0.000000000000 0.00000442 0.00000009 0.0000181 0.7000 + 1 -204.7067343687 -0.000000002077 0.00000336 0.00000008 0.0000144 0.7000 + ***Turning on DIIS*** + 2 -204.7067343706 -0.000000001836 0.00000787 0.00000020 0.0000112 0.0000 + 3 -204.7067406889 -0.000006318300 0.00000363 0.00000008 0.0000030 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 4 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70673365 Eh -5570.35341 eV + +Components: +Nuclear Repulsion : 68.40362572 Eh 1861.35729 eV +Electronic Energy : -273.11035937 Eh -7431.71070 eV +One Electron Energy: -416.52285430 Eh -11334.16308 eV +Two Electron Energy: 143.41249493 Eh 3902.45238 eV + +Virial components: +Potential Energy : -408.93629748 Eh -11127.72238 eV +Kinetic Energy : 204.22956382 Eh 5557.36896 eV +Virial Ratio : 2.00233644 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 7.0379e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.0058e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.6583e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.5963e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.690813 -563.0257 + 1 1.0000 -20.616880 -561.0138 + 2 1.0000 -15.804626 -430.0657 + 3 1.0000 -1.617264 -44.0080 + 4 1.0000 -1.372540 -37.3487 + 5 1.0000 -0.953476 -25.9454 + 6 1.0000 -0.769355 -20.9352 + 7 1.0000 -0.731069 -19.8934 + 8 1.0000 -0.698946 -19.0193 + 9 1.0000 -0.607407 -16.5284 + 10 1.0000 -0.528565 -14.3830 + 11 1.0000 -0.457984 -12.4624 + 12 0.0000 0.030590 0.8324 + 13 0.0000 0.068329 1.8593 + 14 0.0000 0.091590 2.4923 + 15 0.0000 0.101713 2.7677 + 16 0.0000 0.114200 3.1076 + 17 0.0000 0.154806 4.2125 + 18 0.0000 0.157219 4.2781 + 19 0.0000 0.173338 4.7168 + 20 0.0000 0.182981 4.9792 + 21 0.0000 0.189735 5.1630 + 22 0.0000 0.201107 5.4724 + 23 0.0000 0.236599 6.4382 + 24 0.0000 0.269819 7.3421 + 25 0.0000 0.286453 7.7948 + 26 0.0000 0.304151 8.2764 + 27 0.0000 0.329393 8.9632 + 28 0.0000 0.333560 9.0766 + 29 0.0000 0.354847 9.6559 + 30 0.0000 0.425079 11.5670 + 31 0.0000 0.506088 13.7714 + 32 0.0000 0.525178 14.2908 + 33 0.0000 0.543907 14.8005 + 34 0.0000 0.572506 15.5787 + 35 0.0000 0.603275 16.4159 + 36 0.0000 0.630160 17.1475 + 37 0.0000 0.650591 17.7035 + 38 0.0000 0.699126 19.0242 + 39 0.0000 0.720695 19.6111 + 40 0.0000 0.740075 20.1385 + 41 0.0000 0.749502 20.3950 + 42 0.0000 0.769491 20.9389 + 43 0.0000 0.792391 21.5621 + 44 0.0000 0.809444 22.0261 + 45 0.0000 0.817017 22.2322 + 46 0.0000 0.855686 23.2844 + 47 0.0000 0.870175 23.6787 + 48 0.0000 0.900726 24.5100 + 49 0.0000 0.938519 25.5384 + 50 0.0000 0.957845 26.0643 + 51 0.0000 0.990718 26.9588 + 52 0.0000 0.997805 27.1516 + 53 0.0000 1.025863 27.9152 + 54 0.0000 1.048417 28.5289 + 55 0.0000 1.115593 30.3568 + 56 0.0000 1.138960 30.9927 + 57 0.0000 1.235257 33.6131 + 58 0.0000 1.247439 33.9446 + 59 0.0000 1.279528 34.8177 + 60 0.0000 1.324045 36.0291 + 61 0.0000 1.417898 38.5830 + 62 0.0000 1.435592 39.0645 + 63 0.0000 1.513869 41.1945 + 64 0.0000 1.523830 41.4655 + 65 0.0000 1.564849 42.5817 + 66 0.0000 1.583490 43.0889 + 67 0.0000 1.637203 44.5505 + 68 0.0000 1.649982 44.8983 + 69 0.0000 1.704633 46.3854 + 70 0.0000 1.775624 48.3172 + 71 0.0000 1.793371 48.8001 + 72 0.0000 1.882470 51.2246 + 73 0.0000 1.930530 52.5324 + 74 0.0000 1.975917 53.7674 + 75 0.0000 2.030370 55.2492 + 76 0.0000 2.062752 56.1303 + 77 0.0000 2.074325 56.4453 + 78 0.0000 2.143183 58.3190 + 79 0.0000 2.216687 60.3191 + 80 0.0000 2.239654 60.9441 + 81 0.0000 2.300051 62.5876 + 82 0.0000 2.307971 62.8031 + 83 0.0000 2.373556 64.5877 + 84 0.0000 2.410245 65.5861 + 85 0.0000 2.453294 66.7575 + 86 0.0000 2.461407 66.9783 + 87 0.0000 2.477021 67.4032 + 88 0.0000 2.508491 68.2595 + 89 0.0000 2.552543 69.4582 + 90 0.0000 2.562209 69.7212 + 91 0.0000 2.599222 70.7284 + 92 0.0000 2.675575 72.8061 + 93 0.0000 2.713089 73.8269 + 94 0.0000 2.757975 75.0483 + 95 0.0000 2.806401 76.3660 + 96 0.0000 2.843321 77.3707 + 97 0.0000 2.883096 78.4530 + 98 0.0000 2.952763 80.3488 + 99 0.0000 2.996117 81.5285 + 100 0.0000 3.053456 83.0888 + 101 0.0000 3.163091 86.0721 + 102 0.0000 3.234222 88.0077 + 103 0.0000 3.487024 94.8868 + 104 0.0000 3.732568 101.5683 + 105 0.0000 3.817281 103.8735 + 106 0.0000 4.053518 110.3018 + 107 0.0000 4.174665 113.5984 + 108 0.0000 4.188250 113.9681 + 109 0.0000 4.305731 117.1649 + 110 0.0000 4.344541 118.2210 + 111 0.0000 4.392951 119.5383 + 112 0.0000 4.534177 123.3812 + 113 0.0000 4.611840 125.4945 + 114 0.0000 4.674397 127.1968 + 115 0.0000 4.721296 128.4730 + 116 0.0000 4.807668 130.8233 + 117 0.0000 4.895369 133.2098 + 118 0.0000 4.933616 134.2505 + 119 0.0000 4.954708 134.8245 + 120 0.0000 5.056820 137.6031 + 121 0.0000 5.096177 138.6740 + 122 0.0000 5.179011 140.9281 + 123 0.0000 5.198776 141.4659 + 124 0.0000 5.213695 141.8718 + 125 0.0000 5.340339 145.3180 + 126 0.0000 5.371480 146.1654 + 127 0.0000 5.471743 148.8937 + 128 0.0000 5.527685 150.4159 + 129 0.0000 5.728146 155.8708 + 130 0.0000 5.752274 156.5273 + 131 0.0000 5.933668 161.4633 + 132 0.0000 6.176650 168.0752 + 133 0.0000 6.410228 174.4312 + 134 0.0000 6.487135 176.5239 + 135 0.0000 6.501115 176.9043 + 136 0.0000 6.701606 182.3600 + 137 0.0000 6.724208 182.9750 + 138 0.0000 6.772428 184.2871 + 139 0.0000 6.809206 185.2879 + 140 0.0000 6.831247 185.8877 + 141 0.0000 7.061639 192.1570 + 142 0.0000 7.104133 193.3133 + 143 0.0000 7.120552 193.7601 + 144 0.0000 7.201677 195.9676 + 145 0.0000 7.258008 197.5004 + 146 0.0000 7.281860 198.1495 + 147 0.0000 7.351468 200.0436 + 148 0.0000 7.393533 201.1883 + 149 0.0000 7.446584 202.6319 + 150 0.0000 7.461009 203.0244 + 151 0.0000 7.545509 205.3237 + 152 0.0000 7.594569 206.6587 + 153 0.0000 7.600491 206.8199 + 154 0.0000 7.762086 211.2171 + 155 0.0000 7.902955 215.0503 + 156 0.0000 7.939258 216.0382 + 157 0.0000 8.395311 228.4480 + 158 0.0000 14.073217 382.9517 + 159 0.0000 14.819658 403.2634 + 160 0.0000 16.116250 438.5455 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.690813 -563.0257 + 1 1.0000 -20.616880 -561.0138 + 2 1.0000 -15.804626 -430.0657 + 3 1.0000 -1.617264 -44.0080 + 4 1.0000 -1.372540 -37.3487 + 5 1.0000 -0.953476 -25.9454 + 6 1.0000 -0.769355 -20.9352 + 7 1.0000 -0.731069 -19.8934 + 8 1.0000 -0.698946 -19.0193 + 9 1.0000 -0.607407 -16.5284 + 10 1.0000 -0.528565 -14.3830 + 11 1.0000 -0.457984 -12.4624 + 12 0.0000 0.030590 0.8324 + 13 0.0000 0.068329 1.8593 + 14 0.0000 0.091590 2.4923 + 15 0.0000 0.101713 2.7677 + 16 0.0000 0.114200 3.1076 + 17 0.0000 0.154806 4.2125 + 18 0.0000 0.157219 4.2781 + 19 0.0000 0.173338 4.7168 + 20 0.0000 0.182981 4.9792 + 21 0.0000 0.189735 5.1630 + 22 0.0000 0.201107 5.4724 + 23 0.0000 0.236599 6.4382 + 24 0.0000 0.269819 7.3421 + 25 0.0000 0.286453 7.7948 + 26 0.0000 0.304151 8.2764 + 27 0.0000 0.329393 8.9632 + 28 0.0000 0.333560 9.0766 + 29 0.0000 0.354847 9.6559 + 30 0.0000 0.425079 11.5670 + 31 0.0000 0.506088 13.7714 + 32 0.0000 0.525178 14.2908 + 33 0.0000 0.543907 14.8005 + 34 0.0000 0.572506 15.5787 + 35 0.0000 0.603275 16.4159 + 36 0.0000 0.630160 17.1475 + 37 0.0000 0.650591 17.7035 + 38 0.0000 0.699126 19.0242 + 39 0.0000 0.720695 19.6111 + 40 0.0000 0.740075 20.1385 + 41 0.0000 0.749502 20.3950 + 42 0.0000 0.769491 20.9389 + 43 0.0000 0.792391 21.5621 + 44 0.0000 0.809444 22.0261 + 45 0.0000 0.817017 22.2322 + 46 0.0000 0.855686 23.2844 + 47 0.0000 0.870175 23.6787 + 48 0.0000 0.900726 24.5100 + 49 0.0000 0.938519 25.5384 + 50 0.0000 0.957845 26.0643 + 51 0.0000 0.990718 26.9588 + 52 0.0000 0.997805 27.1516 + 53 0.0000 1.025863 27.9152 + 54 0.0000 1.048417 28.5289 + 55 0.0000 1.115593 30.3568 + 56 0.0000 1.138960 30.9927 + 57 0.0000 1.235257 33.6131 + 58 0.0000 1.247439 33.9446 + 59 0.0000 1.279528 34.8177 + 60 0.0000 1.324045 36.0291 + 61 0.0000 1.417898 38.5830 + 62 0.0000 1.435592 39.0645 + 63 0.0000 1.513869 41.1945 + 64 0.0000 1.523830 41.4655 + 65 0.0000 1.564849 42.5817 + 66 0.0000 1.583490 43.0889 + 67 0.0000 1.637203 44.5505 + 68 0.0000 1.649982 44.8983 + 69 0.0000 1.704633 46.3854 + 70 0.0000 1.775624 48.3172 + 71 0.0000 1.793371 48.8001 + 72 0.0000 1.882470 51.2246 + 73 0.0000 1.930530 52.5324 + 74 0.0000 1.975917 53.7674 + 75 0.0000 2.030370 55.2492 + 76 0.0000 2.062752 56.1303 + 77 0.0000 2.074325 56.4453 + 78 0.0000 2.143183 58.3190 + 79 0.0000 2.216687 60.3191 + 80 0.0000 2.239654 60.9441 + 81 0.0000 2.300051 62.5876 + 82 0.0000 2.307971 62.8031 + 83 0.0000 2.373556 64.5877 + 84 0.0000 2.410245 65.5861 + 85 0.0000 2.453294 66.7575 + 86 0.0000 2.461407 66.9783 + 87 0.0000 2.477021 67.4032 + 88 0.0000 2.508491 68.2595 + 89 0.0000 2.552543 69.4582 + 90 0.0000 2.562209 69.7212 + 91 0.0000 2.599222 70.7284 + 92 0.0000 2.675575 72.8061 + 93 0.0000 2.713089 73.8269 + 94 0.0000 2.757975 75.0483 + 95 0.0000 2.806401 76.3660 + 96 0.0000 2.843321 77.3707 + 97 0.0000 2.883096 78.4530 + 98 0.0000 2.952763 80.3488 + 99 0.0000 2.996117 81.5285 + 100 0.0000 3.053456 83.0888 + 101 0.0000 3.163091 86.0721 + 102 0.0000 3.234222 88.0077 + 103 0.0000 3.487024 94.8868 + 104 0.0000 3.732568 101.5683 + 105 0.0000 3.817281 103.8735 + 106 0.0000 4.053518 110.3018 + 107 0.0000 4.174665 113.5984 + 108 0.0000 4.188250 113.9681 + 109 0.0000 4.305731 117.1649 + 110 0.0000 4.344541 118.2210 + 111 0.0000 4.392951 119.5383 + 112 0.0000 4.534177 123.3812 + 113 0.0000 4.611840 125.4945 + 114 0.0000 4.674397 127.1968 + 115 0.0000 4.721296 128.4730 + 116 0.0000 4.807668 130.8233 + 117 0.0000 4.895369 133.2098 + 118 0.0000 4.933616 134.2505 + 119 0.0000 4.954708 134.8245 + 120 0.0000 5.056820 137.6031 + 121 0.0000 5.096177 138.6740 + 122 0.0000 5.179011 140.9281 + 123 0.0000 5.198776 141.4659 + 124 0.0000 5.213695 141.8718 + 125 0.0000 5.340339 145.3180 + 126 0.0000 5.371480 146.1654 + 127 0.0000 5.471743 148.8937 + 128 0.0000 5.527685 150.4159 + 129 0.0000 5.728146 155.8708 + 130 0.0000 5.752274 156.5273 + 131 0.0000 5.933668 161.4633 + 132 0.0000 6.176650 168.0752 + 133 0.0000 6.410228 174.4312 + 134 0.0000 6.487135 176.5239 + 135 0.0000 6.501115 176.9043 + 136 0.0000 6.701606 182.3600 + 137 0.0000 6.724208 182.9750 + 138 0.0000 6.772428 184.2871 + 139 0.0000 6.809206 185.2879 + 140 0.0000 6.831247 185.8877 + 141 0.0000 7.061639 192.1570 + 142 0.0000 7.104133 193.3133 + 143 0.0000 7.120552 193.7601 + 144 0.0000 7.201677 195.9676 + 145 0.0000 7.258008 197.5004 + 146 0.0000 7.281860 198.1495 + 147 0.0000 7.351468 200.0436 + 148 0.0000 7.393533 201.1883 + 149 0.0000 7.446584 202.6319 + 150 0.0000 7.461009 203.0244 + 151 0.0000 7.545509 205.3237 + 152 0.0000 7.594569 206.6587 + 153 0.0000 7.600491 206.8199 + 154 0.0000 7.762086 211.2171 + 155 0.0000 7.902955 215.0503 + 156 0.0000 7.939258 216.0382 + 157 0.0000 8.395311 228.4480 + 158 0.0000 14.073217 382.9517 + 159 0.0000 14.819658 403.2634 + 160 0.0000 16.116250 438.5455 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.376701 0.000000 + 1 N : 0.354765 0.000000 + 2 O : -0.229781 0.000000 + 3 H : 0.251717 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.869338 s : 3.869338 + pz : 1.288960 p : 4.479458 + px : 1.498079 + py : 1.692419 + dz2 : 0.010417 d : 0.023545 + dxz : 0.007112 + dyz : 0.004265 + dx2y2 : 0.000479 + dxy : 0.001272 + f0 : 0.001638 f : 0.004360 + f+1 : 0.000718 + f-1 : 0.000807 + f+2 : 0.000122 + f-2 : 0.000304 + f+3 : 0.000159 + f-3 : 0.000612 + 1 N s : 3.822007 s : 3.822007 + pz : 0.854883 p : 2.657597 + px : 0.890960 + py : 0.911754 + dz2 : 0.027768 d : 0.135179 + dxz : 0.040654 + dyz : 0.018709 + dx2y2 : 0.028558 + dxy : 0.019490 + f0 : 0.008600 f : 0.030453 + f+1 : 0.003638 + f-1 : 0.005460 + f+2 : 0.002285 + f-2 : 0.004612 + f+3 : 0.003976 + f-3 : 0.001882 + 2 O s : 3.875847 s : 3.875847 + pz : 1.780133 p : 4.282881 + px : 1.200257 + py : 1.302490 + dz2 : 0.004699 d : 0.063506 + dxz : 0.011452 + dyz : 0.006376 + dx2y2 : 0.026578 + dxy : 0.014401 + f0 : 0.001205 f : 0.007547 + f+1 : 0.000775 + f-1 : 0.000531 + f+2 : 0.000103 + f-2 : 0.001103 + f+3 : 0.002751 + f-3 : 0.001079 + 3 H s : 0.641536 s : 0.641536 + pz : 0.019581 p : 0.086315 + px : 0.031465 + py : 0.035269 + dz2 : 0.001219 d : 0.020432 + dxz : 0.005172 + dyz : 0.003150 + dx2y2 : 0.009801 + dxy : 0.001091 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.575674 0.000000 + 1 N : -0.233389 0.000000 + 2 O : 0.249269 0.000000 + 3 H : -0.591554 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.136114 s : 3.136114 + pz : 1.214858 p : 3.956419 + px : 1.317537 + py : 1.424023 + dz2 : 0.095152 d : 0.256870 + dxz : 0.066064 + dyz : 0.048811 + dx2y2 : 0.015500 + dxy : 0.031342 + f0 : 0.021526 f : 0.074924 + f+1 : 0.016753 + f-1 : 0.014762 + f+2 : 0.008852 + f-2 : 0.007663 + f+3 : 0.001647 + f-3 : 0.003720 + 1 N s : 3.035944 s : 3.035944 + pz : 0.887019 p : 2.839154 + px : 1.024129 + py : 0.928006 + dz2 : 0.203218 d : 0.920758 + dxz : 0.271801 + dyz : 0.120330 + dx2y2 : 0.141174 + dxy : 0.184235 + f0 : 0.105128 f : 0.437532 + f+1 : 0.059971 + f-1 : 0.055697 + f+2 : 0.034767 + f-2 : 0.068450 + f+3 : 0.060928 + f-3 : 0.052591 + 2 O s : 3.315786 s : 3.315786 + pz : 1.454301 p : 3.985355 + px : 1.308479 + py : 1.222576 + dz2 : 0.049681 d : 0.331439 + dxz : 0.087140 + dyz : 0.022636 + dx2y2 : 0.061962 + dxy : 0.110020 + f0 : 0.014055 f : 0.118150 + f+1 : 0.017406 + f-1 : 0.008821 + f+2 : 0.010184 + f-2 : 0.017178 + f+3 : 0.025031 + f-3 : 0.025475 + 3 H s : 0.627666 s : 0.627666 + pz : 0.145909 p : 0.572888 + px : 0.222605 + py : 0.204375 + dz2 : 0.032677 d : 0.391000 + dxz : 0.092785 + dyz : 0.051161 + dx2y2 : 0.118635 + dxy : 0.095742 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3767 8.0000 -0.3767 1.8304 1.8304 0.0000 + 1 N 6.6452 7.0000 0.3548 2.5910 2.5910 0.0000 + 2 O 8.2298 8.0000 -0.2298 1.8080 1.8080 0.0000 + 3 H 0.7483 1.0000 0.2517 0.9841 0.9841 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8155 B( 0-O , 3-H ) : 0.9591 B( 1-N , 2-O ) : 1.7513 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.003 sec +Sum of individual times .... 0.700 sec ( 69.8%) + +Fock matrix formation .... 0.502 sec ( 50.1%) +Diagonalization .... 0.056 sec ( 5.6%) +Density matrix formation .... 0.004 sec ( 0.4%) +Population analysis .... 0.091 sec ( 9.1%) +Initial guess .... 0.009 sec ( 0.9%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.5%) +DIIS solution .... 0.037 sec ( 3.7%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.209 sec +Reference energy ... -204.706734375 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.366 sec +AO-integral generation ... 0.146 sec +Half transformation ... 0.080 sec +K-integral sorting ... 5.373 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.025 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.029 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.038 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.023 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.353 sec +AO-integral generation ... 0.247 sec +Half transformation ... 0.042 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.156 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.257 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090072438 +EMP2(bb)= -0.090072438 +EMP2(ab)= -0.517508470 + +Initial guess performed in 0.133 sec +E(0) ... -204.706734375 +E(MP2) ... -0.697653345 +Initial E(tot) ... -205.404387720 + ... 0.189616124 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.404387720 -0.697653345 -0.000000000 0.019099021 2.73 0.000001472 + *** Turning on DIIS *** + 1 -205.375944430 -0.669210056 0.028443289 0.010125153 2.72 0.055721602 + 2 -205.395495824 -0.688761450 -0.019551394 0.003764063 2.77 0.058449343 + 3 -205.399318942 -0.692584568 -0.003823118 0.001910623 2.84 0.071509899 + 4 -205.400858112 -0.694123737 -0.001539169 0.000912160 2.80 0.077328081 + 5 -205.401349567 -0.694615192 -0.000491455 0.000576248 2.88 0.081735434 + 6 -205.401430508 -0.694696134 -0.000080942 0.000395850 2.88 0.083788715 + 7 -205.401463627 -0.694729252 -0.000033118 0.000236649 2.91 0.084734631 + 8 -205.401471597 -0.694737222 -0.000007970 0.000142101 2.90 0.085153881 + 9 -205.401468254 -0.694733879 0.000003342 0.000084367 2.83 0.085320806 + 10 -205.401473221 -0.694738846 -0.000004967 0.000049933 2.78 0.085403756 + 11 -205.401469744 -0.694735369 0.000003477 0.000031002 2.77 0.085414981 + 12 -205.401472405 -0.694738030 -0.000002661 0.000018027 2.77 0.085433790 + 13 -205.401472297 -0.694737922 0.000000108 0.000010481 2.82 0.085432815 + 14 -205.401472735 -0.694738360 -0.000000437 0.000005434 2.88 0.085438865 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.706734375 +E(CORR) ... -0.694738360 +E(TOT) ... -205.401472735 +Singles norm **1/2 ... 0.085438865 ( 0.042719432, 0.042719432) +T1 diagnostic ... 0.020138134 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.058341 + 8a-> 13a 8b-> 13b 0.053957 + 9a-> 13a 8b-> 13b 0.046417 + 8a-> 13a 9b-> 13b 0.046417 + 5a-> 13a 5b-> 13b 0.029905 + 8a-> 13a -1a-> -1a 0.027752 + 8b-> 13b -1b-> -1b 0.027752 + 11a-> 13a 11b-> 13b 0.027575 + 11a-> 25a 11b-> 25b 0.022897 + 11a-> 24a 11b-> 24b 0.022567 + 9a-> 13a 9b-> 22b 0.022145 + 9a-> 22a 9b-> 13b 0.022145 + 11a-> 24a 11b-> 25b 0.021361 + 11a-> 25a 11b-> 24b 0.021361 + 11a-> 25a -1a-> -1a 0.019931 + 11b-> 25b -1b-> -1b 0.019931 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034533138 + alpha-alpha-alpha ... -0.000863496 ( 2.5%) + alpha-alpha-beta ... -0.016403073 ( 47.5%) + alpha-beta -beta ... -0.016403073 ( 47.5%) + beta -beta -beta ... -0.000863496 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034533138 + +Final correlation energy ... -0.729271498 +E(CCSD) ... -205.401472735 +E(CCSD(T)) ... -205.436005872 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210501921 sqrt= 1.100228122 +W(HF) = 0.826103604 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.315984 -0.000000 + 1 N : 0.181153 0.000000 + 2 O : -0.104677 -0.000000 + 3 H : 0.239507 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.845900 s : 3.845900 + pz : 1.272260 p : 4.407223 + px : 1.483065 + py : 1.651898 + dz2 : 0.015051 d : 0.054757 + dxz : 0.012478 + dyz : 0.011523 + dx2y2 : 0.007885 + dxy : 0.007819 + f0 : 0.001948 f : 0.008104 + f+1 : 0.001069 + f-1 : 0.001350 + f+2 : 0.000742 + f-2 : 0.000947 + f+3 : 0.000796 + f-3 : 0.001251 + 1 N s : 3.876366 s : 3.876366 + pz : 0.899901 p : 2.748076 + px : 0.906362 + py : 0.941813 + dz2 : 0.034512 d : 0.164889 + dxz : 0.049691 + dyz : 0.026967 + dx2y2 : 0.029576 + dxy : 0.024142 + f0 : 0.008198 f : 0.029517 + f+1 : 0.003406 + f-1 : 0.005525 + f+2 : 0.002767 + f-2 : 0.004536 + f+3 : 0.003137 + f-3 : 0.001947 + 2 O s : 3.863062 s : 3.863062 + pz : 1.692697 p : 4.147373 + px : 1.183557 + py : 1.271120 + dz2 : 0.009988 d : 0.084324 + dxz : 0.018594 + dyz : 0.012331 + dx2y2 : 0.026509 + dxy : 0.016902 + f0 : 0.001660 f : 0.009917 + f+1 : 0.001246 + f-1 : 0.000982 + f+2 : 0.000717 + f-2 : 0.001511 + f+3 : 0.002472 + f-3 : 0.001331 + 3 H s : 0.649287 s : 0.649287 + pz : 0.023071 p : 0.093730 + px : 0.030764 + py : 0.039896 + dz2 : 0.001194 d : 0.017475 + dxz : 0.004599 + dyz : 0.002740 + dx2y2 : 0.008501 + dxy : 0.000441 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.581741 -0.000000 + 1 N : -0.277690 0.000000 + 2 O : 0.291448 -0.000000 + 3 H : -0.595498 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.140356 s : 3.140356 + pz : 1.211191 p : 3.908421 + px : 1.307122 + py : 1.390108 + dz2 : 0.101312 d : 0.287702 + dxz : 0.072496 + dyz : 0.054046 + dx2y2 : 0.021616 + dxy : 0.038233 + f0 : 0.022870 f : 0.081779 + f+1 : 0.018579 + f-1 : 0.015359 + f+2 : 0.009430 + f-2 : 0.008599 + f+3 : 0.002296 + f-3 : 0.004646 + 1 N s : 3.040757 s : 3.040757 + pz : 0.907098 p : 2.879792 + px : 1.029625 + py : 0.943069 + dz2 : 0.209895 d : 0.929173 + dxz : 0.271344 + dyz : 0.121054 + dx2y2 : 0.137848 + dxy : 0.189032 + f0 : 0.102146 f : 0.427968 + f+1 : 0.060391 + f-1 : 0.054585 + f+2 : 0.033260 + f-2 : 0.064695 + f+3 : 0.059758 + f-3 : 0.053133 + 2 O s : 3.318519 s : 3.318519 + pz : 1.398358 p : 3.904217 + px : 1.299587 + py : 1.206273 + dz2 : 0.055467 d : 0.359311 + dxz : 0.089928 + dyz : 0.028587 + dx2y2 : 0.070019 + dxy : 0.115310 + f0 : 0.014866 f : 0.126505 + f+1 : 0.018075 + f-1 : 0.009267 + f+2 : 0.010489 + f-2 : 0.018450 + f+3 : 0.029003 + f-3 : 0.026355 + 3 H s : 0.627768 s : 0.627768 + pz : 0.146474 p : 0.586837 + px : 0.228195 + py : 0.212168 + dz2 : 0.033801 d : 0.380893 + dxz : 0.089411 + dyz : 0.049484 + dx2y2 : 0.113647 + dxy : 0.094550 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3160 8.0000 -0.3160 2.1746 1.7109 0.4637 + 1 N 6.8188 7.0000 0.1812 2.8555 2.3619 0.4936 + 2 O 8.1047 8.0000 -0.1047 2.1942 1.6959 0.4984 + 3 H 0.7605 1.0000 0.2395 1.0065 0.9324 0.0741 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7267 B( 0-O , 3-H ) : 0.8962 B( 1-N , 2-O ) : 1.6035 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 57.645 sec + +Fock Matrix Formation ... 0.209 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 1.898 sec ( 3.3%) +State Vector Update ... 0.096 sec ( 0.2%) +Sigma-vector construction ... 40.291 sec ( 69.9%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.025 sec ( 0.1% of sigma) + (0-ext) ... 0.074 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (2-ext) ... 0.997 sec ( 2.5% of sigma) + (4-ext) ... 22.308 sec ( 55.4% of sigma) + ... 1.404 sec ( 3.5% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.115 sec ( 0.3% of sigma) + Fock-dressing ... 2.213 sec ( 5.5% of sigma) + (ik|jl)-dressing ... 0.079 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.310 sec ( 25.6% of sigma) + Pair energies ... 0.006 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.933 sec ( 12.0% of ALL) + I/O of integral and amplitudes ... 0.834 sec ( 12.0% of (T)) + External N**7 contributions ... 4.040 sec ( 58.3% of (T)) + Internal N**7 contributions ... 0.311 sec ( 4.5% of (T)) + N**6 triples energy contributions ... 1.692 sec ( 24.4% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.436005872322 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.036.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.036.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.646781, -0.204393 -0.299917) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.81077 -0.16098 -0.93639 +Nuclear contribution : -1.35479 0.47248 0.69371 + ----------------------------------------- +Total Dipole Moment : -0.54402 0.31151 -0.24268 + ----------------------------------------- +Magnitude (a.u.) : 0.67222 +Magnitude (Debye) : 1.70866 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.762194 0.399615 0.360615 +Rotational constants in MHz : 82808.491862 11980.147045 10810.977204 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.177066 -0.225658 0.607957 +x,y,z [Debye]: -0.450067 -0.573577 1.545305 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.646781, -0.204393 -0.299917) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.98343 -0.11639 -0.95136 +Nuclear contribution : -1.35479 0.47248 0.69371 + ----------------------------------------- +Total Dipole Moment : -0.37137 0.35609 -0.25764 + ----------------------------------------- +Magnitude (a.u.) : 0.57541 +Magnitude (Debye) : 1.46257 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.762194 0.399615 0.360615 +Rotational constants in MHz : 82808.491862 11980.147045 10810.977204 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.039648 -0.121043 0.561135 +x,y,z [Debye]: -0.100778 -0.307667 1.426292 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 37 * + * * + * Dihedral ( 2, 1, 0, 3) : 114.54545455 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0397453863 RMS(Int)= 0.0000926356 + Iter 1: RMS(Cart)= 0.0000257832 RMS(Int)= 0.0000002968 + Iter 2: RMS(Cart)= 0.0000000826 RMS(Int)= 0.0000000010 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.5024 0.000000 + 2. B(O 2,N 1) 1.1667 0.000000 + 3. B(H 3,O 0) 0.9722 0.000000 + 4. A(N 1,O 0,H 3) 102.3743 0.000000 + 5. A(O 0,N 1,O 2) 110.4997 0.000000 + 6. D(O 2,N 1,O 0,H 3) 114.5455 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.329503 -0.152476 0.766347 + N 0.220130 -0.379606 -0.613291 + O 1.242673 0.167570 -0.740945 + H -1.133300 0.364511 0.587888 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.622670 -0.288137 1.448186 + 1 N 7.0000 0 14.007 0.415986 -0.717351 -1.158952 + 2 O 8.0000 0 15.999 2.348312 0.316661 -1.400182 + 3 H 1.0000 0 1.008 -2.141626 0.688827 1.110948 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.502071463809 0.00000000 0.00000000 + O 2 1 0 1.164727406705 110.58240067 0.00000000 + H 1 2 3 0.969506097968 102.45212100 106.36363642 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.838503700177 0.00000000 0.00000000 + O 2 1 0 2.201015819344 110.58240067 0.00000000 + H 1 2 3 1.832101010325 102.45212100 106.36363642 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2225 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 548 shell pairs + la=1 lb=0: 534 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 393 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.306893507758 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.3068935078 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.953e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7028297265 0.000000000000 0.00144695 0.00005191 0.0196450 0.7000 + 1 -204.7037346291 -0.000904902532 0.00139164 0.00004746 0.0162636 0.7000 + ***Turning on DIIS*** + 2 -204.7045105465 -0.000775917384 0.00389798 0.00013002 0.0132222 0.0000 + 3 -204.7077117014 -0.003201154970 0.00179291 0.00005738 0.0050010 0.0000 + 4 -204.7064032972 0.001308404227 0.00086079 0.00002922 0.0019300 0.0000 + 5 -204.7081528875 -0.001749590258 0.00083181 0.00002437 0.0011282 0.0000 + 6 -204.7072680248 0.000884862638 0.00084010 0.00002895 0.0007249 0.0000 + 7 -204.7069900766 0.000277948185 0.00041482 0.00001409 0.0003115 0.0000 + 8 -204.7077348780 -0.000744801346 0.00021864 0.00000816 0.0002146 0.0000 + 9 -204.7072633145 0.000471563443 0.00014733 0.00000577 0.0001321 0.0000 + 10 -204.7074435007 -0.000180186135 0.00006284 0.00000241 0.0000641 0.0000 + 11 -204.7075155877 -0.000072087046 0.00003160 0.00000095 0.0000340 0.0000 + 12 -204.7074344375 0.000081150190 0.00000708 0.00000027 0.0000113 0.0000 + 13 -204.7074568743 -0.000022436721 0.00000271 0.00000009 0.0000033 0.0000 + 14 -204.7074516342 0.000005240050 0.00000120 0.00000004 0.0000026 0.0000 + 15 -204.7074526095 -0.000000975323 0.00000094 0.00000003 0.0000020 0.0000 + 16 -204.7074541869 -0.000001577341 0.00000072 0.00000002 0.0000010 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 17 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70745341 Eh -5570.37300 eV + +Components: +Nuclear Repulsion : 68.30689351 Eh 1858.72507 eV +Electronic Energy : -273.01434692 Eh -7429.09807 eV +One Electron Energy: -416.34125192 Eh -11329.22143 eV +Two Electron Energy: 143.32690500 Eh 3900.12336 eV + +Virial components: +Potential Energy : -408.91576519 Eh -11127.16366 eV +Kinetic Energy : 204.20831178 Eh 5556.79067 eV +Virial Ratio : 2.00244428 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 7.7776e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.8512e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.3502e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.2013e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.689761 -562.9970 + 1 1.0000 -20.618573 -561.0599 + 2 1.0000 -15.805069 -430.0778 + 3 1.0000 -1.614590 -43.9352 + 4 1.0000 -1.372526 -37.3483 + 5 1.0000 -0.952880 -25.9292 + 6 1.0000 -0.769216 -20.9314 + 7 1.0000 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0.0000 0.030397 0.8271 + 13 0.0000 0.068718 1.8699 + 14 0.0000 0.091589 2.4923 + 15 0.0000 0.101018 2.7489 + 16 0.0000 0.115443 3.1414 + 17 0.0000 0.154021 4.1911 + 18 0.0000 0.157157 4.2765 + 19 0.0000 0.173017 4.7080 + 20 0.0000 0.184212 5.0127 + 21 0.0000 0.190010 5.1704 + 22 0.0000 0.201364 5.4794 + 23 0.0000 0.236425 6.4335 + 24 0.0000 0.269776 7.3410 + 25 0.0000 0.281281 7.6541 + 26 0.0000 0.305822 8.3218 + 27 0.0000 0.328598 8.9416 + 28 0.0000 0.335834 9.1385 + 29 0.0000 0.356706 9.7065 + 30 0.0000 0.424426 11.5492 + 31 0.0000 0.507971 13.8226 + 32 0.0000 0.522605 14.2208 + 33 0.0000 0.543542 14.7905 + 34 0.0000 0.572369 15.5750 + 35 0.0000 0.605556 16.4780 + 36 0.0000 0.630127 17.1466 + 37 0.0000 0.650239 17.6939 + 38 0.0000 0.697616 18.9831 + 39 0.0000 0.722358 19.6564 + 40 0.0000 0.740096 20.1390 + 41 0.0000 0.744100 20.2480 + 42 0.0000 0.774426 21.0732 + 43 0.0000 0.792173 21.5561 + 44 0.0000 0.806166 21.9369 + 45 0.0000 0.820737 22.3334 + 46 0.0000 0.850867 23.1533 + 47 0.0000 0.866642 23.5825 + 48 0.0000 0.909277 24.7427 + 49 0.0000 0.939382 25.5619 + 50 0.0000 0.957502 26.0550 + 51 0.0000 0.994915 27.0730 + 52 0.0000 1.000577 27.2271 + 53 0.0000 1.023834 27.8599 + 54 0.0000 1.047326 28.4992 + 55 0.0000 1.108137 30.1539 + 56 0.0000 1.137591 30.9554 + 57 0.0000 1.230700 33.4890 + 58 0.0000 1.247722 33.9522 + 59 0.0000 1.288839 35.0711 + 60 0.0000 1.336388 36.3650 + 61 0.0000 1.419217 38.6189 + 62 0.0000 1.433461 39.0065 + 63 0.0000 1.510210 41.0949 + 64 0.0000 1.526577 41.5403 + 65 0.0000 1.560768 42.4707 + 66 0.0000 1.577385 42.9228 + 67 0.0000 1.639493 44.6129 + 68 0.0000 1.653163 44.9848 + 69 0.0000 1.700190 46.2645 + 70 0.0000 1.775557 48.3154 + 71 0.0000 1.793658 48.8079 + 72 0.0000 1.880674 51.1757 + 73 0.0000 1.933967 52.6259 + 74 0.0000 1.964660 53.4611 + 75 0.0000 2.032998 55.3207 + 76 0.0000 2.055239 55.9259 + 77 0.0000 2.076058 56.4924 + 78 0.0000 2.148444 58.4621 + 79 0.0000 2.208175 60.0875 + 80 0.0000 2.244654 61.0801 + 81 0.0000 2.298307 62.5401 + 82 0.0000 2.304424 62.7066 + 83 0.0000 2.379507 64.7497 + 84 0.0000 2.410273 65.5869 + 85 0.0000 2.455214 66.8098 + 86 0.0000 2.462371 67.0045 + 87 0.0000 2.476954 67.4014 + 88 0.0000 2.510400 68.3114 + 89 0.0000 2.545223 69.2590 + 90 0.0000 2.557274 69.5870 + 91 0.0000 2.601606 70.7933 + 92 0.0000 2.672433 72.7206 + 93 0.0000 2.701283 73.5057 + 94 0.0000 2.753451 74.9252 + 95 0.0000 2.798022 76.1380 + 96 0.0000 2.842331 77.3438 + 97 0.0000 2.881821 78.4183 + 98 0.0000 2.950134 80.2772 + 99 0.0000 3.008100 81.8546 + 100 0.0000 3.056473 83.1709 + 101 0.0000 3.162751 86.0628 + 102 0.0000 3.240956 88.1909 + 103 0.0000 3.484374 94.8146 + 104 0.0000 3.729468 101.4840 + 105 0.0000 3.825839 104.1064 + 106 0.0000 4.050543 110.2209 + 107 0.0000 4.165618 113.3522 + 108 0.0000 4.191792 114.0644 + 109 0.0000 4.310552 117.2961 + 110 0.0000 4.336270 117.9959 + 111 0.0000 4.388988 119.4304 + 112 0.0000 4.545649 123.6934 + 113 0.0000 4.615087 125.5829 + 114 0.0000 4.682053 127.4051 + 115 0.0000 4.719698 128.4295 + 116 0.0000 4.792910 130.4217 + 117 0.0000 4.888423 133.0208 + 118 0.0000 4.934925 134.2861 + 119 0.0000 4.962380 135.0332 + 120 0.0000 5.059938 137.6879 + 121 0.0000 5.091695 138.5521 + 122 0.0000 5.165198 140.5522 + 123 0.0000 5.197297 141.4257 + 124 0.0000 5.221059 142.0722 + 125 0.0000 5.333151 145.1224 + 126 0.0000 5.370406 146.1362 + 127 0.0000 5.441189 148.0623 + 128 0.0000 5.519980 150.2063 + 129 0.0000 5.716451 155.5525 + 130 0.0000 5.760657 156.7554 + 131 0.0000 5.933693 161.4640 + 132 0.0000 6.167316 167.8212 + 133 0.0000 6.403620 174.2514 + 134 0.0000 6.488926 176.5727 + 135 0.0000 6.499702 176.8659 + 136 0.0000 6.700208 182.3219 + 137 0.0000 6.717777 182.8000 + 138 0.0000 6.773088 184.3051 + 139 0.0000 6.806094 185.2032 + 140 0.0000 6.836825 186.0395 + 141 0.0000 7.053040 191.9230 + 142 0.0000 7.108005 193.4186 + 143 0.0000 7.119795 193.7395 + 144 0.0000 7.197320 195.8490 + 145 0.0000 7.254074 197.3934 + 146 0.0000 7.274625 197.9526 + 147 0.0000 7.350317 200.0123 + 148 0.0000 7.392389 201.1571 + 149 0.0000 7.440528 202.4671 + 150 0.0000 7.459920 202.9947 + 151 0.0000 7.537783 205.1135 + 152 0.0000 7.588652 206.4977 + 153 0.0000 7.595060 206.6721 + 154 0.0000 7.784816 211.8356 + 155 0.0000 7.900868 214.9935 + 156 0.0000 7.944834 216.1899 + 157 0.0000 8.380973 228.0579 + 158 0.0000 14.046751 382.2315 + 159 0.0000 14.751097 401.3978 + 160 0.0000 16.081893 437.6105 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.379386 0.000000 + 1 N : 0.356817 0.000000 + 2 O : -0.234334 0.000000 + 3 H : 0.256903 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.871560 s : 3.871560 + pz : 1.286037 p : 4.480291 + px : 1.468899 + py : 1.725354 + dz2 : 0.010418 d : 0.023144 + dxz : 0.006768 + dyz : 0.004372 + dx2y2 : 0.000570 + dxy : 0.001016 + f0 : 0.001700 f : 0.004392 + f+1 : 0.000662 + f-1 : 0.000846 + f+2 : 0.000107 + f-2 : 0.000283 + f+3 : 0.000125 + f-3 : 0.000668 + 1 N s : 3.822887 s : 3.822887 + pz : 0.862370 p : 2.656096 + px : 0.912013 + py : 0.881714 + dz2 : 0.028053 d : 0.133970 + dxz : 0.041219 + dyz : 0.018228 + dx2y2 : 0.025540 + dxy : 0.020929 + f0 : 0.008701 f : 0.030231 + f+1 : 0.003795 + f-1 : 0.005514 + f+2 : 0.002406 + f-2 : 0.004147 + f+3 : 0.003920 + f-3 : 0.001747 + 2 O s : 3.877274 s : 3.877274 + pz : 1.794404 p : 4.285792 + px : 1.196471 + py : 1.294918 + dz2 : 0.004763 d : 0.063689 + dxz : 0.012510 + dyz : 0.005008 + dx2y2 : 0.025035 + dxy : 0.016373 + f0 : 0.001206 f : 0.007578 + f+1 : 0.000829 + f-1 : 0.000500 + f+2 : 0.000244 + f-2 : 0.000953 + f+3 : 0.002761 + f-3 : 0.001085 + 3 H s : 0.637879 s : 0.637879 + pz : 0.019043 p : 0.084808 + px : 0.029073 + py : 0.036692 + dz2 : 0.001026 d : 0.020410 + dxz : 0.005838 + dyz : 0.002649 + dx2y2 : 0.008938 + dxy : 0.001958 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.573365 0.000000 + 1 N : -0.232765 0.000000 + 2 O : 0.246532 0.000000 + 3 H : -0.587132 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.137894 s : 3.137894 + pz : 1.213473 p : 3.956105 + px : 1.308032 + py : 1.434600 + dz2 : 0.099001 d : 0.257599 + dxz : 0.064824 + dyz : 0.047350 + dx2y2 : 0.017814 + dxy : 0.028610 + f0 : 0.022912 f : 0.075038 + f+1 : 0.016955 + f-1 : 0.014384 + f+2 : 0.008597 + f-2 : 0.007035 + f+3 : 0.001046 + f-3 : 0.004109 + 1 N s : 3.036641 s : 3.036641 + pz : 0.894491 p : 2.838510 + px : 1.056668 + py : 0.887351 + dz2 : 0.204481 d : 0.920971 + dxz : 0.280475 + dyz : 0.114916 + dx2y2 : 0.141925 + dxy : 0.179175 + f0 : 0.107240 f : 0.436642 + f+1 : 0.061419 + f-1 : 0.055563 + f+2 : 0.040168 + f-2 : 0.060827 + f+3 : 0.059204 + f-3 : 0.052220 + 2 O s : 3.317632 s : 3.317632 + pz : 1.464821 p : 3.987595 + px : 1.326366 + py : 1.196408 + dz2 : 0.049237 d : 0.330507 + dxz : 0.091968 + dyz : 0.019034 + dx2y2 : 0.065965 + dxy : 0.104303 + f0 : 0.014338 f : 0.117734 + f+1 : 0.018413 + f-1 : 0.007496 + f+2 : 0.012620 + f-2 : 0.014975 + f+3 : 0.023729 + f-3 : 0.026163 + 3 H s : 0.627049 s : 0.627049 + pz : 0.143692 p : 0.569220 + px : 0.229601 + py : 0.195927 + dz2 : 0.033040 d : 0.390863 + dxz : 0.100162 + dyz : 0.042905 + dx2y2 : 0.115672 + dxy : 0.099084 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3794 8.0000 -0.3794 1.8419 1.8419 0.0000 + 1 N 6.6432 7.0000 0.3568 2.5866 2.5866 -0.0000 + 2 O 8.2343 8.0000 -0.2343 1.8029 1.8029 0.0000 + 3 H 0.7431 1.0000 0.2569 0.9769 0.9769 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8261 B( 0-O , 3-H ) : 0.9584 B( 1-N , 2-O ) : 1.7438 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.705 sec +Sum of individual times .... 2.386 sec ( 88.2%) + +Fock matrix formation .... 1.918 sec ( 70.9%) +Diagonalization .... 0.199 sec ( 7.4%) +Density matrix formation .... 0.015 sec ( 0.5%) +Population analysis .... 0.074 sec ( 2.7%) +Initial guess .... 0.010 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.2%) +DIIS solution .... 0.171 sec ( 6.3%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.207 sec +Reference energy ... -204.707453941 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.368 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.377 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.024 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.029 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.045 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.041 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.360 sec +AO-integral generation ... 0.254 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.152 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.256 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090261181 +EMP2(bb)= -0.090261181 +EMP2(ab)= -0.518224482 + +Initial guess performed in 0.134 sec +E(0) ... -204.707453941 +E(MP2) ... -0.698746844 +Initial E(tot) ... -205.406200784 + ... 0.190470276 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.406200784 -0.698746844 -0.000000000 0.019773186 2.68 0.000001841 + *** Turning on DIIS *** + 1 -205.377171754 -0.669717813 0.029029030 0.009321045 2.70 0.056501839 + 2 -205.396894197 -0.689440256 -0.019722443 0.003937457 2.77 0.059213947 + 3 -205.400740510 -0.693286569 -0.003846313 0.001719444 2.81 0.072667971 + 4 -205.402306950 -0.694853009 -0.001566440 0.001244714 2.78 0.078765195 + 5 -205.402825188 -0.695371247 -0.000518238 0.000790764 2.88 0.083576749 + 6 -205.402916661 -0.695462720 -0.000091473 0.000527521 2.82 0.085941244 + 7 -205.402956307 -0.695502367 -0.000039647 0.000290500 2.88 0.087111515 + 8 -205.402966944 -0.695513004 -0.000010637 0.000163909 2.87 0.087637067 + 9 -205.402963210 -0.695509270 0.000003734 0.000068426 2.79 0.087833923 + 10 -205.402968972 -0.695515031 -0.000005761 0.000044765 2.76 0.087921284 + 11 -205.402965372 -0.695511432 0.000003599 0.000031589 2.76 0.087921577 + 12 -205.402967750 -0.695513809 -0.000002377 0.000020399 2.78 0.087942316 + 13 -205.402967628 -0.695513688 0.000000122 0.000012474 2.82 0.087938020 + 14 -205.402967978 -0.695514038 -0.000000350 0.000006614 2.78 0.087944268 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.707453941 +E(CORR) ... -0.695514038 +E(TOT) ... -205.402967978 +Singles norm **1/2 ... 0.087944268 ( 0.043972134, 0.043972134) +T1 diagnostic ... 0.020728663 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.054698 + 9a-> 13a 9b-> 13b 0.054030 + 9a-> 13a 8b-> 13b 0.045352 + 8a-> 13a 9b-> 13b 0.045352 + 5a-> 13a 5b-> 13b 0.029805 + 8b-> 13b -1b-> -1b 0.029061 + 8a-> 13a -1a-> -1a 0.029061 + 11a-> 13a 11b-> 13b 0.027379 + 10a-> 13a -1a-> -1a 0.025167 + 10b-> 13b -1b-> -1b 0.025167 + 11a-> 25a 11b-> 25b 0.023072 + 11a-> 24a 11b-> 24b 0.020965 + 11a-> 25a 11b-> 24b 0.020614 + 11a-> 24a 11b-> 25b 0.020614 + 11b-> 25b -1b-> -1b 0.020318 + 11a-> 25a -1a-> -1a 0.020318 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034795230 + alpha-alpha-alpha ... -0.000871560 ( 2.5%) + alpha-alpha-beta ... -0.016526055 ( 47.5%) + alpha-beta -beta ... -0.016526055 ( 47.5%) + beta -beta -beta ... -0.000871560 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034795230 + +Final correlation energy ... -0.730309267 +E(CCSD) ... -205.402967978 +E(CCSD(T)) ... -205.437763208 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.212019158 sqrt= 1.100917416 +W(HF) = 0.825069467 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.313990 -0.000000 + 1 N : 0.179696 0.000000 + 2 O : -0.109652 -0.000000 + 3 H : 0.243946 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.847748 s : 3.847748 + pz : 1.271012 p : 4.403561 + px : 1.454395 + py : 1.678155 + dz2 : 0.015043 d : 0.054528 + dxz : 0.012218 + dyz : 0.011697 + dx2y2 : 0.007924 + dxy : 0.007647 + f0 : 0.001984 f : 0.008152 + f+1 : 0.001041 + f-1 : 0.001394 + f+2 : 0.000739 + f-2 : 0.000930 + f+3 : 0.000763 + f-3 : 0.001301 + 1 N s : 3.876852 s : 3.876852 + pz : 0.906904 p : 2.750173 + px : 0.920914 + py : 0.922355 + dz2 : 0.034571 d : 0.163925 + dxz : 0.050556 + dyz : 0.026753 + dx2y2 : 0.026812 + dxy : 0.025232 + f0 : 0.008318 f : 0.029354 + f+1 : 0.003550 + f-1 : 0.005567 + f+2 : 0.002856 + f-2 : 0.004170 + f+3 : 0.003017 + f-3 : 0.001878 + 2 O s : 3.864342 s : 3.864342 + pz : 1.705779 p : 4.150859 + px : 1.181480 + py : 1.263600 + dz2 : 0.009998 d : 0.084493 + dxz : 0.019797 + dyz : 0.011119 + dx2y2 : 0.025048 + dxy : 0.018532 + f0 : 0.001668 f : 0.009957 + f+1 : 0.001298 + f-1 : 0.000952 + f+2 : 0.000837 + f-2 : 0.001400 + f+3 : 0.002469 + f-3 : 0.001334 + 3 H s : 0.646647 s : 0.646647 + pz : 0.022562 p : 0.091964 + px : 0.027371 + py : 0.042031 + dz2 : 0.001067 d : 0.017443 + dxz : 0.005185 + dyz : 0.002326 + dx2y2 : 0.007635 + dxy : 0.001230 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.581155 -0.000000 + 1 N : -0.278604 0.000000 + 2 O : 0.287855 0.000000 + 3 H : -0.590406 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.142444 s : 3.142444 + pz : 1.211558 p : 3.905876 + px : 1.298417 + py : 1.395901 + dz2 : 0.105299 d : 0.288596 + dxz : 0.071151 + dyz : 0.052635 + dx2y2 : 0.024120 + dxy : 0.035390 + f0 : 0.024219 f : 0.081929 + f+1 : 0.018769 + f-1 : 0.015098 + f+2 : 0.009181 + f-2 : 0.007932 + f+3 : 0.001665 + f-3 : 0.005065 + 1 N s : 3.041424 s : 3.041424 + pz : 0.914083 p : 2.880662 + px : 1.057372 + py : 0.909208 + dz2 : 0.211201 d : 0.929671 + dxz : 0.279425 + dyz : 0.116406 + dx2y2 : 0.139614 + dxy : 0.183025 + f0 : 0.104424 f : 0.426848 + f+1 : 0.061722 + f-1 : 0.054254 + f+2 : 0.037968 + f-2 : 0.057447 + f+3 : 0.058274 + f-3 : 0.052758 + 2 O s : 3.320237 s : 3.320237 + pz : 1.407838 p : 3.907001 + px : 1.318395 + py : 1.180769 + dz2 : 0.055000 d : 0.358736 + dxz : 0.094501 + dyz : 0.025156 + dx2y2 : 0.073978 + dxy : 0.110101 + f0 : 0.015113 f : 0.126170 + f+1 : 0.019055 + f-1 : 0.007989 + f+2 : 0.012837 + f-2 : 0.016277 + f+3 : 0.027967 + f-3 : 0.026932 + 3 H s : 0.627326 s : 0.627326 + pz : 0.144330 p : 0.582493 + px : 0.234726 + py : 0.203437 + dz2 : 0.034297 d : 0.380587 + dxz : 0.096536 + dyz : 0.041423 + dx2y2 : 0.110984 + dxy : 0.097348 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3140 8.0000 -0.3140 2.1929 1.7265 0.4665 + 1 N 6.8203 7.0000 0.1797 2.8559 2.3618 0.4940 + 2 O 8.1097 8.0000 -0.1097 2.1926 1.6929 0.4997 + 3 H 0.7561 1.0000 0.2439 0.9999 0.9258 0.0741 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7400 B( 0-O , 3-H ) : 0.8948 B( 1-N , 2-O ) : 1.5961 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 57.217 sec + +Fock Matrix Formation ... 0.207 sec ( 0.4%) +Initial Guess ... 0.134 sec ( 0.2%) +DIIS Solver ... 1.899 sec ( 3.3%) +State Vector Update ... 0.089 sec ( 0.2%) +Sigma-vector construction ... 39.875 sec ( 69.7%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.025 sec ( 0.1% of sigma) + (0-ext) ... 0.072 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (2-ext) ... 0.988 sec ( 2.5% of sigma) + (4-ext) ... 22.178 sec ( 55.6% of sigma) + ... 1.398 sec ( 3.5% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.115 sec ( 0.3% of sigma) + Fock-dressing ... 2.221 sec ( 5.6% of sigma) + (ik|jl)-dressing ... 0.078 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.949 sec ( 25.0% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.961 sec ( 12.2% of ALL) + I/O of integral and amplitudes ... 0.665 sec ( 9.5% of (T)) + External N**7 contributions ... 3.882 sec ( 55.8% of (T)) + Internal N**7 contributions ... 0.307 sec ( 4.4% of (T)) + N**6 triples energy contributions ... 1.548 sec ( 22.2% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.437763207956 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.004651384 -0.007064306 0.000946655 + 2 N : 0.002706805 -0.007991312 0.001614137 + 3 O : 0.000145400 0.007095342 -0.003039160 + 4 H : 0.001799180 0.007960275 0.000478368 + +Norm of the cartesian gradient ... 0.016512499 +RMS gradient ... 0.004766748 +MAX gradient ... 0.007991312 + +------- +TIMINGS +------- + +Total numerical gradient time ... 361.782 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: -386.87 cm**-1 ***imaginary mode*** + 7: 544.12 cm**-1 + 8: 775.51 cm**-1 + 9: 1144.54 cm**-1 + 10: 1707.82 cm**-1 + 11: 3729.06 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 -0.052858 -0.376769 0.130043 -0.037300 0.011133 -0.052261 + 1 -0.044247 -0.024155 0.183223 0.010666 -0.017381 0.032846 + 2 0.019731 0.489728 0.165999 -0.064043 -0.087000 -0.010616 + 3 0.048354 0.238421 0.030611 0.024132 0.636296 -0.000844 + 4 -0.064961 0.102553 -0.244179 -0.022707 0.376645 -0.000808 + 5 -0.006690 -0.211611 -0.601535 0.032464 0.030415 -0.000077 + 6 -0.021321 0.198903 -0.148976 0.030888 -0.567787 0.000595 + 7 0.047376 -0.042851 0.035449 0.006655 -0.311782 0.000845 + 8 -0.016786 -0.305212 0.323371 -0.025282 0.051022 -0.000254 + 9 0.505445 -0.489981 -0.124841 -0.233556 -0.006646 0.831788 + 10 0.853032 -0.361540 -0.077692 0.040613 -0.009321 -0.523511 + 11 0.046220 0.011884 0.591538 0.966647 0.148398 0.173609 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 7: 544.12 0.025045 126.57 0.014364 ( 0.074731 -0.009710 -0.093192) + 8: 775.51 0.016496 83.36 0.006638 ( 0.044365 -0.011879 -0.067295) + 9: 1144.54 0.019159 96.82 0.005224 (-0.035464 0.016846 0.060682) + 10: 1707.82 0.033272 168.14 0.006080 ( 0.058397 0.009638 -0.050760) + 11: 3729.06 0.012615 63.75 0.001056 ( 0.027839 -0.013991 -0.009213) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 7 +The total number of vibrations considered is 5 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 544.12 E(vib) ... 0.12 +freq. 775.51 E(vib) ... 0.05 +freq. 1144.54 E(vib) ... 0.01 +freq. 1707.82 E(vib) ... 0.00 +freq. 3729.06 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.43776321 Eh +Zero point energy ... 0.01799990 Eh 11.30 kcal/mol +Thermal vibrational correction ... 0.00030222 Eh 0.19 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.41662855 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00313476 Eh 1.97 kcal/mol +Non-thermal (ZPE) correction 0.01799990 Eh 11.30 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02113466 Eh 13.26 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.41662855 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.41568434 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.784305 0.398515 0.358908 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00040026 Eh 0.25 kcal/mol +Rotational entropy ... 0.00994546 Eh 6.24 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02814804 Eh 17.66 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00994546 Eh 6.24 kcal/mol| +| sn= 2 | S(rot)= 0.00929101 Eh 5.83 kcal/mol| +| sn= 3 | S(rot)= 0.00890818 Eh 5.59 kcal/mol| +| sn= 4 | S(rot)= 0.00863655 Eh 5.42 kcal/mol| +| sn= 5 | S(rot)= 0.00842586 Eh 5.29 kcal/mol| +| sn= 6 | S(rot)= 0.00825372 Eh 5.18 kcal/mol| +| sn= 7 | S(rot)= 0.00810817 Eh 5.09 kcal/mol| +| sn= 8 | S(rot)= 0.00798210 Eh 5.01 kcal/mol| +| sn= 9 | S(rot)= 0.00787089 Eh 4.94 kcal/mol| +| sn=10 | S(rot)= 0.00777141 Eh 4.88 kcal/mol| +| sn=11 | S(rot)= 0.00768142 Eh 4.82 kcal/mol| +| sn=12 | S(rot)= 0.00759926 Eh 4.77 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.41568434 Eh +Total entropy correction ... -0.02814804 Eh -17.66 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44383238 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00606917 Eh -3.81 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.437763207 Eh +Current gradient norm .... 0.016512499 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + -0.017223395 0.097498921 0.152682605 0.474655250 0.499874257 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999841518 +Lowest eigenvalues of augmented Hessian: + -0.000064955 0.096316324 0.152161437 0.474576920 0.499802846 +Length of the computed step .... 0.017805597 +The final length of the internal step .... 0.017805597 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0072691044 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0054577842 RMS(Int)= 0.0072682061 + Iter 1: RMS(Cart)= 0.0000032199 RMS(Int)= 0.0000040090 + Iter 2: RMS(Cart)= 0.0000000125 RMS(Int)= 0.0000000145 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000003 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0022098824 0.0001000000 NO + MAX gradient 0.0037876168 0.0003000000 NO + RMS step 0.0072691044 0.0020000000 NO + MAX step 0.0168244034 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0089 Max(Angles) 0.07 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.5024 0.002488 -0.0089 1.4935 + 2. B(O 2,N 1) 1.1667 0.003788 -0.0011 1.1656 + 3. B(H 3,O 0) 0.9722 0.002658 -0.0028 0.9694 + 4. A(N 1,O 0,H 3) 102.37 0.000782 -0.07 102.30 + 5. A(O 0,N 1,O 2) 110.50 0.001046 -0.01 110.49 + 6. D(O 2,N 1,O 0,H 3) 114.55 -0.013855 0.00 114.55 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.327333 -0.152553 0.762776 + N 0.217120 -0.378496 -0.609425 + O 1.238780 0.167757 -0.738077 + H -1.128566 0.363292 0.584725 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.618570 -0.288283 1.441438 + 1 N 7.0000 0 14.007 0.410298 -0.715254 -1.151646 + 2 O 8.0000 0 15.999 2.340954 0.317015 -1.394763 + 3 H 1.0000 0 1.008 -2.132680 0.686522 1.104971 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.493457145655 0.00000000 0.00000000 + O 2 1 0 1.165646325289 110.48958975 0.00000000 + H 1 2 3 0.969418226378 102.30170982 114.54545483 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.822224998036 0.00000000 0.00000000 + O 2 1 0 2.202752323808 110.48958975 0.00000000 + H 1 2 3 1.831934957086 102.30170982 114.54545483 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2225 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2692 + la=0 lb=0: 548 shell pairs + la=1 lb=0: 534 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 393 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.538318436656 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.933e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7085840518 0.000000000000 0.00033721 0.00000721 0.0014608 0.7000 + 1 -204.7085918315 -0.000007779726 0.00026074 0.00000591 0.0011162 0.7000 + ***Turning on DIIS*** + 2 -204.7085982245 -0.000006393023 0.00059763 0.00001527 0.0008419 0.0000 + 3 -204.7080482447 0.000549979801 0.00023352 0.00000569 0.0001904 0.0000 + 4 -204.7086685415 -0.000620296794 0.00006094 0.00000194 0.0000752 0.0000 + 5 -204.7088117150 -0.000143173484 0.00002901 0.00000088 0.0000304 0.0000 + 6 -204.7085018326 0.000309882420 0.00001736 0.00000056 0.0000234 0.0000 + 7 -204.7086247946 -0.000122962028 0.00001096 0.00000038 0.0000145 0.0000 + 8 -204.7086125871 0.000012207552 0.00000992 0.00000033 0.0000076 0.0000 + 9 -204.7086045010 0.000008086076 0.00000559 0.00000023 0.0000044 0.0000 + 10 -204.7086302469 -0.000025745958 0.00000223 0.00000009 0.0000023 0.0000 + 11 -204.7086177503 0.000012496690 0.00000121 0.00000005 0.0000011 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + +Total Energy : -204.70862006 Eh -5570.40475 eV + Last Energy change ... -2.3111e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.0662e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.205 sec +Reference energy ... -204.708619205 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.405 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.407 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.024 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.029 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.349 sec +AO-integral generation ... 0.241 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.155 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.250 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090120069 +EMP2(bb)= -0.090120069 +EMP2(ab)= -0.517321632 + +Initial guess performed in 0.132 sec +E(0) ... -204.708619205 +E(MP2) ... -0.697561770 +Initial E(tot) ... -205.406180975 + ... 0.189347269 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.406180975 -0.697561770 -0.000000000 0.019671439 2.68 0.000000625 + *** Turning on DIIS *** + 1 -205.377707758 -0.669088554 0.028473216 0.009332523 2.70 0.056020280 + 2 -205.397238752 -0.688619548 -0.019530994 0.003927075 2.77 0.058822778 + 3 -205.401052201 -0.692432996 -0.003813448 0.001721115 2.79 0.072149004 + 4 -205.402596900 -0.693977695 -0.001544699 0.001226491 2.81 0.078186110 + 5 -205.403104221 -0.694485016 -0.000507321 0.000778968 2.86 0.082921407 + 6 -205.403194254 -0.694575049 -0.000090033 0.000517357 3.01 0.085241065 + 7 -205.403232721 -0.694613516 -0.000038467 0.000284847 3.33 0.086371671 + 8 -205.403242831 -0.694623626 -0.000010110 0.000159942 3.19 0.086876446 + 9 -205.403239223 -0.694620018 0.000003608 0.000066939 3.03 0.087065009 + 10 -205.403244677 -0.694625472 -0.000005454 0.000043889 3.05 0.087147828 + 11 -205.403241263 -0.694622059 0.000003414 0.000030966 3.15 0.087148347 + 12 -205.403243535 -0.694624330 -0.000002272 0.000020021 3.51 0.087167750 + 13 -205.403243421 -0.694624216 0.000000114 0.000012110 3.89 0.087163940 + 14 -205.403243763 -0.694624558 -0.000000342 0.000006376 4.56 0.087169929 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.708619205 +E(CORR) ... -0.694624558 +E(TOT) ... -205.403243763 +Singles norm **1/2 ... 0.087169929 ( 0.043584964, 0.043584964) +T1 diagnostic ... 0.020546149 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.054584 + 8a-> 13a 8b-> 13b 0.053185 + 8a-> 13a 9b-> 13b 0.044806 + 9a-> 13a 8b-> 13b 0.044806 + 5a-> 13a 5b-> 13b 0.029437 + 8a-> 13a -1a-> -1a 0.028973 + 8b-> 13b -1b-> -1b 0.028973 + 11a-> 13a 11b-> 13b 0.027649 + 11a-> 25a 11b-> 25b 0.025721 + 10b-> 13b -1b-> -1b 0.024701 + 10a-> 13a -1a-> -1a 0.024701 + 11b-> 25b -1b-> -1b 0.021819 + 11a-> 25a -1a-> -1a 0.021819 + 9a-> 22a 9b-> 13b 0.020407 + 9a-> 13a 9b-> 22b 0.020407 + 9a-> 13a 10b-> 13b 0.019915 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034551504 + alpha-alpha-alpha ... -0.000868765 ( 2.5%) + alpha-alpha-beta ... -0.016406987 ( 47.5%) + alpha-beta -beta ... -0.016406987 ( 47.5%) + beta -beta -beta ... -0.000868765 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034551504 + +Final correlation energy ... -0.729176062 +E(CCSD) ... -205.403243763 +E(CCSD(T)) ... -205.437795267 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210707479 sqrt= 1.100321534 +W(HF) = 0.825963346 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 69.231 sec + +Fock Matrix Formation ... 0.205 sec ( 0.3%) +Initial Guess ... 0.132 sec ( 0.2%) +DIIS Solver ... 2.428 sec ( 3.5%) +State Vector Update ... 0.105 sec ( 0.2%) +Sigma-vector construction ... 44.799 sec ( 64.7%) + <0|H|D> ... 0.005 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.030 sec ( 0.1% of sigma) + (0-ext) ... 0.082 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.030 sec ( 0.1% of sigma) + (2-ext) ... 1.099 sec ( 2.5% of sigma) + (4-ext) ... 25.045 sec ( 55.9% of sigma) + ... 1.802 sec ( 4.0% of sigma) + ... 0.003 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.131 sec ( 0.3% of sigma) + Fock-dressing ... 2.473 sec ( 5.5% of sigma) + (ik|jl)-dressing ... 0.087 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 11.126 sec ( 24.8% of sigma) + Pair energies ... 0.009 sec ( 0.0% of sigma) +Total Time for computing (T) ... 12.702 sec ( 18.3% of ALL) + I/O of integral and amplitudes ... 1.196 sec ( 9.4% of (T)) + External N**7 contributions ... 6.265 sec ( 49.3% of (T)) + Internal N**7 contributions ... 0.538 sec ( 4.2% of (T)) + N**6 triples energy contributions ... 2.330 sec ( 18.3% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.437795266707 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.005617872 -0.006086863 -0.001299773 + 2 N : 0.004776067 -0.006169442 0.002952725 + 3 O : -0.003341715 0.005571636 -0.002203300 + 4 H : 0.004183520 0.006684669 0.000550349 + +Norm of the cartesian gradient ... 0.015793842 +RMS gradient ... 0.004559290 +MAX gradient ... 0.006684669 + +------- +TIMINGS +------- + +Total numerical gradient time ... 651.895 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.437795267 Eh +Current gradient norm .... 0.015793842 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999842 +Lowest eigenvalues of augmented Hessian: + -0.000000042 0.097764050 0.152931798 0.474556015 0.497809950 +Length of the computed step .... 0.000561782 +The final length of the internal step .... 0.000561782 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0002293467 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001460469 RMS(Int)= 0.0002293482 + Iter 1: RMS(Cart)= 0.0000000035 RMS(Int)= 0.0000000053 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000320600 0.0000050000 NO + RMS gradient 0.0000449272 0.0001000000 YES + MAX gradient 0.0000752397 0.0003000000 YES + RMS step 0.0002293467 0.0020000000 YES + MAX step 0.0005612013 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0003 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4935 -0.000075 0.0003 1.4938 + 2. B(O 2,N 1) 1.1656 -0.000075 0.0000 1.1656 + 3. B(H 3,O 0) 0.9694 -0.000002 0.0000 0.9694 + 4. A(N 1,O 0,H 3) 102.30 -0.000013 -0.00 102.30 + 5. A(O 0,N 1,O 2) 110.49 -0.000027 0.00 110.49 + 6. D(O 2,N 1,O 0,H 3) 114.55 -0.014152 -0.00 114.55 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.327423 -0.152535 0.762903 + N 0.217205 -0.378515 -0.609545 + O 1.238868 0.167748 -0.738150 + H -1.128649 0.363303 0.584792 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.618740 -0.288250 1.441678 + 1 N 7.0000 0 14.007 0.410458 -0.715290 -1.151874 + 2 O 8.0000 0 15.999 2.341122 0.316998 -1.394902 + 3 H 1.0000 0 1.008 -2.132838 0.686542 1.105098 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.493754120578 0.00000000 0.00000000 + O 2 1 0 1.165649541654 110.48971572 0.00000000 + H 1 2 3 0.969419804958 102.30030408 114.54545483 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.822786199310 0.00000000 0.00000000 + O 2 1 0 2.202758401856 110.48971572 0.00000000 + H 1 2 3 1.831937940169 102.30030408 114.54545483 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2225 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2692 + la=0 lb=0: 548 shell pairs + la=1 lb=0: 534 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 393 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.532090214658 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.5320902147 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.933e-04 +Time for diagonalization ... 0.005 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.005 sec +Total time needed ... 0.016 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7085905912 0.000000000000 0.00000907 0.00000019 0.0000434 0.7000 + 1 -204.7085906001 -0.000000008837 0.00000689 0.00000016 0.0000343 0.7000 + ***Turning on DIIS*** + 2 -204.7085906074 -0.000000007315 0.00001675 0.00000042 0.0000267 0.0000 + 3 -204.7085987890 -0.000008181650 0.00000697 0.00000019 0.0000070 0.0000 + 4 -204.7085877391 0.000011049947 0.00000220 0.00000006 0.0000023 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70858680 Eh -5570.40384 eV + +Components: +Nuclear Repulsion : 68.53209021 Eh 1864.85298 eV +Electronic Energy : -273.24067701 Eh -7435.25682 eV +One Electron Energy: -416.78205495 Eh -11341.21629 eV +Two Electron Energy: 143.54137794 Eh 3905.95947 eV + +Virial components: +Potential Energy : -408.94071215 Eh -11127.84251 eV +Kinetic Energy : 204.23212535 Eh 5557.43867 eV +Virial Ratio : 2.00233294 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 9.3964e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.0378e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.3345e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.0319e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.688159 -562.9534 + 1 1.0000 -20.619172 -561.0762 + 2 1.0000 -15.803680 -430.0400 + 3 1.0000 -1.615502 -43.9600 + 4 1.0000 -1.375810 -37.4377 + 5 1.0000 -0.952466 -25.9179 + 6 1.0000 -0.771005 -20.9801 + 7 1.0000 -0.730157 -19.8686 + 8 1.0000 -0.697752 -18.9868 + 9 1.0000 -0.608686 -16.5632 + 10 1.0000 -0.528890 -14.3918 + 11 1.0000 -0.458373 -12.4730 + 12 0.0000 0.030309 0.8248 + 13 0.0000 0.069866 1.9012 + 14 0.0000 0.091775 2.4973 + 15 0.0000 0.101125 2.7517 + 16 0.0000 0.115257 3.1363 + 17 0.0000 0.154083 4.1928 + 18 0.0000 0.157185 4.2772 + 19 0.0000 0.173047 4.7088 + 20 0.0000 0.184389 5.0175 + 21 0.0000 0.189940 5.1685 + 22 0.0000 0.201624 5.4865 + 23 0.0000 0.236885 6.4460 + 24 0.0000 0.271373 7.3844 + 25 0.0000 0.283301 7.7090 + 26 0.0000 0.306773 8.3477 + 27 0.0000 0.328958 8.9514 + 28 0.0000 0.336171 9.1477 + 29 0.0000 0.356863 9.7107 + 30 0.0000 0.424718 11.5572 + 31 0.0000 0.508092 13.8259 + 32 0.0000 0.522800 14.2261 + 33 0.0000 0.544151 14.8071 + 34 0.0000 0.572391 15.5756 + 35 0.0000 0.605907 16.4876 + 36 0.0000 0.630631 17.1603 + 37 0.0000 0.650761 17.7081 + 38 0.0000 0.697953 18.9923 + 39 0.0000 0.722139 19.6504 + 40 0.0000 0.740431 20.1481 + 41 0.0000 0.744947 20.2711 + 42 0.0000 0.774196 21.0669 + 43 0.0000 0.792844 21.5744 + 44 0.0000 0.806098 21.9350 + 45 0.0000 0.821127 22.3440 + 46 0.0000 0.851373 23.1670 + 47 0.0000 0.867491 23.6056 + 48 0.0000 0.909357 24.7449 + 49 0.0000 0.940067 25.5805 + 50 0.0000 0.957674 26.0596 + 51 0.0000 0.995249 27.0821 + 52 0.0000 1.000635 27.2287 + 53 0.0000 1.024474 27.8773 + 54 0.0000 1.048243 28.5241 + 55 0.0000 1.110052 30.2061 + 56 0.0000 1.138510 30.9804 + 57 0.0000 1.232018 33.5249 + 58 0.0000 1.248982 33.9865 + 59 0.0000 1.289415 35.0868 + 60 0.0000 1.337036 36.3826 + 61 0.0000 1.419861 38.6364 + 62 0.0000 1.432383 38.9771 + 63 0.0000 1.510414 41.1005 + 64 0.0000 1.528130 41.5825 + 65 0.0000 1.561966 42.5033 + 66 0.0000 1.577563 42.9277 + 67 0.0000 1.640702 44.6458 + 68 0.0000 1.654101 45.0104 + 69 0.0000 1.701979 46.3132 + 70 0.0000 1.776965 48.3537 + 71 0.0000 1.794866 48.8408 + 72 0.0000 1.882747 51.2322 + 73 0.0000 1.935301 52.6622 + 74 0.0000 1.966978 53.5242 + 75 0.0000 2.036855 55.4256 + 76 0.0000 2.057397 55.9846 + 77 0.0000 2.079678 56.5909 + 78 0.0000 2.148433 58.4618 + 79 0.0000 2.209466 60.1226 + 80 0.0000 2.246898 61.1412 + 81 0.0000 2.299921 62.5840 + 82 0.0000 2.305067 62.7241 + 83 0.0000 2.379095 64.7385 + 84 0.0000 2.411897 65.6310 + 85 0.0000 2.456133 66.8348 + 86 0.0000 2.466140 67.1071 + 87 0.0000 2.477656 67.4205 + 88 0.0000 2.511700 68.3468 + 89 0.0000 2.547828 69.3299 + 90 0.0000 2.557521 69.5937 + 91 0.0000 2.601336 70.7860 + 92 0.0000 2.674241 72.7698 + 93 0.0000 2.704179 73.5844 + 94 0.0000 2.754412 74.9513 + 95 0.0000 2.799522 76.1789 + 96 0.0000 2.847568 77.4863 + 97 0.0000 2.887287 78.5671 + 98 0.0000 2.955226 80.4158 + 99 0.0000 3.013458 82.0003 + 100 0.0000 3.061912 83.3189 + 101 0.0000 3.163004 86.0697 + 102 0.0000 3.242820 88.2416 + 103 0.0000 3.486795 94.8805 + 104 0.0000 3.733225 101.5862 + 105 0.0000 3.830500 104.2332 + 106 0.0000 4.050785 110.2275 + 107 0.0000 4.169136 113.4480 + 108 0.0000 4.194514 114.1385 + 109 0.0000 4.315190 117.4223 + 110 0.0000 4.339290 118.0781 + 111 0.0000 4.393191 119.5448 + 112 0.0000 4.545949 123.7016 + 113 0.0000 4.619133 125.6930 + 114 0.0000 4.689857 127.6175 + 115 0.0000 4.724158 128.5509 + 116 0.0000 4.795721 130.4982 + 117 0.0000 4.888404 133.0202 + 118 0.0000 4.936462 134.3280 + 119 0.0000 4.963505 135.0638 + 120 0.0000 5.062715 137.7635 + 121 0.0000 5.093513 138.6015 + 122 0.0000 5.170461 140.6954 + 123 0.0000 5.199665 141.4901 + 124 0.0000 5.224798 142.1740 + 125 0.0000 5.339126 145.2850 + 126 0.0000 5.377401 146.3265 + 127 0.0000 5.449114 148.2779 + 128 0.0000 5.526267 150.3774 + 129 0.0000 5.721351 155.6859 + 130 0.0000 5.769868 157.0061 + 131 0.0000 5.945301 161.7799 + 132 0.0000 6.168353 167.8494 + 133 0.0000 6.406056 174.3177 + 134 0.0000 6.490241 176.6084 + 135 0.0000 6.501752 176.9217 + 136 0.0000 6.700747 182.3366 + 137 0.0000 6.718023 182.8067 + 138 0.0000 6.770869 184.2447 + 139 0.0000 6.811559 185.3519 + 140 0.0000 6.843186 186.2126 + 141 0.0000 7.062143 192.1707 + 142 0.0000 7.110531 193.4874 + 143 0.0000 7.122645 193.8170 + 144 0.0000 7.201825 195.9716 + 145 0.0000 7.256431 197.4575 + 146 0.0000 7.279578 198.0874 + 147 0.0000 7.355682 200.1583 + 148 0.0000 7.398515 201.3238 + 149 0.0000 7.448534 202.6849 + 150 0.0000 7.461830 203.0467 + 151 0.0000 7.539341 205.1559 + 152 0.0000 7.598188 206.7572 + 153 0.0000 7.602274 206.8684 + 154 0.0000 7.793828 212.0808 + 155 0.0000 7.905662 215.1240 + 156 0.0000 7.960456 216.6150 + 157 0.0000 8.391195 228.3360 + 158 0.0000 14.078990 383.1088 + 159 0.0000 14.817478 403.2041 + 160 0.0000 16.135836 439.0784 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.688159 -562.9534 + 1 1.0000 -20.619172 -561.0762 + 2 1.0000 -15.803680 -430.0400 + 3 1.0000 -1.615502 -43.9600 + 4 1.0000 -1.375810 -37.4377 + 5 1.0000 -0.952466 -25.9179 + 6 1.0000 -0.771005 -20.9801 + 7 1.0000 -0.730157 -19.8686 + 8 1.0000 -0.697752 -18.9868 + 9 1.0000 -0.608686 -16.5632 + 10 1.0000 -0.528890 -14.3918 + 11 1.0000 -0.458373 -12.4730 + 12 0.0000 0.030309 0.8248 + 13 0.0000 0.069866 1.9012 + 14 0.0000 0.091775 2.4973 + 15 0.0000 0.101125 2.7517 + 16 0.0000 0.115257 3.1363 + 17 0.0000 0.154083 4.1928 + 18 0.0000 0.157185 4.2772 + 19 0.0000 0.173047 4.7088 + 20 0.0000 0.184389 5.0175 + 21 0.0000 0.189940 5.1685 + 22 0.0000 0.201624 5.4865 + 23 0.0000 0.236885 6.4460 + 24 0.0000 0.271373 7.3844 + 25 0.0000 0.283301 7.7090 + 26 0.0000 0.306773 8.3477 + 27 0.0000 0.328958 8.9514 + 28 0.0000 0.336171 9.1477 + 29 0.0000 0.356863 9.7107 + 30 0.0000 0.424718 11.5572 + 31 0.0000 0.508092 13.8259 + 32 0.0000 0.522800 14.2261 + 33 0.0000 0.544151 14.8071 + 34 0.0000 0.572391 15.5756 + 35 0.0000 0.605907 16.4876 + 36 0.0000 0.630631 17.1603 + 37 0.0000 0.650761 17.7081 + 38 0.0000 0.697953 18.9923 + 39 0.0000 0.722139 19.6504 + 40 0.0000 0.740431 20.1481 + 41 0.0000 0.744947 20.2711 + 42 0.0000 0.774196 21.0669 + 43 0.0000 0.792844 21.5744 + 44 0.0000 0.806098 21.9350 + 45 0.0000 0.821127 22.3440 + 46 0.0000 0.851373 23.1670 + 47 0.0000 0.867491 23.6056 + 48 0.0000 0.909357 24.7449 + 49 0.0000 0.940067 25.5805 + 50 0.0000 0.957674 26.0596 + 51 0.0000 0.995249 27.0821 + 52 0.0000 1.000635 27.2287 + 53 0.0000 1.024474 27.8773 + 54 0.0000 1.048243 28.5241 + 55 0.0000 1.110052 30.2061 + 56 0.0000 1.138510 30.9804 + 57 0.0000 1.232018 33.5249 + 58 0.0000 1.248982 33.9865 + 59 0.0000 1.289415 35.0868 + 60 0.0000 1.337036 36.3826 + 61 0.0000 1.419861 38.6364 + 62 0.0000 1.432383 38.9771 + 63 0.0000 1.510414 41.1005 + 64 0.0000 1.528130 41.5825 + 65 0.0000 1.561966 42.5033 + 66 0.0000 1.577563 42.9277 + 67 0.0000 1.640702 44.6458 + 68 0.0000 1.654101 45.0104 + 69 0.0000 1.701979 46.3132 + 70 0.0000 1.776965 48.3537 + 71 0.0000 1.794866 48.8408 + 72 0.0000 1.882747 51.2322 + 73 0.0000 1.935301 52.6622 + 74 0.0000 1.966978 53.5242 + 75 0.0000 2.036855 55.4256 + 76 0.0000 2.057397 55.9846 + 77 0.0000 2.079678 56.5909 + 78 0.0000 2.148433 58.4618 + 79 0.0000 2.209466 60.1226 + 80 0.0000 2.246898 61.1412 + 81 0.0000 2.299921 62.5840 + 82 0.0000 2.305067 62.7241 + 83 0.0000 2.379095 64.7385 + 84 0.0000 2.411897 65.6310 + 85 0.0000 2.456133 66.8348 + 86 0.0000 2.466140 67.1071 + 87 0.0000 2.477656 67.4205 + 88 0.0000 2.511700 68.3468 + 89 0.0000 2.547828 69.3299 + 90 0.0000 2.557521 69.5937 + 91 0.0000 2.601336 70.7860 + 92 0.0000 2.674241 72.7698 + 93 0.0000 2.704179 73.5844 + 94 0.0000 2.754412 74.9513 + 95 0.0000 2.799522 76.1789 + 96 0.0000 2.847568 77.4863 + 97 0.0000 2.887287 78.5671 + 98 0.0000 2.955226 80.4158 + 99 0.0000 3.013458 82.0003 + 100 0.0000 3.061912 83.3189 + 101 0.0000 3.163004 86.0697 + 102 0.0000 3.242820 88.2416 + 103 0.0000 3.486795 94.8805 + 104 0.0000 3.733225 101.5862 + 105 0.0000 3.830500 104.2332 + 106 0.0000 4.050785 110.2275 + 107 0.0000 4.169136 113.4480 + 108 0.0000 4.194514 114.1385 + 109 0.0000 4.315190 117.4223 + 110 0.0000 4.339290 118.0781 + 111 0.0000 4.393191 119.5448 + 112 0.0000 4.545949 123.7016 + 113 0.0000 4.619133 125.6930 + 114 0.0000 4.689857 127.6175 + 115 0.0000 4.724158 128.5509 + 116 0.0000 4.795721 130.4982 + 117 0.0000 4.888404 133.0202 + 118 0.0000 4.936462 134.3280 + 119 0.0000 4.963505 135.0638 + 120 0.0000 5.062715 137.7635 + 121 0.0000 5.093513 138.6015 + 122 0.0000 5.170461 140.6954 + 123 0.0000 5.199665 141.4901 + 124 0.0000 5.224798 142.1740 + 125 0.0000 5.339126 145.2850 + 126 0.0000 5.377401 146.3265 + 127 0.0000 5.449114 148.2779 + 128 0.0000 5.526267 150.3774 + 129 0.0000 5.721351 155.6859 + 130 0.0000 5.769868 157.0061 + 131 0.0000 5.945301 161.7799 + 132 0.0000 6.168353 167.8494 + 133 0.0000 6.406056 174.3177 + 134 0.0000 6.490241 176.6084 + 135 0.0000 6.501752 176.9217 + 136 0.0000 6.700747 182.3366 + 137 0.0000 6.718023 182.8067 + 138 0.0000 6.770869 184.2447 + 139 0.0000 6.811559 185.3519 + 140 0.0000 6.843186 186.2126 + 141 0.0000 7.062143 192.1707 + 142 0.0000 7.110531 193.4874 + 143 0.0000 7.122645 193.8170 + 144 0.0000 7.201825 195.9716 + 145 0.0000 7.256431 197.4575 + 146 0.0000 7.279578 198.0874 + 147 0.0000 7.355682 200.1583 + 148 0.0000 7.398515 201.3238 + 149 0.0000 7.448534 202.6849 + 150 0.0000 7.461830 203.0467 + 151 0.0000 7.539341 205.1559 + 152 0.0000 7.598188 206.7572 + 153 0.0000 7.602274 206.8684 + 154 0.0000 7.793828 212.0808 + 155 0.0000 7.905662 215.1240 + 156 0.0000 7.960456 216.6150 + 157 0.0000 8.391195 228.3360 + 158 0.0000 14.078990 383.1088 + 159 0.0000 14.817478 403.2041 + 160 0.0000 16.135836 439.0784 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.373007 0.000000 + 1 N : 0.354364 0.000000 + 2 O : -0.236317 0.000000 + 3 H : 0.254960 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.870200 s : 3.870200 + pz : 1.284131 p : 4.475345 + px : 1.467965 + py : 1.723248 + dz2 : 0.010405 d : 0.023033 + dxz : 0.006729 + dyz : 0.004473 + dx2y2 : 0.000539 + dxy : 0.000886 + f0 : 0.001733 f : 0.004430 + f+1 : 0.000660 + f-1 : 0.000864 + f+2 : 0.000102 + f-2 : 0.000288 + f+3 : 0.000123 + f-3 : 0.000659 + 1 N s : 3.823046 s : 3.823046 + pz : 0.863059 p : 2.657496 + px : 0.912350 + py : 0.882087 + dz2 : 0.028341 d : 0.134689 + dxz : 0.041240 + dyz : 0.018507 + dx2y2 : 0.025562 + dxy : 0.021038 + f0 : 0.008778 f : 0.030406 + f+1 : 0.003813 + f-1 : 0.005579 + f+2 : 0.002434 + f-2 : 0.004132 + f+3 : 0.003917 + f-3 : 0.001752 + 2 O s : 3.876893 s : 3.876893 + pz : 1.797205 p : 4.288212 + px : 1.196580 + py : 1.294427 + dz2 : 0.004782 d : 0.063643 + dxz : 0.012432 + dyz : 0.004983 + dx2y2 : 0.025058 + dxy : 0.016387 + f0 : 0.001199 f : 0.007570 + f+1 : 0.000837 + f-1 : 0.000501 + f+2 : 0.000243 + f-2 : 0.000946 + f+3 : 0.002765 + f-3 : 0.001079 + 3 H s : 0.638882 s : 0.638882 + pz : 0.019257 p : 0.085440 + px : 0.029261 + py : 0.036922 + dz2 : 0.001025 d : 0.020719 + dxz : 0.005950 + dyz : 0.002701 + dx2y2 : 0.009040 + dxy : 0.002002 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.578787 0.000000 + 1 N : -0.237833 0.000000 + 2 O : 0.247983 0.000000 + 3 H : -0.588937 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.133366 s : 3.133366 + pz : 1.213570 p : 3.950270 + px : 1.305968 + py : 1.430732 + dz2 : 0.100163 d : 0.260994 + dxz : 0.065548 + dyz : 0.048309 + dx2y2 : 0.018100 + dxy : 0.028874 + f0 : 0.023376 f : 0.076583 + f+1 : 0.017206 + f-1 : 0.014753 + f+2 : 0.008860 + f-2 : 0.007192 + f+3 : 0.001069 + f-3 : 0.004126 + 1 N s : 3.031876 s : 3.031876 + pz : 0.897099 p : 2.839163 + px : 1.055739 + py : 0.886324 + dz2 : 0.206387 d : 0.926829 + dxz : 0.281893 + dyz : 0.116487 + dx2y2 : 0.142273 + dxy : 0.179789 + f0 : 0.108281 f : 0.439965 + f+1 : 0.061946 + f-1 : 0.056388 + f+2 : 0.040641 + f-2 : 0.061097 + f+3 : 0.059301 + f-3 : 0.052312 + 2 O s : 3.316065 s : 3.316065 + pz : 1.465688 p : 3.986896 + px : 1.326055 + py : 1.195153 + dz2 : 0.049271 d : 0.330830 + dxz : 0.092385 + dyz : 0.019162 + dx2y2 : 0.065921 + dxy : 0.104091 + f0 : 0.014428 f : 0.118227 + f+1 : 0.018523 + f-1 : 0.007518 + f+2 : 0.012779 + f-2 : 0.015087 + f+3 : 0.023760 + f-3 : 0.026131 + 3 H s : 0.626887 s : 0.626887 + pz : 0.144271 p : 0.570423 + px : 0.229844 + py : 0.196308 + dz2 : 0.033160 d : 0.391627 + dxz : 0.100518 + dyz : 0.043272 + dx2y2 : 0.115707 + dxy : 0.098970 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3730 8.0000 -0.3730 1.8411 1.8411 -0.0000 + 1 N 6.6456 7.0000 0.3544 2.5818 2.5818 0.0000 + 2 O 8.2363 8.0000 -0.2363 1.7974 1.7974 -0.0000 + 3 H 0.7450 1.0000 0.2550 0.9780 0.9780 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8256 B( 0-O , 3-H ) : 0.9597 B( 1-N , 2-O ) : 1.7397 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.952 sec +Sum of individual times .... 2.282 sec ( 77.3%) + +Fock matrix formation .... 1.846 sec ( 62.5%) +Diagonalization .... 0.128 sec ( 4.3%) +Density matrix formation .... 0.010 sec ( 0.3%) +Population analysis .... 0.179 sec ( 6.1%) +Initial guess .... 0.022 sec ( 0.7%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.014 sec ( 0.5%) +DIIS solution .... 0.097 sec ( 3.3%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.586 sec +Reference energy ... -204.708590630 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 10.170 sec +AO-integral generation ... 0.350 sec +Half transformation ... 0.173 sec +K-integral sorting ... 7.645 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.073 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.069 s ( 0.000 ms/b) + 277134 b 0 skpd 0.079 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.092 s ( 0.001 ms/b) +: 159120 b 0 skpd 0.046 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.097 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.075 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.060 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.104 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.059 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.867 sec +AO-integral generation ... 0.697 sec +Half transformation ... 0.060 sec +J-integral sorting ... 0.077 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.266 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.364 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090123506 +EMP2(bb)= -0.090123506 +EMP2(ab)= -0.517344490 + +Initial guess performed in 0.178 sec +E(0) ... -204.708590630 +E(MP2) ... -0.697591503 +Initial E(tot) ... -205.406182133 + ... 0.189375789 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.406182133 -0.697591503 -0.000000000 0.019673157 5.50 0.000002196 + *** Turning on DIIS *** + 1 -205.377694582 -0.669103952 0.028487551 0.009330782 5.74 0.056033599 + 2 -205.397230521 -0.688639891 -0.019535939 0.003926940 5.99 0.058833636 + 3 -205.401044795 -0.692454165 -0.003814274 0.001720895 6.71 0.072163489 + 4 -205.402590063 -0.693999433 -0.001545268 0.001227091 6.94 0.078202375 + 5 -205.403097684 -0.694507054 -0.000507621 0.000779331 6.87 0.082940041 + 6 -205.403187764 -0.694597133 -0.000090080 0.000517659 7.03 0.085261243 + 7 -205.403226268 -0.694635638 -0.000038504 0.000284992 6.95 0.086393193 + 8 -205.403236395 -0.694645765 -0.000010127 0.000160044 8.26 0.086898652 + 9 -205.403232784 -0.694642153 0.000003612 0.000067022 8.59 0.087087483 + 10 -205.403238248 -0.694647617 -0.000005464 0.000043933 8.43 0.087170469 + 11 -205.403234828 -0.694644198 0.000003420 0.000030995 6.67 0.087170987 + 12 -205.403237104 -0.694646473 -0.000002276 0.000020035 6.17 0.087190443 + 13 -205.403236989 -0.694646359 0.000000115 0.000012120 6.61 0.087186618 + 14 -205.403237331 -0.694646701 -0.000000342 0.000006381 6.70 0.087192617 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.708590630 +E(CORR) ... -0.694646701 +E(TOT) ... -205.403237331 +Singles norm **1/2 ... 0.087192617 ( 0.043596309, 0.043596309) +T1 diagnostic ... 0.020551497 + +------------------ +LARGEST AMPLITUDES +------------------ + 9a-> 13a 9b-> 13b 0.054560 + 8a-> 13a 8b-> 13b 0.053231 + 9a-> 13a 8b-> 13b 0.044820 + 8a-> 13a 9b-> 13b 0.044820 + 5a-> 13a 5b-> 13b 0.029448 + 8b-> 13b -1b-> -1b 0.028971 + 8a-> 13a -1a-> -1a 0.028971 + 11a-> 13a 11b-> 13b 0.027639 + 11a-> 25a 11b-> 25b 0.025672 + 10a-> 13a -1a-> -1a 0.024716 + 10b-> 13b -1b-> -1b 0.024716 + 11a-> 25a -1a-> -1a 0.021786 + 11b-> 25b -1b-> -1b 0.021786 + 9a-> 13a 9b-> 22b 0.020396 + 9a-> 22a 9b-> 13b 0.020396 + 9a-> 13a 10b-> 13b 0.019895 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034557950 + alpha-alpha-alpha ... -0.000868832 ( 2.5%) + alpha-alpha-beta ... -0.016410143 ( 47.5%) + alpha-beta -beta ... -0.016410143 ( 47.5%) + beta -beta -beta ... -0.000868832 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034557950 + +Final correlation energy ... -0.729204651 +E(CCSD) ... -205.403237331 +E(CCSD(T)) ... -205.437795281 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210741650 sqrt= 1.100337062 +W(HF) = 0.825940034 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.308081 0.000000 + 1 N : 0.177993 -0.000000 + 2 O : -0.112520 -0.000000 + 3 H : 0.242607 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.846418 s : 3.846418 + pz : 1.269404 p : 4.399056 + px : 1.453444 + py : 1.676208 + dz2 : 0.015011 d : 0.054426 + dxz : 0.012188 + dyz : 0.011792 + dx2y2 : 0.007902 + dxy : 0.007533 + f0 : 0.002010 f : 0.008182 + f+1 : 0.001043 + f-1 : 0.001407 + f+2 : 0.000735 + f-2 : 0.000934 + f+3 : 0.000760 + f-3 : 0.001292 + 1 N s : 3.877323 s : 3.877323 + pz : 0.906233 p : 2.750407 + px : 0.921258 + py : 0.922916 + dz2 : 0.034862 d : 0.164739 + dxz : 0.050678 + dyz : 0.027004 + dx2y2 : 0.026841 + dxy : 0.025353 + f0 : 0.008393 f : 0.029538 + f+1 : 0.003565 + f-1 : 0.005627 + f+2 : 0.002886 + f-2 : 0.004167 + f+3 : 0.003016 + f-3 : 0.001884 + 2 O s : 3.863943 s : 3.863943 + pz : 1.709569 p : 4.154092 + px : 1.181351 + py : 1.263171 + dz2 : 0.010026 d : 0.084520 + dxz : 0.019745 + dyz : 0.011107 + dx2y2 : 0.025091 + dxy : 0.018552 + f0 : 0.001664 f : 0.009965 + f+1 : 0.001308 + f-1 : 0.000953 + f+2 : 0.000838 + f-2 : 0.001396 + f+3 : 0.002476 + f-3 : 0.001331 + 3 H s : 0.647219 s : 0.647219 + pz : 0.022744 p : 0.092427 + px : 0.027520 + py : 0.042163 + dz2 : 0.001077 d : 0.017747 + dxz : 0.005293 + dyz : 0.002375 + dx2y2 : 0.007730 + dxy : 0.001272 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.586510 0.000000 + 1 N : -0.283021 -0.000000 + 2 O : 0.288748 -0.000000 + 3 H : -0.592236 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.137990 s : 3.137990 + pz : 1.211607 p : 3.900208 + px : 1.296290 + py : 1.392311 + dz2 : 0.106412 d : 0.291848 + dxz : 0.071839 + dyz : 0.053572 + dx2y2 : 0.024394 + dxy : 0.035630 + f0 : 0.024692 f : 0.083444 + f+1 : 0.018991 + f-1 : 0.015470 + f+2 : 0.009432 + f-2 : 0.008091 + f+3 : 0.001688 + f-3 : 0.005079 + 1 N s : 3.036739 s : 3.036739 + pz : 0.915632 p : 2.880444 + px : 1.056498 + py : 0.908314 + dz2 : 0.213156 d : 0.935714 + dxz : 0.281096 + dyz : 0.117882 + dx2y2 : 0.139988 + dxy : 0.183592 + f0 : 0.105476 f : 0.430123 + f+1 : 0.062203 + f-1 : 0.055035 + f+2 : 0.038443 + f-2 : 0.057741 + f+3 : 0.058381 + f-3 : 0.052844 + 2 O s : 3.318655 s : 3.318655 + pz : 1.409438 p : 3.906916 + px : 1.317920 + py : 1.179558 + dz2 : 0.055048 d : 0.359081 + dxz : 0.094926 + dyz : 0.025275 + dx2y2 : 0.073938 + dxy : 0.109894 + f0 : 0.015179 f : 0.126601 + f+1 : 0.019169 + f-1 : 0.008012 + f+2 : 0.012986 + f-2 : 0.016358 + f+3 : 0.027995 + f-3 : 0.026902 + 3 H s : 0.627179 s : 0.627179 + pz : 0.145002 p : 0.583598 + px : 0.234926 + py : 0.203671 + dz2 : 0.034423 d : 0.381460 + dxz : 0.096944 + dyz : 0.041796 + dx2y2 : 0.111040 + dxy : 0.097257 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3081 8.0000 -0.3081 2.1902 1.7270 0.4632 + 1 N 6.8220 7.0000 0.1780 2.8504 2.3590 0.4914 + 2 O 8.1125 8.0000 -0.1125 2.1859 1.6875 0.4984 + 3 H 0.7574 1.0000 0.2426 1.0005 0.9268 0.0736 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7412 B( 0-O , 3-H ) : 0.8959 B( 1-N , 2-O ) : 1.5922 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 132.714 sec + +Fock Matrix Formation ... 0.586 sec ( 0.4%) +Initial Guess ... 0.178 sec ( 0.1%) +DIIS Solver ... 6.012 sec ( 4.5%) +State Vector Update ... 0.300 sec ( 0.2%) +Sigma-vector construction ... 96.834 sec ( 73.0%) + <0|H|D> ... 0.009 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.053 sec ( 0.1% of sigma) + (0-ext) ... 0.190 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.064 sec ( 0.1% of sigma) + (2-ext) ... 2.295 sec ( 2.4% of sigma) + (4-ext) ... 58.492 sec ( 60.4% of sigma) + ... 4.113 sec ( 4.2% of sigma) + ... 0.007 sec ( 0.0% of sigma) + (1-ext) ... 0.023 sec ( 0.0% of sigma) + (1-ext) ... 0.231 sec ( 0.2% of sigma) + Fock-dressing ... 6.292 sec ( 6.5% of sigma) + (ik|jl)-dressing ... 0.200 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 20.302 sec ( 21.0% of sigma) + Pair energies ... 0.025 sec ( 0.0% of sigma) +Total Time for computing (T) ... 15.165 sec ( 11.4% of ALL) + I/O of integral and amplitudes ... 1.578 sec ( 10.4% of (T)) + External N**7 contributions ... 9.698 sec ( 64.0% of (T)) + Internal N**7 contributions ... 0.848 sec ( 5.6% of (T)) + N**6 triples energy contributions ... 2.811 sec ( 18.5% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.437795280867 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.037.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.037.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.662705, -0.188609 -0.303575) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.78964 -0.15944 -0.92169 +Nuclear contribution : -1.38551 0.43612 0.70200 + ----------------------------------------- +Total Dipole Moment : -0.59587 0.27668 -0.21969 + ----------------------------------------- +Magnitude (a.u.) : 0.69273 +Magnitude (Debye) : 1.76078 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.798692 0.401770 0.361732 +Rotational constants in MHz : 83902.687259 12044.751572 10844.453702 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.241509 -0.310650 0.570125 +x,y,z [Debye]: -0.613868 -0.789610 1.449142 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.662705, -0.188609 -0.303575) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.96207 -0.12024 -0.92687 +Nuclear contribution : -1.38551 0.43612 0.70200 + ----------------------------------------- +Total Dipole Moment : -0.42344 0.31588 -0.22487 + ----------------------------------------- +Magnitude (a.u.) : 0.57415 +Magnitude (Debye) : 1.45938 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.798692 0.401770 0.361732 +Rotational constants in MHz : 83902.687259 12044.751572 10844.453702 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.111927 -0.198164 0.527118 +x,y,z [Debye]: -0.284495 -0.503693 1.339827 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 38 * + * * + * Dihedral ( 2, 1, 0, 3) : 122.72727273 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0398968555 RMS(Int)= 0.0001355378 + Iter 1: RMS(Cart)= 0.0000378680 RMS(Int)= 0.0000005102 + Iter 2: RMS(Cart)= 0.0000001425 RMS(Int)= 0.0000000019 + Iter 3: RMS(Cart)= 0.0000000005 RMS(Int)= 0.0000000000 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4940 0.000000 + 2. B(O 2,N 1) 1.1677 0.000000 + 3. B(H 3,O 0) 0.9722 0.000000 + 4. A(N 1,O 0,H 3) 102.2330 0.000000 + 5. A(O 0,N 1,O 2) 110.4144 0.000000 + 6. D(O 2,N 1,O 0,H 3) 122.7273 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.313666 -0.123520 0.763593 + N 0.207199 -0.347430 -0.618627 + O 1.262032 0.138482 -0.740082 + H -1.155564 0.332468 0.595116 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.592742 -0.233420 1.442981 + 1 N 7.0000 0 14.007 0.391550 -0.656547 -1.169035 + 2 O 8.0000 0 15.999 2.384894 0.261693 -1.398552 + 3 H 1.0000 0 1.008 -2.183700 0.628274 1.124606 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.493754120578 0.00000000 0.00000000 + O 2 1 0 1.165649541654 110.48971572 0.00000000 + H 1 2 3 0.969419804958 102.30030408 114.54545483 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.822786199310 0.00000000 0.00000000 + O 2 1 0 2.202758401856 110.48971572 0.00000000 + H 1 2 3 1.831937940169 102.30030408 114.54545483 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.1 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2223 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2688 + la=0 lb=0: 547 shell pairs + la=1 lb=0: 534 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 392 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.437516364622 Eh + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.4375163646 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.965e-04 +Time for diagonalization ... 0.005 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.004 sec +Total time needed ... 0.040 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7049723008 0.000000000000 0.00150923 0.00005258 0.0198060 0.7000 + 1 -204.7058828923 -0.000910591450 0.00148471 0.00004793 0.0163922 0.7000 + ***Turning on DIIS*** + 2 -204.7066627373 -0.000779845026 0.00413926 0.00013090 0.0133217 0.0000 + 3 -204.7098471721 -0.003184434771 0.00178120 0.00005668 0.0050818 0.0000 + 4 -204.7085875075 0.001259664607 0.00082907 0.00002826 0.0019700 0.0000 + 5 -204.7102812828 -0.001693775317 0.00076398 0.00002334 0.0011159 0.0000 + 6 -204.7093927012 0.000888581607 0.00077610 0.00002769 0.0006939 0.0000 + 7 -204.7091601484 0.000232552778 0.00037897 0.00001352 0.0003042 0.0000 + 8 -204.7098594448 -0.000699296436 0.00019756 0.00000786 0.0002141 0.0000 + 9 -204.7094164175 0.000443027368 0.00013749 0.00000573 0.0001336 0.0000 + 10 -204.7096174576 -0.000201040101 0.00006030 0.00000231 0.0000611 0.0000 + 11 -204.7096475799 -0.000030122387 0.00002615 0.00000080 0.0000339 0.0000 + 12 -204.7095779475 0.000069632431 0.00000656 0.00000026 0.0000111 0.0000 + 13 -204.7095996378 -0.000021690246 0.00000266 0.00000008 0.0000027 0.0000 + 14 -204.7095944660 0.000005171710 0.00000119 0.00000004 0.0000023 0.0000 + 15 -204.7095955091 -0.000001043052 0.00000079 0.00000002 0.0000018 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 16 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.70959718 Eh -5570.43133 eV + +Components: +Nuclear Repulsion : 68.43751636 Eh 1862.27950 eV +Electronic Energy : -273.14711354 Eh -7432.71083 eV +One Electron Energy: -416.60357233 Eh -11336.35953 eV +Two Electron Energy: 143.45645878 Eh 3903.64870 eV + +Virial components: +Potential Energy : -408.91932849 Eh -11127.26063 eV +Kinetic Energy : 204.20973131 Eh 5556.82929 eV +Virial Ratio : 2.00244781 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.6687e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.0542e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.8779e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.9246e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.686870 -562.9184 + 1 1.0000 -20.621243 -561.1325 + 2 1.0000 -15.804308 -430.0571 + 3 1.0000 -1.612811 -43.8868 + 4 1.0000 -1.375951 -37.4415 + 5 1.0000 -0.951918 -25.9030 + 6 1.0000 -0.770934 -20.9782 + 7 1.0000 -0.729038 -19.8381 + 8 1.0000 -0.694641 -18.9021 + 9 1.0000 -0.610636 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2.4981 + 15 0.0000 0.100449 2.7334 + 16 0.0000 0.116903 3.1811 + 17 0.0000 0.153041 4.1645 + 18 0.0000 0.157115 4.2753 + 19 0.0000 0.172880 4.7043 + 20 0.0000 0.185423 5.0456 + 21 0.0000 0.190464 5.1828 + 22 0.0000 0.201978 5.4961 + 23 0.0000 0.236392 6.4326 + 24 0.0000 0.270884 7.3711 + 25 0.0000 0.278845 7.5878 + 26 0.0000 0.307165 8.3584 + 27 0.0000 0.328411 8.9365 + 28 0.0000 0.340125 9.2553 + 29 0.0000 0.358872 9.7654 + 30 0.0000 0.424081 11.5398 + 31 0.0000 0.510828 13.9003 + 32 0.0000 0.519793 14.1443 + 33 0.0000 0.543911 14.8006 + 34 0.0000 0.571608 15.5542 + 35 0.0000 0.607827 16.5398 + 36 0.0000 0.630858 17.1665 + 37 0.0000 0.649525 17.6745 + 38 0.0000 0.698547 19.0084 + 39 0.0000 0.723425 19.6854 + 40 0.0000 0.738001 20.0820 + 41 0.0000 0.741393 20.1743 + 42 0.0000 0.778384 21.1809 + 43 0.0000 0.792211 21.5572 + 44 0.0000 0.803703 21.8699 + 45 0.0000 0.823696 22.4139 + 46 0.0000 0.847038 23.0491 + 47 0.0000 0.862884 23.4803 + 48 0.0000 0.916810 24.9477 + 49 0.0000 0.943694 25.6792 + 50 0.0000 0.958527 26.0829 + 51 0.0000 0.999794 27.2058 + 52 0.0000 1.005396 27.3582 + 53 0.0000 1.023167 27.8418 + 54 0.0000 1.046410 28.4743 + 55 0.0000 1.098989 29.9050 + 56 0.0000 1.141308 31.0566 + 57 0.0000 1.221163 33.2295 + 58 0.0000 1.251726 34.0612 + 59 0.0000 1.297878 35.3170 + 60 0.0000 1.352077 36.7919 + 61 0.0000 1.416415 38.5426 + 62 0.0000 1.436833 39.0982 + 63 0.0000 1.509674 41.0803 + 64 0.0000 1.532538 41.7025 + 65 0.0000 1.558257 42.4023 + 66 0.0000 1.565975 42.6124 + 67 0.0000 1.638948 44.5980 + 68 0.0000 1.658787 45.1379 + 69 0.0000 1.701086 46.2889 + 70 0.0000 1.776395 48.3382 + 71 0.0000 1.794494 48.8307 + 72 0.0000 1.880948 51.1832 + 73 0.0000 1.934522 52.6410 + 74 0.0000 1.959922 53.3322 + 75 0.0000 2.028881 55.2087 + 76 0.0000 2.054245 55.8988 + 77 0.0000 2.083769 56.7022 + 78 0.0000 2.154977 58.6399 + 79 0.0000 2.198574 59.8262 + 80 0.0000 2.256561 61.4042 + 81 0.0000 2.291383 62.3517 + 82 0.0000 2.307927 62.8019 + 83 0.0000 2.379680 64.7544 + 84 0.0000 2.416485 65.7559 + 85 0.0000 2.460487 66.9532 + 86 0.0000 2.468148 67.1617 + 87 0.0000 2.478648 67.4475 + 88 0.0000 2.511840 68.3506 + 89 0.0000 2.536963 69.0343 + 90 0.0000 2.562611 69.7322 + 91 0.0000 2.603828 70.8538 + 92 0.0000 2.671839 72.7044 + 93 0.0000 2.692864 73.2766 + 94 0.0000 2.741787 74.6078 + 95 0.0000 2.796608 76.0996 + 96 0.0000 2.834236 77.1235 + 97 0.0000 2.881792 78.4175 + 98 0.0000 2.955224 80.4157 + 99 0.0000 3.027751 82.3893 + 100 0.0000 3.072265 83.6006 + 101 0.0000 3.164126 86.1003 + 102 0.0000 3.249465 88.4224 + 103 0.0000 3.481650 94.7405 + 104 0.0000 3.729474 101.4842 + 105 0.0000 3.842104 104.5490 + 106 0.0000 4.046161 110.1016 + 107 0.0000 4.160509 113.2132 + 108 0.0000 4.197426 114.2178 + 109 0.0000 4.312136 117.3392 + 110 0.0000 4.341358 118.1344 + 111 0.0000 4.387617 119.3931 + 112 0.0000 4.555183 123.9528 + 113 0.0000 4.617859 125.6583 + 114 0.0000 4.701112 127.9238 + 115 0.0000 4.726283 128.6087 + 116 0.0000 4.783095 130.1546 + 117 0.0000 4.883984 132.9000 + 118 0.0000 4.938613 134.3865 + 119 0.0000 4.972120 135.2983 + 120 0.0000 5.064038 137.7995 + 121 0.0000 5.090369 138.5160 + 122 0.0000 5.163217 140.4983 + 123 0.0000 5.197533 141.4321 + 124 0.0000 5.233097 142.3998 + 125 0.0000 5.329106 145.0124 + 126 0.0000 5.377325 146.3245 + 127 0.0000 5.411929 147.2661 + 128 0.0000 5.525382 150.3533 + 129 0.0000 5.708935 155.3480 + 130 0.0000 5.772970 157.0905 + 131 0.0000 5.947817 161.8483 + 132 0.0000 6.155210 167.4918 + 133 0.0000 6.399533 174.1401 + 134 0.0000 6.490193 176.6071 + 135 0.0000 6.501940 176.9268 + 136 0.0000 6.699608 182.3056 + 137 0.0000 6.711708 182.6349 + 138 0.0000 6.764985 184.0846 + 139 0.0000 6.813484 185.4043 + 140 0.0000 6.852748 186.4727 + 141 0.0000 7.053785 191.9432 + 142 0.0000 7.112354 193.5370 + 143 0.0000 7.125952 193.9070 + 144 0.0000 7.194383 195.7691 + 145 0.0000 7.249076 197.2574 + 146 0.0000 7.271580 197.8698 + 147 0.0000 7.352818 200.0804 + 148 0.0000 7.396619 201.2722 + 149 0.0000 7.440959 202.4788 + 150 0.0000 7.464706 203.1250 + 151 0.0000 7.537121 205.0955 + 152 0.0000 7.595757 206.6910 + 153 0.0000 7.601344 206.8431 + 154 0.0000 7.816583 212.7000 + 155 0.0000 7.904642 215.0963 + 156 0.0000 7.956613 216.5104 + 157 0.0000 8.375825 227.9178 + 158 0.0000 14.046528 382.2255 + 159 0.0000 14.754473 401.4896 + 160 0.0000 16.101091 438.1330 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.375726 0.000000 + 1 N : 0.356119 0.000000 + 2 O : -0.241006 0.000000 + 3 H : 0.260613 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.871997 s : 3.871997 + pz : 1.283421 p : 4.476461 + px : 1.439680 + py : 1.753360 + dz2 : 0.010284 d : 0.022834 + dxz : 0.006316 + dyz : 0.004753 + dx2y2 : 0.000824 + dxy : 0.000656 + f0 : 0.001781 f : 0.004434 + f+1 : 0.000598 + f-1 : 0.000911 + f+2 : 0.000103 + f-2 : 0.000255 + f+3 : 0.000121 + f-3 : 0.000665 + 1 N s : 3.824427 s : 3.824427 + pz : 0.869149 p : 2.655277 + px : 0.932480 + py : 0.853648 + dz2 : 0.028707 d : 0.134007 + dxz : 0.041972 + dyz : 0.017915 + dx2y2 : 0.022446 + dxy : 0.022967 + f0 : 0.008831 f : 0.030170 + f+1 : 0.003937 + f-1 : 0.005620 + f+2 : 0.002619 + f-2 : 0.003622 + f+3 : 0.003744 + f-3 : 0.001797 + 2 O s : 3.878275 s : 3.878275 + pz : 1.809598 p : 4.291272 + px : 1.192495 + py : 1.289180 + dz2 : 0.004832 d : 0.063846 + dxz : 0.013444 + dyz : 0.003772 + dx2y2 : 0.023035 + dxy : 0.018762 + f0 : 0.001198 f : 0.007613 + f+1 : 0.000884 + f-1 : 0.000471 + f+2 : 0.000416 + f-2 : 0.000778 + f+3 : 0.002664 + f-3 : 0.001202 + 3 H s : 0.634855 s : 0.634855 + pz : 0.018895 p : 0.083801 + px : 0.026683 + py : 0.038224 + dz2 : 0.000833 d : 0.020731 + dxz : 0.006630 + dyz : 0.002196 + dx2y2 : 0.007862 + dxy : 0.003210 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.576805 0.000000 + 1 N : -0.236982 0.000000 + 2 O : 0.244926 0.000000 + 3 H : -0.584750 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.135202 s : 3.135202 + pz : 1.213165 p : 3.949398 + px : 1.296286 + py : 1.439947 + dz2 : 0.103694 d : 0.261895 + dxz : 0.064516 + dyz : 0.046727 + dx2y2 : 0.021227 + dxy : 0.025731 + f0 : 0.024602 f : 0.076700 + f+1 : 0.017537 + f-1 : 0.014275 + f+2 : 0.008623 + f-2 : 0.006667 + f+3 : 0.000812 + f-3 : 0.004185 + 1 N s : 3.032522 s : 3.032522 + pz : 0.903389 p : 2.837967 + px : 1.086281 + py : 0.848296 + dz2 : 0.207376 d : 0.927271 + dxz : 0.290085 + dyz : 0.111083 + dx2y2 : 0.144981 + dxy : 0.173746 + f0 : 0.110093 f : 0.439222 + f+1 : 0.063297 + f-1 : 0.056235 + f+2 : 0.046982 + f-2 : 0.052795 + f+3 : 0.057542 + f-3 : 0.052278 + 2 O s : 3.317698 s : 3.317698 + pz : 1.475055 p : 3.989721 + px : 1.342528 + py : 1.172138 + dz2 : 0.048775 d : 0.329873 + dxz : 0.096844 + dyz : 0.015735 + dx2y2 : 0.071451 + dxy : 0.097067 + f0 : 0.014673 f : 0.117781 + f+1 : 0.019406 + f-1 : 0.006288 + f+2 : 0.015413 + f-2 : 0.012668 + f+3 : 0.022832 + f-3 : 0.026501 + 3 H s : 0.626296 s : 0.626296 + pz : 0.142122 p : 0.566780 + px : 0.236520 + py : 0.188138 + dz2 : 0.033647 d : 0.391673 + dxz : 0.107510 + dyz : 0.035274 + dx2y2 : 0.112123 + dxy : 0.103119 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3757 8.0000 -0.3757 1.8558 1.8558 0.0000 + 1 N 6.6439 7.0000 0.3561 2.5769 2.5769 0.0000 + 2 O 8.2410 8.0000 -0.2410 1.7914 1.7914 0.0000 + 3 H 0.7394 1.0000 0.2606 0.9703 0.9703 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8386 B( 0-O , 3-H ) : 0.9592 B( 1-N , 2-O ) : 1.7303 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 8 sec + +Total time .... 8.414 sec +Sum of individual times .... 7.561 sec ( 89.9%) + +Fock matrix formation .... 5.423 sec ( 64.5%) +Diagonalization .... 1.026 sec ( 12.2%) +Density matrix formation .... 0.036 sec ( 0.4%) +Population analysis .... 0.242 sec ( 2.9%) +Initial guess .... 0.031 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.023 sec ( 0.3%) +DIIS solution .... 0.803 sec ( 9.5%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.587 sec +Reference energy ... -204.709596895 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 12.493 sec +AO-integral generation ... 0.366 sec +Half transformation ... 0.183 sec +K-integral sorting ... 8.526 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.069 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.087 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.117 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.106 s ( 0.001 ms/b) +: 159120 b 0 skpd 0.046 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.125 s ( 0.001 ms/b) +: 119340 b 0 skpd 0.132 s ( 0.001 ms/b) + 87516 b 0 skpd 0.062 s ( 0.001 ms/b) +: : 87516 b 0 skpd 0.115 s ( 0.001 ms/b) + 27846 b 0 skpd 0.061 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 1.316 sec +AO-integral generation ... 0.832 sec +Half transformation ... 0.093 sec +J-integral sorting ... 0.153 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 1.481 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.612 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090343414 +EMP2(bb)= -0.090343414 +EMP2(ab)= -0.518136490 + +Initial guess performed in 0.500 sec +E(0) ... -204.709596895 +E(MP2) ... -0.698823318 +Initial E(tot) ... -205.408420214 + ... 0.190316513 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.408420214 -0.698823318 -0.000000000 0.020558457 6.76 0.000002693 + *** Turning on DIIS *** + 1 -205.379252476 -0.669655581 0.029167737 0.009356101 8.30 0.056947328 + 2 -205.398982316 -0.689385420 -0.019729839 0.004161406 6.68 0.059718733 + 3 -205.402819227 -0.693222332 -0.003836911 0.001757792 5.30 0.073492818 + 4 -205.404395153 -0.694798258 -0.001575926 0.001512859 5.38 0.079842557 + 5 -205.404933100 -0.695336204 -0.000537946 0.000930269 6.14 0.085031089 + 6 -205.405034765 -0.695437870 -0.000101666 0.000602689 8.12 0.087683363 + 7 -205.405079954 -0.695483058 -0.000045188 0.000303648 8.34 0.089036559 + 8 -205.405092654 -0.695495759 -0.000012701 0.000164015 8.26 0.089626527 + 9 -205.405088570 -0.695491675 0.000004084 0.000056170 7.11 0.089831171 + 10 -205.405094651 -0.695497756 -0.000006081 0.000038921 7.51 0.089913875 + 11 -205.405091114 -0.695494219 0.000003537 0.000028907 7.29 0.089908399 + 12 -205.405093089 -0.695496194 -0.000001975 0.000019940 6.89 0.089928191 + 13 -205.405092922 -0.695496026 0.000000167 0.000012318 7.24 0.089922545 + 14 -205.405093286 -0.695496390 -0.000000364 0.000006837 7.23 0.089928406 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.709596895 +E(CORR) ... -0.695496390 +E(TOT) ... -205.405093286 +Singles norm **1/2 ... 0.089928406 ( 0.044964203, 0.044964203) +T1 diagnostic ... 0.021196328 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.054755 + 9a-> 13a 9b-> 13b 0.048567 + 9a-> 13a 8b-> 13b 0.043086 + 8a-> 13a 9b-> 13b 0.043086 + 11a-> 25a 11b-> 25b 0.031265 + 8a-> 13a -1a-> -1a 0.030768 + 8b-> 13b -1b-> -1b 0.030768 + 10b-> 13b -1b-> -1b 0.030723 + 10a-> 13a -1a-> -1a 0.030723 + 5a-> 13a 5b-> 13b 0.029290 + 11a-> 13a 11b-> 13b 0.027445 + 11b-> 25b -1b-> -1b 0.024498 + 11a-> 25a -1a-> -1a 0.024498 + 9a-> 13a 10b-> 13b 0.023409 + 10a-> 13a 9b-> 13b 0.023409 + 11a-> 25a 11b-> 26b 0.020886 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034859316 + alpha-alpha-alpha ... -0.000878310 ( 2.5%) + alpha-alpha-beta ... -0.016551348 ( 47.5%) + alpha-beta -beta ... -0.016551348 ( 47.5%) + beta -beta -beta ... -0.000878310 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034859316 + +Final correlation energy ... -0.730355706 +E(CCSD) ... -205.405093286 +E(CCSD(T)) ... -205.439952602 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.212372163 sqrt= 1.101077728 +W(HF) = 0.824829232 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.305479 0.000000 + 1 N : 0.175794 -0.000000 + 2 O : -0.117821 0.000000 + 3 H : 0.247506 -0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.848266 s : 3.848266 + pz : 1.270209 p : 4.394592 + px : 1.425515 + py : 1.698869 + dz2 : 0.014932 d : 0.054412 + dxz : 0.011868 + dyz : 0.012122 + dx2y2 : 0.008089 + dxy : 0.007401 + f0 : 0.002038 f : 0.008208 + f+1 : 0.001009 + f-1 : 0.001458 + f+2 : 0.000746 + f-2 : 0.000905 + f+3 : 0.000760 + f-3 : 0.001291 + 1 N s : 3.878013 s : 3.878013 + pz : 0.911542 p : 2.752619 + px : 0.935472 + py : 0.905606 + dz2 : 0.035016 d : 0.164216 + dxz : 0.051647 + dyz : 0.026617 + dx2y2 : 0.024125 + dxy : 0.026811 + f0 : 0.008466 f : 0.029358 + f+1 : 0.003676 + f-1 : 0.005655 + f+2 : 0.003031 + f-2 : 0.003760 + f+3 : 0.002854 + f-3 : 0.001915 + 2 O s : 3.865176 s : 3.865176 + pz : 1.721049 p : 4.157902 + px : 1.178778 + py : 1.258074 + dz2 : 0.010019 d : 0.084726 + dxz : 0.020903 + dyz : 0.010006 + dx2y2 : 0.023289 + dxy : 0.020509 + f0 : 0.001668 f : 0.010018 + f+1 : 0.001353 + f-1 : 0.000925 + f+2 : 0.000988 + f-2 : 0.001267 + f+3 : 0.002402 + f-3 : 0.001416 + 3 H s : 0.644337 s : 0.644337 + pz : 0.022444 p : 0.090425 + px : 0.023984 + py : 0.043998 + dz2 : 0.000946 d : 0.017732 + dxz : 0.005896 + dyz : 0.001955 + dx2y2 : 0.006565 + dxy : 0.002370 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.586579 0.000000 + 1 N : -0.283958 -0.000000 + 2 O : 0.284650 0.000000 + 3 H : -0.587271 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.140219 s : 3.140219 + pz : 1.212853 p : 3.896644 + px : 1.287316 + py : 1.396476 + dz2 : 0.110058 d : 0.292952 + dxz : 0.070688 + dyz : 0.052104 + dx2y2 : 0.027760 + dxy : 0.032342 + f0 : 0.025869 f : 0.083606 + f+1 : 0.019298 + f-1 : 0.015134 + f+2 : 0.009212 + f-2 : 0.007523 + f+3 : 0.001430 + f-3 : 0.005141 + 1 N s : 3.037348 s : 3.037348 + pz : 0.921215 p : 2.881187 + px : 1.082516 + py : 0.877456 + dz2 : 0.214166 d : 0.936311 + dxz : 0.288623 + dyz : 0.113008 + dx2y2 : 0.143987 + dxy : 0.176528 + f0 : 0.107441 f : 0.429113 + f+1 : 0.063479 + f-1 : 0.054659 + f+2 : 0.044006 + f-2 : 0.049927 + f+3 : 0.056890 + f-3 : 0.052709 + 2 O s : 3.320129 s : 3.320129 + pz : 1.417976 p : 3.910355 + px : 1.335015 + py : 1.157364 + dz2 : 0.054533 d : 0.358607 + dxz : 0.099168 + dyz : 0.021995 + dx2y2 : 0.079311 + dxy : 0.103601 + f0 : 0.015381 f : 0.126259 + f+1 : 0.020037 + f-1 : 0.006827 + f+2 : 0.015541 + f-2 : 0.013954 + f+3 : 0.027103 + f-3 : 0.027415 + 3 H s : 0.626821 s : 0.626821 + pz : 0.142942 p : 0.579159 + px : 0.241102 + py : 0.195115 + dz2 : 0.035005 d : 0.381291 + dxz : 0.103700 + dyz : 0.033990 + dx2y2 : 0.107947 + dxy : 0.100650 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3055 8.0000 -0.3055 2.2125 1.7461 0.4664 + 1 N 6.8242 7.0000 0.1758 2.8509 2.3593 0.4916 + 2 O 8.1178 8.0000 -0.1178 2.1836 1.6841 0.4996 + 3 H 0.7525 1.0000 0.2475 0.9933 0.9197 0.0737 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7574 B( 0-O , 3-H ) : 0.8943 B( 1-N , 2-O ) : 1.5831 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 142.990 sec + +Fock Matrix Formation ... 0.587 sec ( 0.4%) +Initial Guess ... 0.500 sec ( 0.3%) +DIIS Solver ... 6.224 sec ( 4.4%) +State Vector Update ... 0.308 sec ( 0.2%) +Sigma-vector construction ... 100.016 sec ( 69.9%) + <0|H|D> ... 0.008 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.051 sec ( 0.1% of sigma) + (0-ext) ... 0.165 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.070 sec ( 0.1% of sigma) + (2-ext) ... 2.477 sec ( 2.5% of sigma) + (4-ext) ... 56.552 sec ( 56.5% of sigma) + ... 5.953 sec ( 6.0% of sigma) + ... 0.020 sec ( 0.0% of sigma) + (1-ext) ... 0.025 sec ( 0.0% of sigma) + (1-ext) ... 0.264 sec ( 0.3% of sigma) + Fock-dressing ... 6.310 sec ( 6.3% of sigma) + (ik|jl)-dressing ... 0.187 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 22.869 sec ( 22.9% of sigma) + Pair energies ... 0.028 sec ( 0.0% of sigma) +Total Time for computing (T) ... 16.877 sec ( 11.8% of ALL) + I/O of integral and amplitudes ... 1.728 sec ( 10.2% of (T)) + External N**7 contributions ... 9.286 sec ( 55.0% of (T)) + Internal N**7 contributions ... 0.857 sec ( 5.1% of (T)) + N**6 triples energy contributions ... 2.748 sec ( 16.3% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.439952601838 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.004802084 -0.008019634 0.001639499 + 2 N : 0.002967815 -0.009191317 0.001152158 + 3 O : 0.000018804 0.008044291 -0.003055660 + 4 H : 0.001815466 0.009166660 0.000264003 + +Norm of the cartesian gradient ... 0.018604287 +RMS gradient ... 0.005370595 +MAX gradient ... 0.009191317 + +------- +TIMINGS +------- + +Total numerical gradient time ... 938.420 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: -267.56 cm**-1 ***imaginary mode*** + 7: 554.95 cm**-1 + 8: 776.98 cm**-1 + 9: 1172.60 cm**-1 + 10: 1707.58 cm**-1 + 11: 3731.26 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 -0.052348 -0.350113 -0.112596 -0.044769 0.005437 -0.054662 + 1 -0.044990 -0.010917 -0.155994 0.005739 -0.016507 0.028884 + 2 0.033380 0.454312 -0.153997 -0.064862 -0.092568 -0.010000 + 3 0.047905 0.221941 -0.017121 0.020630 0.651707 -0.000987 + 4 -0.068250 0.103744 0.197868 -0.020590 0.330125 -0.000949 + 5 -0.019606 -0.177790 0.545646 0.040247 0.039166 -0.000099 + 6 -0.017495 0.186757 0.117812 0.039884 -0.574921 0.000673 + 7 0.048831 -0.050991 -0.027326 0.008327 -0.272522 0.000909 + 8 -0.016990 -0.295561 -0.281037 -0.031490 0.044357 -0.000215 + 9 0.442874 -0.491257 0.155118 -0.209134 -0.017140 0.870644 + 10 0.887421 -0.459008 0.160122 0.062858 0.000116 -0.459689 + 11 0.012307 -0.049155 -0.677340 0.970024 0.220967 0.163524 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 7: 554.95 0.023531 118.92 0.013232 ( 0.070095 -0.015501 -0.089881) + 8: 776.98 0.015652 79.10 0.006286 (-0.043270 0.013936 0.064961) + 9: 1172.60 0.021447 108.38 0.005708 (-0.036256 0.016788 0.064119) + 10: 1707.58 0.032193 162.69 0.005883 ( 0.057967 0.008294 -0.049541) + 11: 3731.26 0.013061 66.00 0.001092 ( 0.028864 -0.013024 -0.009464) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 7 +The total number of vibrations considered is 5 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 554.95 E(vib) ... 0.12 +freq. 776.98 E(vib) ... 0.05 +freq. 1172.60 E(vib) ... 0.01 +freq. 1707.58 E(vib) ... 0.00 +freq. 3731.26 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.43995260 Eh +Zero point energy ... 0.01809633 Eh 11.36 kcal/mol +Thermal vibrational correction ... 0.00029261 Eh 0.18 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.41873112 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00312515 Eh 1.96 kcal/mol +Non-thermal (ZPE) correction 0.01809633 Eh 11.36 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02122148 Eh 13.32 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.41873112 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.41778691 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.822554 0.400903 0.359856 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00038623 Eh 0.24 kcal/mol +Rotational entropy ... 0.00993496 Eh 6.23 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02812351 Eh 17.65 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00993496 Eh 6.23 kcal/mol| +| sn= 2 | S(rot)= 0.00928050 Eh 5.82 kcal/mol| +| sn= 3 | S(rot)= 0.00889767 Eh 5.58 kcal/mol| +| sn= 4 | S(rot)= 0.00862604 Eh 5.41 kcal/mol| +| sn= 5 | S(rot)= 0.00841536 Eh 5.28 kcal/mol| +| sn= 6 | S(rot)= 0.00824321 Eh 5.17 kcal/mol| +| sn= 7 | S(rot)= 0.00809767 Eh 5.08 kcal/mol| +| sn= 8 | S(rot)= 0.00797159 Eh 5.00 kcal/mol| +| sn= 9 | S(rot)= 0.00786038 Eh 4.93 kcal/mol| +| sn=10 | S(rot)= 0.00776090 Eh 4.87 kcal/mol| +| sn=11 | S(rot)= 0.00767091 Eh 4.81 kcal/mol| +| sn=12 | S(rot)= 0.00758876 Eh 4.76 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.41778691 Eh +Total entropy correction ... -0.02812351 Eh -17.65 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44591042 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00595782 Eh -3.74 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.439952603 Eh +Current gradient norm .... 0.018604287 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + -0.009182284 0.101534414 0.154667020 0.480229843 0.502124795 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999764377 +Lowest eigenvalues of augmented Hessian: + -0.000081835 0.099692020 0.154028020 0.480216278 0.502028180 +Length of the computed step .... 0.021712045 +The final length of the internal step .... 0.021712045 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0088639051 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0061751648 RMS(Int)= 0.0088624915 + Iter 1: RMS(Cart)= 0.0000036831 RMS(Int)= 0.0000053723 + Iter 2: RMS(Cart)= 0.0000000209 RMS(Int)= 0.0000000243 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0022680684 0.0001000000 NO + MAX gradient 0.0036824239 0.0003000000 NO + RMS step 0.0088639051 0.0020000000 NO + MAX step 0.0209743404 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0111 Max(Angles) 0.04 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4940 0.002974 -0.0111 1.4829 + 2. B(O 2,N 1) 1.1677 0.003682 -0.0007 1.1670 + 3. B(H 3,O 0) 0.9722 0.002681 -0.0028 0.9693 + 4. A(N 1,O 0,H 3) 102.23 0.000785 -0.04 102.19 + 5. A(O 0,N 1,O 2) 110.41 0.000807 0.04 110.46 + 6. D(O 2,N 1,O 0,H 3) 122.73 -0.016063 0.00 122.73 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.311199 -0.123836 0.759108 + N 0.203728 -0.346114 -0.613615 + O 1.258003 0.138685 -0.737206 + H -1.150532 0.331266 0.591713 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.588081 -0.234017 1.434506 + 1 N 7.0000 0 14.007 0.384991 -0.654062 -1.159564 + 2 O 8.0000 0 15.999 2.377282 0.262076 -1.393117 + 3 H 1.0000 0 1.008 -2.174190 0.626003 1.118176 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.482877377331 0.00000000 0.00000000 + O 2 1 0 1.166962097909 110.45584479 0.00000000 + H 1 2 3 0.969339723427 102.19215957 122.72727267 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.802232133343 0.00000000 0.00000000 + O 2 1 0 2.205238773714 110.45584479 0.00000000 + H 1 2 3 1.831786608007 102.19215957 122.72727267 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2225 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2690 + la=0 lb=0: 547 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 392 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.700985944537 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.942e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7108602743 0.000000000000 0.00041104 0.00000852 0.0018464 0.7000 + 1 -204.7108726967 -0.000012422336 0.00031272 0.00000704 0.0014187 0.7000 + ***Turning on DIIS*** + 2 -204.7108829678 -0.000010271186 0.00073941 0.00001804 0.0010769 0.0000 + 3 -204.7102432912 0.000639676671 0.00028712 0.00000752 0.0002601 0.0000 + 4 -204.7109583410 -0.000715049842 0.00008654 0.00000249 0.0001076 0.0000 + 5 -204.7112469263 -0.000288585259 0.00003496 0.00000105 0.0000472 0.0000 + 6 -204.7107742812 0.000472645079 0.00002057 0.00000066 0.0000325 0.0000 + 7 -204.7109097925 -0.000135511325 0.00001126 0.00000042 0.0000159 0.0000 + 8 -204.7109193953 -0.000009602821 0.00001024 0.00000034 0.0000088 0.0000 + 9 -204.7108905708 0.000028824535 0.00000708 0.00000028 0.0000056 0.0000 + 10 -204.7109286391 -0.000038068268 0.00000321 0.00000013 0.0000031 0.0000 + 11 -204.7109155559 0.000013083227 0.00000158 0.00000006 0.0000015 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + +Total Energy : -204.71091607 Eh -5570.46722 eV + Last Energy change ... -5.1035e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.0524e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 2 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.248 sec +Reference energy ... -204.710916739 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.858 sec +AO-integral generation ... 0.165 sec +Half transformation ... 0.092 sec +K-integral sorting ... 5.677 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.029 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.029 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.044 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.044 s ( 0.000 ms/b) + 159120 b 0 skpd 0.021 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.043 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.036 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.028 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.048 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.028 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.421 sec +AO-integral generation ... 0.302 sec +Half transformation ... 0.051 sec +J-integral sorting ... 0.053 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.163 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.267 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090186457 +EMP2(bb)= -0.090186457 +EMP2(ab)= -0.517119010 + +Initial guess performed in 0.141 sec +E(0) ... -204.710916739 +E(MP2) ... -0.697491923 +Initial E(tot) ... -205.408408662 + ... 0.189050566 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.408408662 -0.697491923 -0.000000000 0.020488678 3.11 0.000001086 + *** Turning on DIIS *** + 1 -205.379866337 -0.668949598 0.028542326 0.009062742 3.44 0.056395064 + 2 -205.399379883 -0.688463144 -0.019513546 0.004162318 4.23 0.059271004 + 3 -205.403179522 -0.692262782 -0.003799639 0.001726760 4.77 0.072893134 + 4 -205.404731062 -0.693814323 -0.001551541 0.001479615 4.28 0.079169820 + 5 -205.405255989 -0.694339250 -0.000524927 0.000909772 4.88 0.084256526 + 6 -205.405355548 -0.694438809 -0.000099559 0.000585883 4.56 0.086841992 + 7 -205.405398959 -0.694482220 -0.000043411 0.000295715 4.43 0.088134377 + 8 -205.405410870 -0.694494131 -0.000011911 0.000158569 3.59 0.088694660 + 9 -205.405406929 -0.694490189 0.000003941 0.000054023 3.45 0.088887544 + 10 -205.405412613 -0.694495874 -0.000005685 0.000037968 3.36 0.088964719 + 11 -205.405409283 -0.694492544 0.000003331 0.000028230 3.47 0.088959620 + 12 -205.405411167 -0.694494428 -0.000001884 0.000019464 3.46 0.088977793 + 13 -205.405411004 -0.694494265 0.000000163 0.000011882 3.38 0.088972680 + 14 -205.405411356 -0.694494617 -0.000000352 0.000006526 3.86 0.088978233 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.710916739 +E(CORR) ... -0.694494617 +E(TOT) ... -205.405411356 +Singles norm **1/2 ... 0.088978233 ( 0.044489117, 0.044489117) +T1 diagnostic ... 0.020972371 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.052907 + 9a-> 13a 9b-> 13b 0.049146 + 9a-> 13a 8b-> 13b 0.042418 + 8a-> 13a 9b-> 13b 0.042418 + 8b-> 13b -1b-> -1b 0.030759 + 8a-> 13a -1a-> -1a 0.030759 + 11a-> 25a 11b-> 25b 0.030122 + 10b-> 13b -1b-> -1b 0.029909 + 10a-> 13a -1a-> -1a 0.029909 + 5a-> 13a 5b-> 13b 0.028831 + 11a-> 13a 11b-> 13b 0.027791 + 11a-> 25a -1a-> -1a 0.024500 + 11b-> 25b -1b-> -1b 0.024500 + 9a-> 13a 10b-> 13b 0.024130 + 10a-> 13a 9b-> 13b 0.024130 + 11a-> 25a 11b-> 26b 0.022842 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034581442 + alpha-alpha-alpha ... -0.000875101 ( 2.5%) + alpha-alpha-beta ... -0.016415620 ( 47.5%) + alpha-beta -beta ... -0.016415620 ( 47.5%) + beta -beta -beta ... -0.000875101 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034581442 + +Final correlation energy ... -0.729076059 +E(CCSD) ... -205.405411356 +E(CCSD(T)) ... -205.439992798 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210855155 sqrt= 1.100388638 +W(HF) = 0.825862611 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 77.680 sec + +Fock Matrix Formation ... 0.248 sec ( 0.3%) +Initial Guess ... 0.141 sec ( 0.2%) +DIIS Solver ... 3.026 sec ( 3.9%) +State Vector Update ... 0.147 sec ( 0.2%) +Sigma-vector construction ... 55.075 sec ( 70.9%) + <0|H|D> ... 0.005 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.028 sec ( 0.1% of sigma) + (0-ext) ... 0.086 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.032 sec ( 0.1% of sigma) + (2-ext) ... 1.190 sec ( 2.2% of sigma) + (4-ext) ... 32.394 sec ( 58.8% of sigma) + ... 2.191 sec ( 4.0% of sigma) + ... 0.004 sec ( 0.0% of sigma) + (1-ext) ... 0.010 sec ( 0.0% of sigma) + (1-ext) ... 0.146 sec ( 0.3% of sigma) + Fock-dressing ... 2.987 sec ( 5.4% of sigma) + (ik|jl)-dressing ... 0.096 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 12.830 sec ( 23.3% of sigma) + Pair energies ... 0.011 sec ( 0.0% of sigma) +Total Time for computing (T) ... 10.204 sec ( 13.1% of ALL) + I/O of integral and amplitudes ... 0.878 sec ( 8.6% of (T)) + External N**7 contributions ... 4.521 sec ( 44.3% of (T)) + Internal N**7 contributions ... 0.367 sec ( 3.6% of (T)) + N**6 triples energy contributions ... 1.855 sec ( 18.2% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.439992797901 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.005808898 -0.007369557 -0.001092903 + 2 N : 0.004961816 -0.007510065 0.003151983 + 3 O : -0.003482651 0.006772454 -0.002356957 + 4 H : 0.004329733 0.008107167 0.000297877 + +Norm of the cartesian gradient ... 0.018119479 +RMS gradient ... 0.005230643 +MAX gradient ... 0.008107167 + +------- +TIMINGS +------- + +Total numerical gradient time ... 504.957 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.439992798 Eh +Current gradient norm .... 0.018119479 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999655 +Lowest eigenvalues of augmented Hessian: + -0.000000090 0.101852965 0.155289699 0.479497714 0.500039582 +Length of the computed step .... 0.000830940 +The final length of the internal step .... 0.000830940 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0003392299 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0002143217 RMS(Int)= 0.0003392335 + Iter 1: RMS(Cart)= 0.0000000093 RMS(Int)= 0.0000000139 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000401949 0.0000050000 NO + RMS gradient 0.0000593600 0.0001000000 YES + MAX gradient 0.0001117654 0.0003000000 YES + RMS step 0.0003392299 0.0020000000 YES + MAX step 0.0008303760 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0004 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4829 -0.000112 0.0004 1.4833 + 2. B(O 2,N 1) 1.1670 -0.000083 -0.0000 1.1669 + 3. B(H 3,O 0) 0.9693 0.000006 -0.0000 0.9693 + 4. A(N 1,O 0,H 3) 102.19 -0.000024 0.00 102.19 + 5. A(O 0,N 1,O 2) 110.46 -0.000034 -0.00 110.46 + 6. D(O 2,N 1,O 0,H 3) 122.73 -0.016467 -0.00 122.73 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.311330 -0.123802 0.759284 + N 0.203860 -0.346148 -0.613804 + O 1.258124 0.138669 -0.737303 + H -1.150653 0.331280 0.591822 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.588329 -0.233951 1.434839 + 1 N 7.0000 0 14.007 0.385240 -0.654125 -1.159921 + 2 O 8.0000 0 15.999 2.377509 0.262047 -1.393300 + 3 H 1.0000 0 1.008 -2.174418 0.626029 1.118382 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.483316793364 0.00000000 0.00000000 + O 2 1 0 1.166949212869 110.45515866 0.00000000 + H 1 2 3 0.969332238462 102.19221724 122.72727267 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.803062509304 0.00000000 0.00000000 + O 2 1 0 2.205214424517 110.45515866 0.00000000 + H 1 2 3 1.831772463474 102.19221724 122.72727267 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2225 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2690 + la=0 lb=0: 547 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 392 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.692265216159 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.6922652162 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.943e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.003 sec +Total time needed ... 0.007 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7108780551 0.000000000000 0.00001359 0.00000028 0.0000682 0.7000 + 1 -204.7108780752 -0.000000020136 0.00001028 0.00000024 0.0000537 0.7000 + ***Turning on DIIS*** + 2 -204.7108780921 -0.000000016819 0.00002504 0.00000064 0.0000417 0.0000 + 3 -204.7108882207 -0.000010128634 0.00000994 0.00000028 0.0000109 0.0000 + 4 -204.7108738654 0.000014355343 0.00000337 0.00000009 0.0000034 0.0000 + 5 -204.7108738091 0.000000056292 0.00000149 0.00000004 0.0000014 0.0000 + 6 -204.7108808258 -0.000007016781 0.00000067 0.00000002 0.0000010 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71087854 Eh -5570.46620 eV + +Components: +Nuclear Repulsion : 68.69226522 Eh 1869.21157 eV +Electronic Energy : -273.40314375 Eh -7439.67777 eV +One Electron Energy: -417.10274061 Eh -11349.94259 eV +Two Electron Energy: 143.69959685 Eh 3910.26482 eV + +Virial components: +Potential Energy : -408.94591807 Eh -11127.98417 eV +Kinetic Energy : 204.23503953 Eh 5557.51796 eV +Virial Ratio : 2.00232986 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.2872e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.8095e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.4102e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.3785e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.684825 -562.8627 + 1 1.0000 -20.622246 -561.1598 + 2 1.0000 -15.802660 -430.0122 + 3 1.0000 -1.613410 -43.9031 + 4 1.0000 -1.379970 -37.5509 + 5 1.0000 -0.951488 -25.8913 + 6 1.0000 -0.773014 -21.0348 + 7 1.0000 -0.729506 -19.8509 + 8 1.0000 -0.696069 -18.9410 + 9 1.0000 -0.610377 -16.6092 + 10 1.0000 -0.529259 -14.4019 + 11 1.0000 -0.458948 -12.4886 + 12 0.0000 0.029978 0.8157 + 13 0.0000 0.071635 1.9493 + 14 0.0000 0.092050 2.5048 + 15 0.0000 0.100572 2.7367 + 16 0.0000 0.116694 3.1754 + 17 0.0000 0.153006 4.1635 + 18 0.0000 0.157199 4.2776 + 19 0.0000 0.172882 4.7044 + 20 0.0000 0.185503 5.0478 + 21 0.0000 0.190457 5.1826 + 22 0.0000 0.202287 5.5045 + 23 0.0000 0.236917 6.4468 + 24 0.0000 0.271715 7.3937 + 25 0.0000 0.282118 7.6768 + 26 0.0000 0.308684 8.3997 + 27 0.0000 0.328838 8.9481 + 28 0.0000 0.340342 9.2612 + 29 0.0000 0.359202 9.7744 + 30 0.0000 0.424299 11.5458 + 31 0.0000 0.510985 13.9046 + 32 0.0000 0.520159 14.1543 + 33 0.0000 0.544674 14.8213 + 34 0.0000 0.571722 15.5573 + 35 0.0000 0.608247 16.5512 + 36 0.0000 0.631480 17.1835 + 37 0.0000 0.649811 17.6823 + 38 0.0000 0.698893 19.0178 + 39 0.0000 0.723175 19.6786 + 40 0.0000 0.738897 20.1064 + 41 0.0000 0.741766 20.1845 + 42 0.0000 0.778171 21.1751 + 43 0.0000 0.793049 21.5799 + 44 0.0000 0.803298 21.8588 + 45 0.0000 0.823988 22.4219 + 46 0.0000 0.847868 23.0717 + 47 0.0000 0.863760 23.5041 + 48 0.0000 0.916764 24.9464 + 49 0.0000 0.944272 25.6950 + 50 0.0000 0.958729 26.0884 + 51 0.0000 0.999562 27.1995 + 52 0.0000 1.006040 27.3757 + 53 0.0000 1.023740 27.8574 + 54 0.0000 1.047351 28.4999 + 55 0.0000 1.100901 29.9570 + 56 0.0000 1.142434 31.0872 + 57 0.0000 1.222605 33.2688 + 58 0.0000 1.253452 34.1082 + 59 0.0000 1.298418 35.3317 + 60 0.0000 1.352673 36.8081 + 61 0.0000 1.416916 38.5562 + 62 0.0000 1.435744 39.0686 + 63 0.0000 1.510019 41.0897 + 64 0.0000 1.534307 41.7506 + 65 0.0000 1.559702 42.4416 + 66 0.0000 1.565506 42.5996 + 67 0.0000 1.640467 44.6394 + 68 0.0000 1.660234 45.1773 + 69 0.0000 1.703454 46.3533 + 70 0.0000 1.778071 48.3838 + 71 0.0000 1.796147 48.8756 + 72 0.0000 1.883661 51.2570 + 73 0.0000 1.936164 52.6857 + 74 0.0000 1.961923 53.3866 + 75 0.0000 2.033762 55.3415 + 76 0.0000 2.056378 55.9569 + 77 0.0000 2.087661 56.8082 + 78 0.0000 2.155368 58.6505 + 79 0.0000 2.199330 59.8468 + 80 0.0000 2.259221 61.4765 + 81 0.0000 2.293506 62.4095 + 82 0.0000 2.308374 62.8140 + 83 0.0000 2.379007 64.7361 + 84 0.0000 2.418377 65.8074 + 85 0.0000 2.461636 66.9845 + 86 0.0000 2.471796 67.2610 + 87 0.0000 2.479783 67.4783 + 88 0.0000 2.512927 68.3802 + 89 0.0000 2.541086 69.1465 + 90 0.0000 2.561881 69.7123 + 91 0.0000 2.603149 70.8353 + 92 0.0000 2.673155 72.7402 + 93 0.0000 2.696273 73.3693 + 94 0.0000 2.742172 74.6183 + 95 0.0000 2.799312 76.1732 + 96 0.0000 2.840354 77.2900 + 97 0.0000 2.890149 78.6450 + 98 0.0000 2.960476 80.5587 + 99 0.0000 3.034446 82.5715 + 100 0.0000 3.079044 83.7851 + 101 0.0000 3.164084 86.0991 + 102 0.0000 3.251977 88.4908 + 103 0.0000 3.484606 94.8210 + 104 0.0000 3.733572 101.5957 + 105 0.0000 3.847839 104.7050 + 106 0.0000 4.046094 110.0998 + 107 0.0000 4.163795 113.3026 + 108 0.0000 4.200612 114.3045 + 109 0.0000 4.317819 117.4938 + 110 0.0000 4.343813 118.2012 + 111 0.0000 4.392110 119.5154 + 112 0.0000 4.556062 123.9767 + 113 0.0000 4.621609 125.7604 + 114 0.0000 4.709296 128.1465 + 115 0.0000 4.731163 128.7415 + 116 0.0000 4.786815 130.2559 + 117 0.0000 4.883933 132.8986 + 118 0.0000 4.941066 134.4532 + 119 0.0000 4.973575 135.3379 + 120 0.0000 5.067708 137.8993 + 121 0.0000 5.092311 138.5688 + 122 0.0000 5.168024 140.6291 + 123 0.0000 5.199972 141.4984 + 124 0.0000 5.237748 142.5264 + 125 0.0000 5.335217 145.1786 + 126 0.0000 5.385083 146.5356 + 127 0.0000 5.420116 147.4889 + 128 0.0000 5.532829 150.5559 + 129 0.0000 5.713410 155.4698 + 130 0.0000 5.781866 157.3326 + 131 0.0000 5.961278 162.2146 + 132 0.0000 6.155707 167.5053 + 133 0.0000 6.403274 174.2419 + 134 0.0000 6.491860 176.6525 + 135 0.0000 6.504200 176.9883 + 136 0.0000 6.699709 182.3084 + 137 0.0000 6.712013 182.6432 + 138 0.0000 6.763460 184.0431 + 139 0.0000 6.819262 185.5615 + 140 0.0000 6.859902 186.6674 + 141 0.0000 7.064259 192.2283 + 142 0.0000 7.115610 193.6256 + 143 0.0000 7.129348 193.9994 + 144 0.0000 7.198502 195.8812 + 145 0.0000 7.251451 197.3220 + 146 0.0000 7.276187 197.9951 + 147 0.0000 7.358108 200.2243 + 148 0.0000 7.402196 201.4240 + 149 0.0000 7.449352 202.7072 + 150 0.0000 7.468247 203.2213 + 151 0.0000 7.537867 205.1158 + 152 0.0000 7.606951 206.9957 + 153 0.0000 7.609579 207.0672 + 154 0.0000 7.828831 213.0333 + 155 0.0000 7.907752 215.1809 + 156 0.0000 7.977632 217.0824 + 157 0.0000 8.386081 228.1969 + 158 0.0000 14.079472 383.1219 + 159 0.0000 14.830010 403.5451 + 160 0.0000 16.150603 439.4802 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.684825 -562.8627 + 1 1.0000 -20.622246 -561.1598 + 2 1.0000 -15.802660 -430.0122 + 3 1.0000 -1.613410 -43.9031 + 4 1.0000 -1.379970 -37.5509 + 5 1.0000 -0.951488 -25.8913 + 6 1.0000 -0.773014 -21.0348 + 7 1.0000 -0.729506 -19.8509 + 8 1.0000 -0.696069 -18.9410 + 9 1.0000 -0.610377 -16.6092 + 10 1.0000 -0.529259 -14.4019 + 11 1.0000 -0.458948 -12.4886 + 12 0.0000 0.029978 0.8157 + 13 0.0000 0.071635 1.9493 + 14 0.0000 0.092050 2.5048 + 15 0.0000 0.100572 2.7367 + 16 0.0000 0.116694 3.1754 + 17 0.0000 0.153006 4.1635 + 18 0.0000 0.157199 4.2776 + 19 0.0000 0.172882 4.7044 + 20 0.0000 0.185503 5.0478 + 21 0.0000 0.190457 5.1826 + 22 0.0000 0.202287 5.5045 + 23 0.0000 0.236917 6.4468 + 24 0.0000 0.271715 7.3937 + 25 0.0000 0.282118 7.6768 + 26 0.0000 0.308684 8.3997 + 27 0.0000 0.328838 8.9481 + 28 0.0000 0.340342 9.2612 + 29 0.0000 0.359202 9.7744 + 30 0.0000 0.424299 11.5458 + 31 0.0000 0.510985 13.9046 + 32 0.0000 0.520159 14.1543 + 33 0.0000 0.544674 14.8213 + 34 0.0000 0.571722 15.5573 + 35 0.0000 0.608247 16.5512 + 36 0.0000 0.631480 17.1835 + 37 0.0000 0.649811 17.6823 + 38 0.0000 0.698893 19.0178 + 39 0.0000 0.723175 19.6786 + 40 0.0000 0.738897 20.1064 + 41 0.0000 0.741766 20.1845 + 42 0.0000 0.778171 21.1751 + 43 0.0000 0.793049 21.5799 + 44 0.0000 0.803298 21.8588 + 45 0.0000 0.823988 22.4219 + 46 0.0000 0.847868 23.0717 + 47 0.0000 0.863760 23.5041 + 48 0.0000 0.916764 24.9464 + 49 0.0000 0.944272 25.6950 + 50 0.0000 0.958729 26.0884 + 51 0.0000 0.999562 27.1995 + 52 0.0000 1.006040 27.3757 + 53 0.0000 1.023740 27.8574 + 54 0.0000 1.047351 28.4999 + 55 0.0000 1.100901 29.9570 + 56 0.0000 1.142434 31.0872 + 57 0.0000 1.222605 33.2688 + 58 0.0000 1.253452 34.1082 + 59 0.0000 1.298418 35.3317 + 60 0.0000 1.352673 36.8081 + 61 0.0000 1.416916 38.5562 + 62 0.0000 1.435744 39.0686 + 63 0.0000 1.510019 41.0897 + 64 0.0000 1.534307 41.7506 + 65 0.0000 1.559702 42.4416 + 66 0.0000 1.565506 42.5996 + 67 0.0000 1.640467 44.6394 + 68 0.0000 1.660234 45.1773 + 69 0.0000 1.703454 46.3533 + 70 0.0000 1.778071 48.3838 + 71 0.0000 1.796147 48.8756 + 72 0.0000 1.883661 51.2570 + 73 0.0000 1.936164 52.6857 + 74 0.0000 1.961923 53.3866 + 75 0.0000 2.033762 55.3415 + 76 0.0000 2.056378 55.9569 + 77 0.0000 2.087661 56.8082 + 78 0.0000 2.155368 58.6505 + 79 0.0000 2.199330 59.8468 + 80 0.0000 2.259221 61.4765 + 81 0.0000 2.293506 62.4095 + 82 0.0000 2.308374 62.8140 + 83 0.0000 2.379007 64.7361 + 84 0.0000 2.418377 65.8074 + 85 0.0000 2.461636 66.9845 + 86 0.0000 2.471796 67.2610 + 87 0.0000 2.479783 67.4783 + 88 0.0000 2.512927 68.3802 + 89 0.0000 2.541086 69.1465 + 90 0.0000 2.561881 69.7123 + 91 0.0000 2.603149 70.8353 + 92 0.0000 2.673155 72.7402 + 93 0.0000 2.696273 73.3693 + 94 0.0000 2.742172 74.6183 + 95 0.0000 2.799312 76.1732 + 96 0.0000 2.840354 77.2900 + 97 0.0000 2.890149 78.6450 + 98 0.0000 2.960476 80.5587 + 99 0.0000 3.034446 82.5715 + 100 0.0000 3.079044 83.7851 + 101 0.0000 3.164084 86.0991 + 102 0.0000 3.251977 88.4908 + 103 0.0000 3.484606 94.8210 + 104 0.0000 3.733572 101.5957 + 105 0.0000 3.847839 104.7050 + 106 0.0000 4.046094 110.0998 + 107 0.0000 4.163795 113.3026 + 108 0.0000 4.200612 114.3045 + 109 0.0000 4.317819 117.4938 + 110 0.0000 4.343813 118.2012 + 111 0.0000 4.392110 119.5154 + 112 0.0000 4.556062 123.9767 + 113 0.0000 4.621609 125.7604 + 114 0.0000 4.709296 128.1465 + 115 0.0000 4.731163 128.7415 + 116 0.0000 4.786815 130.2559 + 117 0.0000 4.883933 132.8986 + 118 0.0000 4.941066 134.4532 + 119 0.0000 4.973575 135.3379 + 120 0.0000 5.067708 137.8993 + 121 0.0000 5.092311 138.5688 + 122 0.0000 5.168024 140.6291 + 123 0.0000 5.199972 141.4984 + 124 0.0000 5.237748 142.5264 + 125 0.0000 5.335217 145.1786 + 126 0.0000 5.385083 146.5356 + 127 0.0000 5.420116 147.4889 + 128 0.0000 5.532829 150.5559 + 129 0.0000 5.713410 155.4698 + 130 0.0000 5.781866 157.3326 + 131 0.0000 5.961278 162.2146 + 132 0.0000 6.155707 167.5053 + 133 0.0000 6.403274 174.2419 + 134 0.0000 6.491860 176.6525 + 135 0.0000 6.504200 176.9883 + 136 0.0000 6.699709 182.3084 + 137 0.0000 6.712013 182.6432 + 138 0.0000 6.763460 184.0431 + 139 0.0000 6.819262 185.5615 + 140 0.0000 6.859902 186.6674 + 141 0.0000 7.064259 192.2283 + 142 0.0000 7.115610 193.6256 + 143 0.0000 7.129348 193.9994 + 144 0.0000 7.198502 195.8812 + 145 0.0000 7.251451 197.3220 + 146 0.0000 7.276187 197.9951 + 147 0.0000 7.358108 200.2243 + 148 0.0000 7.402196 201.4240 + 149 0.0000 7.449352 202.7072 + 150 0.0000 7.468247 203.2213 + 151 0.0000 7.537867 205.1158 + 152 0.0000 7.606951 206.9957 + 153 0.0000 7.609579 207.0672 + 154 0.0000 7.828831 213.0333 + 155 0.0000 7.907752 215.1809 + 156 0.0000 7.977632 217.0824 + 157 0.0000 8.386081 228.1969 + 158 0.0000 14.079472 383.1219 + 159 0.0000 14.830010 403.5451 + 160 0.0000 16.150603 439.4802 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.368045 0.000000 + 1 N : 0.353105 0.000000 + 2 O : -0.243893 0.000000 + 3 H : 0.258833 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.870287 s : 3.870287 + pz : 1.281241 p : 4.470511 + px : 1.438469 + py : 1.750800 + dz2 : 0.010275 d : 0.022759 + dxz : 0.006279 + dyz : 0.004893 + dx2y2 : 0.000779 + dxy : 0.000532 + f0 : 0.001823 f : 0.004488 + f+1 : 0.000597 + f-1 : 0.000934 + f+2 : 0.000099 + f-2 : 0.000261 + f+3 : 0.000118 + f-3 : 0.000655 + 1 N s : 3.824594 s : 3.824594 + pz : 0.870009 p : 2.657116 + px : 0.932992 + py : 0.854115 + dz2 : 0.029040 d : 0.134815 + dxz : 0.041920 + dyz : 0.018288 + dx2y2 : 0.022436 + dxy : 0.023132 + f0 : 0.008912 f : 0.030369 + f+1 : 0.003954 + f-1 : 0.005707 + f+2 : 0.002657 + f-2 : 0.003600 + f+3 : 0.003742 + f-3 : 0.001798 + 2 O s : 3.877972 s : 3.877972 + pz : 1.812912 p : 4.294604 + px : 1.192585 + py : 1.289106 + dz2 : 0.004857 d : 0.063721 + dxz : 0.013338 + dyz : 0.003740 + dx2y2 : 0.023012 + dxy : 0.018774 + f0 : 0.001187 f : 0.007597 + f+1 : 0.000894 + f-1 : 0.000470 + f+2 : 0.000414 + f-2 : 0.000769 + f+3 : 0.002664 + f-3 : 0.001198 + 3 H s : 0.635650 s : 0.635650 + pz : 0.019125 p : 0.084438 + px : 0.026852 + py : 0.038461 + dz2 : 0.000823 d : 0.021079 + dxz : 0.006773 + dyz : 0.002242 + dx2y2 : 0.007975 + dxy : 0.003265 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.582759 0.000000 + 1 N : -0.243303 0.000000 + 2 O : 0.246227 0.000000 + 3 H : -0.585683 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.129897 s : 3.129897 + pz : 1.213583 p : 3.942527 + px : 1.293747 + py : 1.435197 + dz2 : 0.105205 d : 0.266185 + dxz : 0.065457 + dyz : 0.047865 + dx2y2 : 0.021596 + dxy : 0.026062 + f0 : 0.025191 f : 0.078631 + f+1 : 0.017892 + f-1 : 0.014713 + f+2 : 0.008938 + f-2 : 0.006853 + f+3 : 0.000833 + f-3 : 0.004210 + 1 N s : 3.026868 s : 3.026868 + pz : 0.906876 p : 2.838813 + px : 1.084946 + py : 0.846991 + dz2 : 0.209751 d : 0.934473 + dxz : 0.291820 + dyz : 0.113023 + dx2y2 : 0.145385 + dxy : 0.174495 + f0 : 0.111250 f : 0.443150 + f+1 : 0.064012 + f-1 : 0.057271 + f+2 : 0.047629 + f-2 : 0.052999 + f+3 : 0.057622 + f-3 : 0.052367 + 2 O s : 3.316218 s : 3.316218 + pz : 1.476309 p : 3.989350 + px : 1.342048 + py : 1.170993 + dz2 : 0.048814 d : 0.329945 + dxz : 0.097181 + dyz : 0.015834 + dx2y2 : 0.071322 + dxy : 0.096793 + f0 : 0.014747 f : 0.118260 + f+1 : 0.019556 + f-1 : 0.006304 + f+2 : 0.015622 + f-2 : 0.012755 + f+3 : 0.022826 + f-3 : 0.026450 + 3 H s : 0.625864 s : 0.625864 + pz : 0.142526 p : 0.567510 + px : 0.236626 + py : 0.188359 + dz2 : 0.033780 d : 0.392309 + dxz : 0.107857 + dyz : 0.035589 + dx2y2 : 0.112080 + dxy : 0.103002 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3680 8.0000 -0.3680 1.8552 1.8552 0.0000 + 1 N 6.6469 7.0000 0.3531 2.5711 2.5711 0.0000 + 2 O 8.2439 8.0000 -0.2439 1.7845 1.7845 0.0000 + 3 H 0.7412 1.0000 0.2588 0.9712 0.9712 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8386 B( 0-O , 3-H ) : 0.9605 B( 1-N , 2-O ) : 1.7251 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.948 sec +Sum of individual times .... 1.566 sec ( 80.4%) + +Fock matrix formation .... 1.278 sec ( 65.6%) +Diagonalization .... 0.094 sec ( 4.8%) +Density matrix formation .... 0.008 sec ( 0.4%) +Population analysis .... 0.100 sec ( 5.2%) +Initial guess .... 0.012 sec ( 0.6%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.3%) +DIIS solution .... 0.074 sec ( 3.8%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.255 sec +Reference energy ... -204.710878147 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.650 sec +AO-integral generation ... 0.179 sec +Half transformation ... 0.102 sec +K-integral sorting ... 5.522 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.027 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) + 277134 b 0 skpd 0.042 s ( 0.000 ms/b) +: : 151164 b 0 skpd 0.043 s ( 0.000 ms/b) + 159120 b 0 skpd 0.020 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.045 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.032 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.028 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.047 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.027 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.407 sec +AO-integral generation ... 0.290 sec +Half transformation ... 0.050 sec +J-integral sorting ... 0.052 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.156 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.259 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090191066 +EMP2(bb)= -0.090191066 +EMP2(ab)= -0.517149941 + +Initial guess performed in 0.136 sec +E(0) ... -204.710878147 +E(MP2) ... -0.697532073 +Initial E(tot) ... -205.408410220 + ... 0.189089326 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.408410220 -0.697532073 -0.000000000 0.020489375 3.05 0.000001442 + *** Turning on DIIS *** + 1 -205.379848297 -0.668970150 0.028561923 0.009073409 3.33 0.056413453 + 2 -205.399368596 -0.688490449 -0.019520299 0.004161694 3.21 0.059285627 + 3 -205.403169324 -0.692291177 -0.003800728 0.001728023 3.06 0.072912779 + 4 -205.404721623 -0.693843476 -0.001552299 0.001480934 3.29 0.079191909 + 5 -205.405246979 -0.694368832 -0.000525356 0.000910542 3.14 0.084282287 + 6 -205.405346615 -0.694468468 -0.000099636 0.000586488 3.35 0.086870360 + 7 -205.405390092 -0.694511945 -0.000043477 0.000295965 3.15 0.088165086 + 8 -205.405402032 -0.694523885 -0.000011940 0.000158743 3.30 0.088726465 + 9 -205.405398085 -0.694519939 0.000003947 0.000054086 3.07 0.088919773 + 10 -205.405403785 -0.694525638 -0.000005699 0.000038025 3.80 0.088997166 + 11 -205.405400447 -0.694522300 0.000003338 0.000028268 4.92 0.088992058 + 12 -205.405402334 -0.694524188 -0.000001888 0.000019487 4.64 0.089010301 + 13 -205.405402171 -0.694524024 0.000000163 0.000011898 3.19 0.089005169 + 14 -205.405402524 -0.694524377 -0.000000353 0.000006535 3.24 0.089010737 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.710878147 +E(CORR) ... -0.694524377 +E(TOT) ... -205.405402524 +Singles norm **1/2 ... 0.089010737 ( 0.044505368, 0.044505368) +T1 diagnostic ... 0.020980032 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.052976 + 9a-> 13a 9b-> 13b 0.049118 + 8a-> 13a 9b-> 13b 0.042440 + 9a-> 13a 8b-> 13b 0.042440 + 8a-> 13a -1a-> -1a 0.030754 + 8b-> 13b -1b-> -1b 0.030754 + 11a-> 25a 11b-> 25b 0.030260 + 10b-> 13b -1b-> -1b 0.029942 + 10a-> 13a -1a-> -1a 0.029942 + 5a-> 13a 5b-> 13b 0.028847 + 11a-> 13a 11b-> 13b 0.027776 + 11b-> 25b -1b-> -1b 0.024536 + 11a-> 25a -1a-> -1a 0.024536 + 10a-> 13a 9b-> 13b 0.024095 + 9a-> 13a 10b-> 13b 0.024095 + 11a-> 25a 11b-> 26b 0.022799 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034590317 + alpha-alpha-alpha ... -0.000875195 ( 2.5%) + alpha-alpha-beta ... -0.016419963 ( 47.5%) + alpha-beta -beta ... -0.016419963 ( 47.5%) + beta -beta -beta ... -0.000875195 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034590317 + +Final correlation energy ... -0.729114694 +E(CCSD) ... -205.405402524 +E(CCSD(T)) ... -205.439992841 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210902460 sqrt= 1.100410133 +W(HF) = 0.825830348 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.298246 0.000000 + 1 N : 0.173528 -0.000000 + 2 O : -0.121646 0.000000 + 3 H : 0.246364 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.846549 s : 3.846549 + pz : 1.268333 p : 4.389104 + px : 1.424280 + py : 1.696491 + dz2 : 0.014898 d : 0.054342 + dxz : 0.011843 + dyz : 0.012253 + dx2y2 : 0.008055 + dxy : 0.007294 + f0 : 0.002071 f : 0.008251 + f+1 : 0.001014 + f-1 : 0.001475 + f+2 : 0.000743 + f-2 : 0.000910 + f+3 : 0.000757 + f-3 : 0.001281 + 1 N s : 3.878613 s : 3.878613 + pz : 0.910698 p : 2.753147 + px : 0.936022 + py : 0.906428 + dz2 : 0.035356 d : 0.165147 + dxz : 0.051731 + dyz : 0.026944 + dx2y2 : 0.024129 + dxy : 0.026987 + f0 : 0.008545 f : 0.029565 + f+1 : 0.003690 + f-1 : 0.005733 + f+2 : 0.003073 + f-2 : 0.003751 + f+3 : 0.002856 + f-3 : 0.001918 + 2 O s : 3.864832 s : 3.864832 + pz : 1.725616 p : 4.162103 + px : 1.178563 + py : 1.257924 + dz2 : 0.010055 d : 0.084689 + dxz : 0.020819 + dyz : 0.009984 + dx2y2 : 0.023297 + dxy : 0.020533 + f0 : 0.001661 f : 0.010022 + f+1 : 0.001365 + f-1 : 0.000926 + f+2 : 0.000988 + f-2 : 0.001261 + f+3 : 0.002407 + f-3 : 0.001414 + 3 H s : 0.644698 s : 0.644698 + pz : 0.022640 p : 0.090855 + px : 0.024107 + py : 0.044108 + dz2 : 0.000953 d : 0.018082 + dxz : 0.006034 + dyz : 0.002001 + dx2y2 : 0.006671 + dxy : 0.002423 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.592433 0.000000 + 1 N : -0.289513 -0.000000 + 2 O : 0.285361 -0.000000 + 3 H : -0.588280 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.135014 s : 3.135014 + pz : 1.213158 p : 3.889968 + px : 1.284704 + py : 1.392106 + dz2 : 0.111504 d : 0.297078 + dxz : 0.071582 + dyz : 0.053228 + dx2y2 : 0.028114 + dxy : 0.032649 + f0 : 0.026465 f : 0.085507 + f+1 : 0.019619 + f-1 : 0.015585 + f+2 : 0.009513 + f-2 : 0.007712 + f+3 : 0.001451 + f-3 : 0.005163 + 1 N s : 3.031800 s : 3.031800 + pz : 0.923370 p : 2.881038 + px : 1.081270 + py : 0.876398 + dz2 : 0.216607 d : 0.943712 + dxz : 0.290697 + dyz : 0.114808 + dx2y2 : 0.144409 + dxy : 0.177192 + f0 : 0.108617 f : 0.432963 + f+1 : 0.064127 + f-1 : 0.055632 + f+2 : 0.044662 + f-2 : 0.050166 + f+3 : 0.056969 + f-3 : 0.052791 + 2 O s : 3.318634 s : 3.318634 + pz : 1.420136 p : 3.910613 + px : 1.334321 + py : 1.156157 + dz2 : 0.054584 d : 0.358724 + dxz : 0.099524 + dyz : 0.022087 + dx2y2 : 0.079193 + dxy : 0.103336 + f0 : 0.015426 f : 0.126668 + f+1 : 0.020190 + f-1 : 0.006844 + f+2 : 0.015733 + f-2 : 0.014011 + f+3 : 0.027095 + f-3 : 0.027368 + 3 H s : 0.626437 s : 0.626437 + pz : 0.143466 p : 0.579772 + px : 0.241156 + py : 0.195150 + dz2 : 0.035146 d : 0.382071 + dxz : 0.104117 + dyz : 0.034311 + dx2y2 : 0.107934 + dxy : 0.100564 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2982 8.0000 -0.2982 2.2096 1.7470 0.4626 + 1 N 6.8265 7.0000 0.1735 2.8445 2.3558 0.4887 + 2 O 8.1216 8.0000 -0.1216 2.1754 1.6771 0.4983 + 3 H 0.7536 1.0000 0.2464 0.9936 0.9204 0.0731 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7594 B( 0-O , 3-H ) : 0.8953 B( 1-N , 2-O ) : 1.5780 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 68.282 sec + +Fock Matrix Formation ... 0.255 sec ( 0.4%) +Initial Guess ... 0.136 sec ( 0.2%) +DIIS Solver ... 2.796 sec ( 4.1%) +State Vector Update ... 0.126 sec ( 0.2%) +Sigma-vector construction ... 48.808 sec ( 71.5%) + <0|H|D> ... 0.005 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.031 sec ( 0.1% of sigma) + (0-ext) ... 0.085 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.031 sec ( 0.1% of sigma) + (2-ext) ... 1.119 sec ( 2.3% of sigma) + (4-ext) ... 28.637 sec ( 58.7% of sigma) + ... 1.684 sec ( 3.5% of sigma) + ... 0.003 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.133 sec ( 0.3% of sigma) + Fock-dressing ... 2.506 sec ( 5.1% of sigma) + (ik|jl)-dressing ... 0.092 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 11.530 sec ( 23.6% of sigma) + Pair energies ... 0.008 sec ( 0.0% of sigma) +Total Time for computing (T) ... 7.555 sec ( 11.1% of ALL) + I/O of integral and amplitudes ... 0.827 sec ( 10.9% of (T)) + External N**7 contributions ... 4.381 sec ( 58.0% of (T)) + Internal N**7 contributions ... 0.342 sec ( 4.5% of (T)) + N**6 triples energy contributions ... 1.744 sec ( 23.1% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.439992841301 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.038.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.038.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.677033, -0.171905 -0.307470) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.76305 -0.15721 -0.89970 +Nuclear contribution : -1.41308 0.39765 0.71053 + ----------------------------------------- +Total Dipole Moment : -0.65003 0.24044 -0.18917 + ----------------------------------------- +Magnitude (a.u.) : 0.71843 +Magnitude (Debye) : 1.82610 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.842455 0.404542 0.363062 +Rotational constants in MHz : 85214.654675 12127.876166 10884.328855 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.312608 -0.385247 0.519615 +x,y,z [Debye]: -0.794587 -0.979220 1.320757 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.677033, -0.171905 -0.307470) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.93424 -0.12287 -0.89375 +Nuclear contribution : -1.41308 0.39765 0.71053 + ----------------------------------------- +Total Dipole Moment : -0.47884 0.27477 -0.18321 + ----------------------------------------- +Magnitude (a.u.) : 0.58169 +Magnitude (Debye) : 1.47853 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.842455 0.404542 0.363062 +Rotational constants in MHz : 85214.654675 12127.876166 10884.328855 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.192185 -0.264721 0.480985 +x,y,z [Debye]: -0.488495 -0.672866 1.222568 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 39 * + * * + * Dihedral ( 2, 1, 0, 3) : 130.90909091 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0399559330 RMS(Int)= 0.0001713649 + Iter 1: RMS(Cart)= 0.0000479486 RMS(Int)= 0.0000007251 + Iter 2: RMS(Cart)= 0.0000002029 RMS(Int)= 0.0000000031 + Iter 3: RMS(Cart)= 0.0000000009 RMS(Int)= 0.0000000000 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4835 0.000000 + 2. B(O 2,N 1) 1.1690 0.000000 + 3. B(H 3,O 0) 0.9721 0.000000 + 4. A(N 1,O 0,H 3) 102.1343 0.000000 + 5. A(O 0,N 1,O 2) 110.3864 0.000000 + 6. D(O 2,N 1,O 0,H 3) 130.9091 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.299409 -0.093482 0.758860 + N 0.195200 -0.313692 -0.622296 + O 1.279147 0.108356 -0.738816 + H -1.174937 0.298818 0.602253 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.565800 -0.176655 1.434037 + 1 N 7.0000 0 14.007 0.368875 -0.592791 -1.175969 + 2 O 8.0000 0 15.999 2.417237 0.204763 -1.396160 + 3 H 1.0000 0 1.008 -2.220310 0.564684 1.138093 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.483316793364 0.00000000 0.00000000 + O 2 1 0 1.166949212869 110.45515866 0.00000000 + H 1 2 3 0.969332238462 102.19221724 122.72727267 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.803062509304 0.00000000 0.00000000 + O 2 1 0 2.205214424517 110.45515866 0.00000000 + H 1 2 3 1.831772463474 102.19221724 122.72727267 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2224 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2688 + la=0 lb=0: 547 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 391 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.600223110354 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.6002231104 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.974e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7074695090 0.000000000000 0.00161209 0.00005335 0.0198921 0.7000 + 1 -204.7083824246 -0.000912915602 0.00157241 0.00004846 0.0164594 0.7000 + ***Turning on DIIS*** + 2 -204.7091633889 -0.000780964317 0.00435947 0.00013188 0.0133717 0.0000 + 3 -204.7123273658 -0.003163976942 0.00181433 0.00005587 0.0051412 0.0000 + 4 -204.7111114712 0.001215894640 0.00084665 0.00002724 0.0019975 0.0000 + 5 -204.7127379283 -0.001626457116 0.00068485 0.00002223 0.0010983 0.0000 + 6 -204.7118634062 0.000874522140 0.00070065 0.00002637 0.0006644 0.0000 + 7 -204.7116602715 0.000203134650 0.00034064 0.00001298 0.0002971 0.0000 + 8 -204.7123249930 -0.000664721455 0.00017561 0.00000758 0.0002123 0.0000 + 9 -204.7119105852 0.000414407822 0.00014606 0.00000566 0.0001337 0.0000 + 10 -204.7121194653 -0.000208880113 0.00006298 0.00000230 0.0000579 0.0000 + 11 -204.7121159483 0.000003517007 0.00001968 0.00000061 0.0000297 0.0000 + 12 -204.7120593605 0.000056587746 0.00000623 0.00000024 0.0000107 0.0000 + 13 -204.7120810373 -0.000021676808 0.00000251 0.00000008 0.0000025 0.0000 + 14 -204.7120756240 0.000005413284 0.00000115 0.00000003 0.0000021 0.0000 + 15 -204.7120767832 -0.000001159190 0.00000067 0.00000002 0.0000015 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 16 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71207859 Eh -5570.49886 eV + +Components: +Nuclear Repulsion : 68.60022311 Eh 1866.70697 eV +Electronic Energy : -273.31230170 Eh -7437.20583 eV +One Electron Energy: -416.92827241 Eh -11345.19507 eV +Two Electron Energy: 143.61597071 Eh 3907.98924 eV + +Virial components: +Potential Energy : -408.92408768 Eh -11127.39013 eV +Kinetic Energy : 204.21200909 Eh 5556.89127 eV +Virial Ratio : 2.00244878 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.8055e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.8909e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.7047e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.5248e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.683368 -562.8230 + 1 1.0000 -20.624589 -561.2236 + 2 1.0000 -15.803422 -430.0330 + 3 1.0000 -1.610739 -43.8304 + 4 1.0000 -1.380212 -37.5575 + 5 1.0000 -0.950998 -25.8780 + 6 1.0000 -0.772980 -21.0339 + 7 1.0000 -0.728640 -19.8273 + 8 1.0000 -0.692478 -18.8433 + 9 1.0000 -0.612836 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2.5065 + 15 0.0000 0.099903 2.7185 + 16 0.0000 0.118692 3.2298 + 17 0.0000 0.151735 4.1289 + 18 0.0000 0.157097 4.2748 + 19 0.0000 0.172845 4.7034 + 20 0.0000 0.186238 5.0678 + 21 0.0000 0.191354 5.2070 + 22 0.0000 0.202644 5.5142 + 23 0.0000 0.236138 6.4256 + 24 0.0000 0.269575 7.3355 + 25 0.0000 0.279889 7.6162 + 26 0.0000 0.307848 8.3770 + 27 0.0000 0.328444 8.9374 + 28 0.0000 0.345597 9.4042 + 29 0.0000 0.361407 9.8344 + 30 0.0000 0.423736 11.5304 + 31 0.0000 0.513574 13.9751 + 32 0.0000 0.517866 14.0918 + 33 0.0000 0.544639 14.8204 + 34 0.0000 0.570758 15.5311 + 35 0.0000 0.609719 16.5913 + 36 0.0000 0.631714 17.1898 + 37 0.0000 0.648218 17.6389 + 38 0.0000 0.700403 19.0589 + 39 0.0000 0.722661 19.6646 + 40 0.0000 0.733972 19.9724 + 41 0.0000 0.742024 20.1915 + 42 0.0000 0.779024 21.1983 + 43 0.0000 0.793308 21.5870 + 44 0.0000 0.801821 21.8187 + 45 0.0000 0.824639 22.4396 + 46 0.0000 0.845300 23.0018 + 47 0.0000 0.860203 23.4073 + 48 0.0000 0.921530 25.0761 + 49 0.0000 0.946515 25.7560 + 50 0.0000 0.960724 26.1426 + 51 0.0000 1.005876 27.3713 + 52 0.0000 1.012759 27.5586 + 53 0.0000 1.023879 27.8612 + 54 0.0000 1.045767 28.4568 + 55 0.0000 1.091238 29.6941 + 56 0.0000 1.146533 31.1987 + 57 0.0000 1.211871 32.9767 + 58 0.0000 1.253817 34.1181 + 59 0.0000 1.305621 35.5278 + 60 0.0000 1.365155 37.1478 + 61 0.0000 1.410941 38.3936 + 62 0.0000 1.446306 39.3560 + 63 0.0000 1.510195 41.0945 + 64 0.0000 1.537352 41.8335 + 65 0.0000 1.549875 42.1742 + 66 0.0000 1.560245 42.4564 + 67 0.0000 1.634168 44.4680 + 68 0.0000 1.663913 45.2774 + 69 0.0000 1.706406 46.4337 + 70 0.0000 1.779040 48.4101 + 71 0.0000 1.794625 48.8342 + 72 0.0000 1.880322 51.1662 + 73 0.0000 1.930863 52.5414 + 74 0.0000 1.959231 53.3134 + 75 0.0000 2.026894 55.1546 + 76 0.0000 2.051999 55.8377 + 77 0.0000 2.092136 56.9299 + 78 0.0000 2.158809 58.7442 + 79 0.0000 2.193470 59.6874 + 80 0.0000 2.269331 61.7516 + 81 0.0000 2.284466 62.1635 + 82 0.0000 2.309999 62.8583 + 83 0.0000 2.377350 64.6910 + 84 0.0000 2.427706 66.0612 + 85 0.0000 2.461803 66.9891 + 86 0.0000 2.476104 67.3782 + 87 0.0000 2.484299 67.6012 + 88 0.0000 2.509890 68.2976 + 89 0.0000 2.532363 68.9091 + 90 0.0000 2.569076 69.9081 + 91 0.0000 2.605006 70.8858 + 92 0.0000 2.666140 72.5494 + 93 0.0000 2.694795 73.3291 + 94 0.0000 2.734117 74.3991 + 95 0.0000 2.798918 76.1624 + 96 0.0000 2.813509 76.5595 + 97 0.0000 2.885408 78.5159 + 98 0.0000 2.956135 80.4405 + 99 0.0000 3.046070 82.8878 + 100 0.0000 3.096905 84.2711 + 101 0.0000 3.167134 86.1821 + 102 0.0000 3.256133 88.6039 + 103 0.0000 3.477025 94.6147 + 104 0.0000 3.731132 101.5293 + 105 0.0000 3.860305 105.0442 + 106 0.0000 4.040728 109.9538 + 107 0.0000 4.156897 113.1149 + 108 0.0000 4.199293 114.2686 + 109 0.0000 4.301724 117.0559 + 110 0.0000 4.358581 118.6030 + 111 0.0000 4.384754 119.3152 + 112 0.0000 4.554095 123.9232 + 113 0.0000 4.621760 125.7645 + 114 0.0000 4.723641 128.5368 + 115 0.0000 4.737325 128.9092 + 116 0.0000 4.778422 130.0275 + 117 0.0000 4.883218 132.8791 + 118 0.0000 4.943929 134.5311 + 119 0.0000 4.981767 135.5608 + 120 0.0000 5.066176 137.8576 + 121 0.0000 5.091546 138.5480 + 122 0.0000 5.168056 140.6299 + 123 0.0000 5.198875 141.4686 + 124 0.0000 5.243837 142.6921 + 125 0.0000 5.325505 144.9144 + 126 0.0000 5.375051 146.2626 + 127 0.0000 5.392643 146.7413 + 128 0.0000 5.533331 150.5696 + 129 0.0000 5.701836 155.1549 + 130 0.0000 5.781278 157.3166 + 131 0.0000 5.965282 162.3236 + 132 0.0000 6.140447 167.0900 + 133 0.0000 6.397805 174.0931 + 134 0.0000 6.491542 176.6438 + 135 0.0000 6.504648 177.0005 + 136 0.0000 6.700149 182.3203 + 137 0.0000 6.705386 182.4628 + 138 0.0000 6.755164 183.8174 + 139 0.0000 6.822446 185.6482 + 140 0.0000 6.871272 186.9768 + 141 0.0000 7.056159 192.0079 + 142 0.0000 7.114926 193.6070 + 143 0.0000 7.137986 194.2345 + 144 0.0000 7.189867 195.6462 + 145 0.0000 7.240948 197.0362 + 146 0.0000 7.268209 197.7780 + 147 0.0000 7.352686 200.0768 + 148 0.0000 7.398326 201.3187 + 149 0.0000 7.439113 202.4285 + 150 0.0000 7.471923 203.3214 + 151 0.0000 7.546117 205.3403 + 152 0.0000 7.603069 206.8900 + 153 0.0000 7.616952 207.2678 + 154 0.0000 7.848522 213.5691 + 155 0.0000 7.899979 214.9693 + 156 0.0000 7.970177 216.8795 + 157 0.0000 8.372163 227.8181 + 158 0.0000 14.044682 382.1752 + 159 0.0000 14.778076 402.1319 + 160 0.0000 16.105019 438.2399 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.370851 0.000000 + 1 N : 0.354371 0.000000 + 2 O : -0.248256 0.000000 + 3 H : 0.264736 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.871637 s : 3.871637 + pz : 1.282211 p : 4.471970 + px : 1.412427 + py : 1.777333 + dz2 : 0.010079 d : 0.022771 + dxz : 0.005813 + dyz : 0.005307 + dx2y2 : 0.001188 + dxy : 0.000384 + f0 : 0.001860 f : 0.004473 + f+1 : 0.000531 + f-1 : 0.000987 + f+2 : 0.000116 + f-2 : 0.000221 + f+3 : 0.000149 + f-3 : 0.000608 + 1 N s : 3.826133 s : 3.826133 + pz : 0.874920 p : 2.654557 + px : 0.951682 + py : 0.827955 + dz2 : 0.029503 d : 0.134828 + dxz : 0.042843 + dyz : 0.017618 + dx2y2 : 0.019451 + dxy : 0.025413 + f0 : 0.008917 f : 0.030112 + f+1 : 0.004044 + f-1 : 0.005733 + f+2 : 0.002886 + f-2 : 0.003065 + f+3 : 0.003465 + f-3 : 0.002002 + 2 O s : 3.879024 s : 3.879024 + pz : 1.823682 p : 4.297651 + px : 1.187905 + py : 1.286064 + dz2 : 0.004895 d : 0.063928 + dxz : 0.014242 + dyz : 0.002725 + dx2y2 : 0.020659 + dxy : 0.021408 + f0 : 0.001186 f : 0.007653 + f+1 : 0.000935 + f-1 : 0.000442 + f+2 : 0.000604 + f-2 : 0.000597 + f+3 : 0.002457 + f-3 : 0.001432 + 3 H s : 0.631507 s : 0.631507 + pz : 0.018888 p : 0.082656 + px : 0.024238 + py : 0.039531 + dz2 : 0.000648 d : 0.021100 + dxz : 0.007458 + dyz : 0.001726 + dx2y2 : 0.006572 + dxy : 0.004696 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.581034 0.000000 + 1 N : -0.242322 0.000000 + 2 O : 0.242957 0.000000 + 3 H : -0.581669 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.131763 s : 3.131763 + pz : 1.213900 p : 3.941264 + px : 1.284404 + py : 1.442960 + dz2 : 0.108420 d : 0.267202 + dxz : 0.064632 + dyz : 0.046246 + dx2y2 : 0.025252 + dxy : 0.022652 + f0 : 0.026256 f : 0.078736 + f+1 : 0.018325 + f-1 : 0.014162 + f+2 : 0.008693 + f-2 : 0.006432 + f+3 : 0.000961 + f-3 : 0.003908 + 1 N s : 3.027456 s : 3.027456 + pz : 0.912198 p : 2.837241 + px : 1.112714 + py : 0.812328 + dz2 : 0.210462 d : 0.935045 + dxz : 0.299356 + dyz : 0.107815 + dx2y2 : 0.149560 + dxy : 0.167851 + f0 : 0.112809 f : 0.442580 + f+1 : 0.065265 + f-1 : 0.057098 + f+2 : 0.054502 + f-2 : 0.044437 + f+3 : 0.055951 + f-3 : 0.052518 + 2 O s : 3.317668 s : 3.317668 + pz : 1.484694 p : 3.992601 + px : 1.356354 + py : 1.151554 + dz2 : 0.048264 d : 0.328976 + dxz : 0.101193 + dyz : 0.012690 + dx2y2 : 0.077858 + dxy : 0.088971 + f0 : 0.014966 f : 0.117798 + f+1 : 0.020284 + f-1 : 0.005193 + f+2 : 0.018315 + f-2 : 0.010259 + f+3 : 0.022343 + f-3 : 0.026437 + 3 H s : 0.625293 s : 0.625293 + pz : 0.140479 p : 0.563937 + px : 0.242805 + py : 0.180652 + dz2 : 0.034376 d : 0.392439 + dxz : 0.114285 + dyz : 0.028023 + dx2y2 : 0.108181 + dxy : 0.107574 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3709 8.0000 -0.3709 1.8720 1.8720 -0.0000 + 1 N 6.6456 7.0000 0.3544 2.5670 2.5670 -0.0000 + 2 O 8.2483 8.0000 -0.2483 1.7784 1.7784 -0.0000 + 3 H 0.7353 1.0000 0.2647 0.9633 0.9633 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8537 B( 0-O , 3-H ) : 0.9601 B( 1-N , 2-O ) : 1.7151 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 3 sec + +Total time .... 3.065 sec +Sum of individual times .... 2.697 sec ( 88.0%) + +Fock matrix formation .... 2.191 sec ( 71.5%) +Diagonalization .... 0.206 sec ( 6.7%) +Density matrix formation .... 0.015 sec ( 0.5%) +Population analysis .... 0.108 sec ( 3.5%) +Initial guess .... 0.010 sec ( 0.3%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.006 sec ( 0.2%) +DIIS solution .... 0.167 sec ( 5.4%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.243 sec +Reference energy ... -204.712078210 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.599 sec +AO-integral generation ... 0.157 sec +Half transformation ... 0.086 sec +K-integral sorting ... 5.540 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.026 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) + 277134 b 0 skpd 0.038 s ( 0.000 ms/b) +: : 151164 b 0 skpd 0.045 s ( 0.000 ms/b) + 159120 b 0 skpd 0.017 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.037 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.032 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.025 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.042 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.025 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.380 sec +AO-integral generation ... 0.272 sec +Half transformation ... 0.043 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.157 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.262 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090427534 +EMP2(bb)= -0.090427534 +EMP2(ab)= -0.517982282 + +Initial guess performed in 0.136 sec +E(0) ... -204.712078210 +E(MP2) ... -0.698837350 +Initial E(tot) ... -205.410915561 + ... 0.190072375 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.410915561 -0.698837350 -0.000000000 0.021541763 3.23 0.000002429 + *** Turning on DIIS *** + 1 -205.381620466 -0.669542256 0.029295095 0.009455760 4.78 0.057376685 + 2 -205.401346436 -0.689268226 -0.019725970 0.004444182 4.93 0.060199664 + 3 -205.405167699 -0.693089489 -0.003821263 0.001969331 3.47 0.074264985 + 4 -205.406751425 -0.694673215 -0.001583726 0.001683005 3.16 0.080842444 + 5 -205.407306669 -0.695228458 -0.000555243 0.001000636 3.34 0.086358844 + 6 -205.407416840 -0.695338629 -0.000110171 0.000631245 3.19 0.089233051 + 7 -205.407465774 -0.695387564 -0.000048935 0.000292893 3.24 0.090696511 + 8 -205.407479723 -0.695401512 -0.000013949 0.000154288 3.09 0.091306248 + 9 -205.407475354 -0.695397144 0.000004369 0.000048268 3.11 0.091504612 + 10 -205.407481406 -0.695403196 -0.000006052 0.000032776 3.32 0.091577990 + 11 -205.407477969 -0.695399759 0.000003438 0.000024976 3.18 0.091570300 + 12 -205.407479690 -0.695401480 -0.000001721 0.000017941 3.14 0.091588011 + 13 -205.407479439 -0.695401229 0.000000251 0.000011290 3.63 0.091581999 + 14 -205.407479839 -0.695401628 -0.000000399 0.000006424 3.65 0.091587547 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.712078210 +E(CORR) ... -0.695401628 +E(TOT) ... -205.407479839 +Singles norm **1/2 ... 0.091587547 ( 0.045793774, 0.045793774) +T1 diagnostic ... 0.021587392 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.055307 + 9a-> 13a 9b-> 13b 0.041916 + 9a-> 13a 8b-> 13b 0.040062 + 8a-> 13a 9b-> 13b 0.040062 + 10a-> 13a -1a-> -1a 0.034291 + 10b-> 13b -1b-> -1b 0.034291 + 11a-> 25a 11b-> 25b 0.033725 + 8a-> 13a -1a-> -1a 0.032949 + 8b-> 13b -1b-> -1b 0.032949 + 5a-> 13a 5b-> 13b 0.028655 + 11a-> 13a 11b-> 13b 0.027584 + 11a-> 25a -1a-> -1a 0.026431 + 11b-> 25b -1b-> -1b 0.026431 + 9a-> 13a 10b-> 13b 0.025737 + 10a-> 13a 9b-> 13b 0.025737 + 10a-> 13a 10b-> 13b 0.025616 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034907776 + alpha-alpha-alpha ... -0.000885094 ( 2.5%) + alpha-alpha-beta ... -0.016568794 ( 47.5%) + alpha-beta -beta ... -0.016568794 ( 47.5%) + beta -beta -beta ... -0.000885094 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034907776 + +Final correlation energy ... -0.730309405 +E(CCSD) ... -205.407479839 +E(CCSD(T)) ... -205.442387615 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.212476105 sqrt= 1.101124927 +W(HF) = 0.824758522 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.295666 0.000000 + 1 N : 0.170911 -0.000000 + 2 O : -0.126770 -0.000000 + 3 H : 0.251525 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.848329 s : 3.848329 + pz : 1.270561 p : 4.384544 + px : 1.398568 + py : 1.715415 + dz2 : 0.014780 d : 0.054533 + dxz : 0.011479 + dyz : 0.012696 + dx2y2 : 0.008333 + dxy : 0.007244 + f0 : 0.002093 f : 0.008260 + f+1 : 0.000974 + f-1 : 0.001532 + f+2 : 0.000769 + f-2 : 0.000871 + f+3 : 0.000792 + f-3 : 0.001229 + 1 N s : 3.879199 s : 3.879199 + pz : 0.914515 p : 2.755323 + px : 0.949262 + py : 0.891545 + dz2 : 0.035617 d : 0.165210 + dxz : 0.052837 + dyz : 0.026424 + dx2y2 : 0.021641 + dxy : 0.028691 + f0 : 0.008572 f : 0.029357 + f+1 : 0.003769 + f-1 : 0.005745 + f+2 : 0.003262 + f-2 : 0.003318 + f+3 : 0.002664 + f-3 : 0.002028 + 2 O s : 3.865855 s : 3.865855 + pz : 1.735705 p : 4.165915 + px : 1.175241 + py : 1.254969 + dz2 : 0.010036 d : 0.084911 + dxz : 0.021869 + dyz : 0.009037 + dx2y2 : 0.021261 + dxy : 0.022708 + f0 : 0.001664 f : 0.010088 + f+1 : 0.001403 + f-1 : 0.000900 + f+2 : 0.001153 + f-2 : 0.001127 + f+3 : 0.002262 + f-3 : 0.001580 + 3 H s : 0.641736 s : 0.641736 + pz : 0.022489 p : 0.088676 + px : 0.020621 + py : 0.045567 + dz2 : 0.000830 d : 0.018062 + dxz : 0.006643 + dyz : 0.001567 + dx2y2 : 0.005305 + dxy : 0.003718 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.592825 0.000000 + 1 N : -0.290388 0.000000 + 2 O : 0.281037 -0.000000 + 3 H : -0.583474 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.137307 s : 3.137307 + pz : 1.214930 p : 3.885895 + px : 1.276040 + py : 1.394925 + dz2 : 0.114800 d : 0.298312 + dxz : 0.070624 + dyz : 0.051789 + dx2y2 : 0.032041 + dxy : 0.029058 + f0 : 0.027467 f : 0.085661 + f+1 : 0.020018 + f-1 : 0.015198 + f+2 : 0.009293 + f-2 : 0.007242 + f+3 : 0.001611 + f-3 : 0.004832 + 1 N s : 3.032351 s : 3.032351 + pz : 0.927774 p : 2.881634 + px : 1.104774 + py : 0.849085 + dz2 : 0.217331 d : 0.944301 + dxz : 0.297520 + dyz : 0.109925 + dx2y2 : 0.150042 + dxy : 0.169484 + f0 : 0.110307 f : 0.432101 + f+1 : 0.065350 + f-1 : 0.055223 + f+2 : 0.050732 + f-2 : 0.042158 + f+3 : 0.055563 + f-3 : 0.052768 + 2 O s : 3.319919 s : 3.319919 + pz : 1.427876 p : 3.914422 + px : 1.349005 + py : 1.137541 + dz2 : 0.054022 d : 0.358303 + dxz : 0.103361 + dyz : 0.019049 + dx2y2 : 0.085401 + dxy : 0.096469 + f0 : 0.015597 f : 0.126320 + f+1 : 0.020915 + f-1 : 0.005776 + f+2 : 0.018356 + f-2 : 0.011514 + f+3 : 0.026390 + f-3 : 0.027771 + 3 H s : 0.626135 s : 0.626135 + pz : 0.141506 p : 0.575365 + px : 0.246846 + py : 0.187013 + dz2 : 0.035795 d : 0.381973 + dxz : 0.110320 + dyz : 0.026947 + dx2y2 : 0.104692 + dxy : 0.104219 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2957 8.0000 -0.2957 2.2338 1.7678 0.4660 + 1 N 6.8291 7.0000 0.1709 2.8457 2.3569 0.4888 + 2 O 8.1268 8.0000 -0.1268 2.1732 1.6739 0.4993 + 3 H 0.7485 1.0000 0.2515 0.9861 0.9131 0.0731 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7774 B( 0-O , 3-H ) : 0.8936 B( 1-N , 2-O ) : 1.5686 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 69.378 sec + +Fock Matrix Formation ... 0.243 sec ( 0.3%) +Initial Guess ... 0.136 sec ( 0.2%) +DIIS Solver ... 2.773 sec ( 4.0%) +State Vector Update ... 0.176 sec ( 0.3%) +Sigma-vector construction ... 49.507 sec ( 71.4%) + <0|H|D> ... 0.005 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (0-ext) ... 0.075 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.028 sec ( 0.1% of sigma) + (2-ext) ... 1.056 sec ( 2.1% of sigma) + (4-ext) ... 28.595 sec ( 57.8% of sigma) + ... 1.910 sec ( 3.9% of sigma) + ... 0.003 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.136 sec ( 0.3% of sigma) + Fock-dressing ... 2.527 sec ( 5.1% of sigma) + (ik|jl)-dressing ... 0.084 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 12.065 sec ( 24.4% of sigma) + Pair energies ... 0.009 sec ( 0.0% of sigma) +Total Time for computing (T) ... 7.989 sec ( 11.5% of ALL) + I/O of integral and amplitudes ... 0.835 sec ( 10.5% of (T)) + External N**7 contributions ... 4.048 sec ( 50.7% of (T)) + Internal N**7 contributions ... 0.318 sec ( 4.0% of (T)) + N**6 triples energy contributions ... 1.715 sec ( 21.5% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.442387615062 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.004278565 -0.008493565 0.002268135 + 2 N : 0.002626942 -0.009818856 0.000652003 + 3 O : 0.000257187 0.008521892 -0.002897818 + 4 H : 0.001394437 0.009790528 -0.000022321 + +Norm of the cartesian gradient ... 0.019447689 +RMS gradient ... 0.005614064 +MAX gradient ... 0.009818856 + +------- +TIMINGS +------- + +Total numerical gradient time ... 403.510 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 104.66 cm**-1 + 7: 568.01 cm**-1 + 8: 781.24 cm**-1 + 9: 1203.01 cm**-1 + 10: 1706.56 cm**-1 + 11: 3733.16 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 0.052275 -0.325996 0.097184 -0.050779 -0.000985 -0.056751 + 1 0.045716 0.001593 0.134554 0.002055 -0.016017 0.024778 + 2 -0.046626 0.415984 0.150887 -0.064790 -0.097633 -0.009262 + 3 -0.047428 0.207495 0.008682 0.016273 0.659526 -0.001148 + 4 0.070691 0.103432 -0.161186 -0.019181 0.281336 -0.001032 + 5 0.030801 -0.141126 -0.508570 0.044697 0.047090 -0.000145 + 6 0.012948 0.174254 -0.094862 0.048449 -0.574798 0.000769 + 7 -0.049861 -0.057877 0.020713 0.009444 -0.231148 0.000928 + 8 0.018559 -0.286099 0.249003 -0.035558 0.037740 -0.000165 + 9 -0.376167 -0.474861 -0.157512 -0.189147 -0.025808 0.904498 + 10 -0.916516 -0.543929 -0.224582 0.084028 0.013614 -0.393654 + 11 0.017478 -0.100470 0.719935 0.971623 0.296261 0.151643 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 104.66 0.036188 182.88 0.107904 (-0.206713 -0.214839 0.137907) + 7: 568.01 0.021788 110.11 0.011970 ( 0.065344 -0.021124 -0.085171) + 8: 781.24 0.015928 80.49 0.006362 ( 0.044332 -0.016347 -0.064263) + 9: 1203.01 0.023536 118.94 0.006105 (-0.037062 0.016405 0.066803) + 10: 1706.56 0.030730 155.30 0.005619 ( 0.057303 0.006888 -0.047835) + 11: 3733.16 0.013475 68.10 0.001126 ( 0.029873 -0.011881 -0.009637) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 104.66 E(vib) ... 0.46 +freq. 568.01 E(vib) ... 0.11 +freq. 781.24 E(vib) ... 0.05 +freq. 1203.01 E(vib) ... 0.01 +freq. 1706.56 E(vib) ... 0.00 +freq. 3733.16 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.44238762 Eh +Zero point energy ... 0.01844548 Eh 11.57 kcal/mol +Thermal vibrational correction ... 0.00100685 Eh 0.63 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42010275 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00383939 Eh 2.41 kcal/mol +Non-thermal (ZPE) correction 0.01844548 Eh 11.57 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02228487 Eh 13.98 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42010275 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.41915854 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.866998 0.403856 0.361109 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00184863 Eh 1.16 kcal/mol +Rotational entropy ... 0.00992248 Eh 6.23 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02957342 Eh 18.56 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00992248 Eh 6.23 kcal/mol| +| sn= 2 | S(rot)= 0.00926802 Eh 5.82 kcal/mol| +| sn= 3 | S(rot)= 0.00888519 Eh 5.58 kcal/mol| +| sn= 4 | S(rot)= 0.00861356 Eh 5.41 kcal/mol| +| sn= 5 | S(rot)= 0.00840288 Eh 5.27 kcal/mol| +| sn= 6 | S(rot)= 0.00823073 Eh 5.16 kcal/mol| +| sn= 7 | S(rot)= 0.00808518 Eh 5.07 kcal/mol| +| sn= 8 | S(rot)= 0.00795911 Eh 4.99 kcal/mol| +| sn= 9 | S(rot)= 0.00784790 Eh 4.92 kcal/mol| +| sn=10 | S(rot)= 0.00774842 Eh 4.86 kcal/mol| +| sn=11 | S(rot)= 0.00765843 Eh 4.81 kcal/mol| +| sn=12 | S(rot)= 0.00757627 Eh 4.75 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.41915854 Eh +Total entropy correction ... -0.02957342 Eh -18.56 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.44873196 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00634435 Eh -3.98 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.442387616 Eh +Current gradient norm .... 0.019447688 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + -0.000344134 0.106488528 0.158709236 0.484475389 0.506130398 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999728451 +Lowest eigenvalues of augmented Hessian: + -0.000091216 0.104265110 0.158018079 0.484478861 0.506038379 +Length of the computed step .... 0.023309209 +The final length of the internal step .... 0.023309209 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0095159447 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0063891877 RMS(Int)= 0.0095143594 + Iter 1: RMS(Cart)= 0.0000036976 RMS(Int)= 0.0000060851 + Iter 2: RMS(Cart)= 0.0000000261 RMS(Int)= 0.0000000300 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0023004540 0.0001000000 NO + MAX gradient 0.0036040220 0.0003000000 NO + RMS step 0.0095159447 0.0020000000 NO + MAX step 0.0226159586 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0120 Max(Angles) 0.07 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4835 0.003245 -0.0120 1.4715 + 2. B(O 2,N 1) 1.1690 0.003604 -0.0006 1.1685 + 3. B(H 3,O 0) 0.9721 0.002698 -0.0028 0.9693 + 4. A(N 1,O 0,H 3) 102.13 0.000754 -0.02 102.12 + 5. A(O 0,N 1,O 2) 110.39 0.000619 0.07 110.46 + 6. D(O 2,N 1,O 0,H 3) 130.91 -0.017074 -0.00 130.91 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.296944 -0.093926 0.753987 + N 0.191669 -0.312312 -0.616751 + O 1.275156 0.108542 -0.736074 + H -1.169879 0.297697 0.598837 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.561144 -0.177495 1.424829 + 1 N 7.0000 0 14.007 0.362201 -0.590185 -1.165490 + 2 O 8.0000 0 15.999 2.409695 0.205114 -1.390978 + 3 H 1.0000 0 1.008 -2.210751 0.562566 1.131639 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.471515206253 0.00000000 0.00000000 + O 2 1 0 1.168460709517 110.46118262 0.00000000 + H 1 2 3 0.969255189961 102.11682626 130.90909107 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.780760741719 0.00000000 0.00000000 + O 2 1 0 2.208070739235 110.46118262 0.00000000 + H 1 2 3 1.831626862909 102.11682626 130.90909107 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2224 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2688 + la=0 lb=0: 547 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 391 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.876250245366 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.951e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7133864918 0.000000000000 0.00044888 0.00000918 0.0020556 0.7000 + 1 -204.7134016898 -0.000015198023 0.00033843 0.00000760 0.0015816 0.7000 + ***Turning on DIIS*** + 2 -204.7134142661 -0.000012576318 0.00079440 0.00001951 0.0012028 0.0000 + 3 -204.7127504418 0.000663824385 0.00030595 0.00000818 0.0002909 0.0000 + 4 -204.7135144270 -0.000763985212 0.00009872 0.00000264 0.0001173 0.0000 + 5 -204.7138047258 -0.000290298824 0.00003472 0.00000105 0.0000517 0.0000 + 6 -204.7133057939 0.000498931920 0.00001879 0.00000063 0.0000320 0.0000 + 7 -204.7134464955 -0.000140701672 0.00000950 0.00000038 0.0000150 0.0000 + 8 -204.7134581992 -0.000011703640 0.00000925 0.00000032 0.0000088 0.0000 + 9 -204.7134281288 0.000030070386 0.00000664 0.00000028 0.0000056 0.0000 + 10 -204.7134665896 -0.000038460805 0.00000324 0.00000013 0.0000031 0.0000 + 11 -204.7134540452 0.000012544433 0.00000163 0.00000006 0.0000015 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + +Total Energy : -204.71345443 Eh -5570.53630 eV + Last Energy change ... -3.8238e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.8736e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.225 sec +Reference energy ... -204.713455493 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.360 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.375 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.024 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.037 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.345 sec +AO-integral generation ... 0.242 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.049 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.143 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.249 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090266829 +EMP2(bb)= -0.090266829 +EMP2(ab)= -0.516929271 + +Initial guess performed in 0.132 sec +E(0) ... -204.713455493 +E(MP2) ... -0.697462929 +Initial E(tot) ... -205.410918422 + ... 0.188762010 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.410918422 -0.697462929 -0.000000000 0.021511355 2.74 0.000001142 + *** Turning on DIIS *** + 1 -205.382266240 -0.668810748 0.028652181 0.009153687 2.72 0.056794393 + 2 -205.401767323 -0.688311831 -0.019501083 0.004454799 3.08 0.059724292 + 3 -205.405549031 -0.692093539 -0.003781708 0.001921661 2.83 0.073619677 + 4 -205.407107140 -0.693651648 -0.001558109 0.001634254 2.87 0.080112325 + 5 -205.407647679 -0.694192187 -0.000540539 0.000971653 2.86 0.085502074 + 6 -205.407754995 -0.694299502 -0.000107316 0.000608841 2.92 0.088288028 + 7 -205.407801618 -0.694346125 -0.000046623 0.000283605 2.92 0.089673360 + 8 -205.407814570 -0.694359078 -0.000012952 0.000148236 2.92 0.090247467 + 9 -205.407810342 -0.694354850 0.000004228 0.000046229 2.82 0.090432127 + 10 -205.407815971 -0.694360478 -0.000005629 0.000031850 2.81 0.090500050 + 11 -205.407812747 -0.694357255 0.000003224 0.000024314 2.83 0.090492754 + 12 -205.407814379 -0.694358886 -0.000001631 0.000017442 2.87 0.090508806 + 13 -205.407814141 -0.694358649 0.000000237 0.000010838 2.90 0.090503335 + 14 -205.407814521 -0.694359028 -0.000000379 0.000006112 2.89 0.090508497 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.713455493 +E(CORR) ... -0.694359028 +E(TOT) ... -205.407814521 +Singles norm **1/2 ... 0.090508497 ( 0.045254248, 0.045254248) +T1 diagnostic ... 0.021333057 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.053390 + 9a-> 13a 9b-> 13b 0.042251 + 8a-> 13a 9b-> 13b 0.039293 + 9a-> 13a 8b-> 13b 0.039293 + 10a-> 13a -1a-> -1a 0.033139 + 10b-> 13b -1b-> -1b 0.033139 + 8a-> 13a -1a-> -1a 0.033003 + 8b-> 13b -1b-> -1b 0.033003 + 5a-> 13a 5b-> 13b 0.028134 + 11a-> 13a 11b-> 13b 0.027932 + 11a-> 25a 11b-> 25b 0.027287 + 10a-> 13a 10b-> 13b 0.026642 + 10a-> 13a 9b-> 13b 0.026481 + 9a-> 13a 10b-> 13b 0.026481 + 11b-> 25b -1b-> -1b 0.024219 + 11a-> 25a -1a-> -1a 0.024219 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034617807 + alpha-alpha-alpha ... -0.000881616 ( 2.5%) + alpha-alpha-beta ... -0.016427287 ( 47.5%) + alpha-beta -beta ... -0.016427287 ( 47.5%) + beta -beta -beta ... -0.000881616 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034617807 + +Final correlation energy ... -0.728976835 +E(CCSD) ... -205.407814521 +E(CCSD(T)) ... -205.442432328 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210854481 sqrt= 1.100388332 +W(HF) = 0.825863071 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 58.020 sec + +Fock Matrix Formation ... 0.225 sec ( 0.4%) +Initial Guess ... 0.132 sec ( 0.2%) +DIIS Solver ... 1.925 sec ( 3.3%) +State Vector Update ... 0.093 sec ( 0.2%) +Sigma-vector construction ... 40.945 sec ( 70.6%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.024 sec ( 0.1% of sigma) + (0-ext) ... 0.074 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (2-ext) ... 0.997 sec ( 2.4% of sigma) + (4-ext) ... 22.923 sec ( 56.0% of sigma) + ... 1.536 sec ( 3.8% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.114 sec ( 0.3% of sigma) + Fock-dressing ... 2.264 sec ( 5.5% of sigma) + (ik|jl)-dressing ... 0.079 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.106 sec ( 24.7% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.743 sec ( 11.6% of ALL) + I/O of integral and amplitudes ... 0.767 sec ( 11.4% of (T)) + External N**7 contributions ... 3.896 sec ( 57.8% of (T)) + Internal N**7 contributions ... 0.314 sec ( 4.7% of (T)) + N**6 triples energy contributions ... 1.685 sec ( 25.0% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.442432328020 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.005368061 -0.008098855 -0.000750041 + 2 N : 0.004620672 -0.008310751 0.003065262 + 3 O : -0.003251166 0.007479348 -0.002302248 + 4 H : 0.003998555 0.008930258 -0.000012973 + +Norm of the cartesian gradient ... 0.019035081 +RMS gradient ... 0.005494955 +MAX gradient ... 0.008930258 + +------- +TIMINGS +------- + +Total numerical gradient time ... 366.780 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.442432328 Eh +Current gradient norm .... 0.019035081 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999543 +Lowest eigenvalues of augmented Hessian: + -0.000000123 0.106848246 0.159493576 0.482718608 0.504838987 +Length of the computed step .... 0.000955805 +The final length of the internal step .... 0.000955805 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0003902057 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0002432599 RMS(Int)= 0.0003902106 + Iter 1: RMS(Cart)= 0.0000000131 RMS(Int)= 0.0000000198 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000447120 0.0000050000 NO + RMS gradient 0.0000673371 0.0001000000 YES + MAX gradient 0.0001325821 0.0003000000 YES + RMS step 0.0003902057 0.0020000000 YES + MAX step 0.0009544506 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0005 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4715 -0.000133 0.0005 1.4720 + 2. B(O 2,N 1) 1.1685 -0.000086 -0.0000 1.1684 + 3. B(H 3,O 0) 0.9693 0.000009 -0.0000 0.9692 + 4. A(N 1,O 0,H 3) 102.12 -0.000029 0.00 102.12 + 5. A(O 0,N 1,O 2) 110.46 -0.000037 -0.00 110.46 + 6. D(O 2,N 1,O 0,H 3) 130.91 -0.017526 -0.00 130.91 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.297092 -0.093885 0.754189 + N 0.191819 -0.312351 -0.616972 + O 1.275287 0.108525 -0.736178 + H -1.170012 0.297712 0.598961 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.561423 -0.177418 1.425210 + 1 N 7.0000 0 14.007 0.362485 -0.590258 -1.165909 + 2 O 8.0000 0 15.999 2.409943 0.205082 -1.391174 + 3 H 1.0000 0 1.008 -2.211003 0.562594 1.131873 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.472020279738 0.00000000 0.00000000 + O 2 1 0 1.168438782730 110.46007613 0.00000000 + H 1 2 3 0.969243714746 102.11712370 130.90909107 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.781715192283 0.00000000 0.00000000 + O 2 1 0 2.208029303611 110.46007613 0.00000000 + H 1 2 3 1.831605177895 102.11712370 130.90909107 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2224 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2688 + la=0 lb=0: 547 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 391 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.866347406980 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.8663474070 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.952e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7134124903 0.000000000000 0.00001589 0.00000033 0.0000820 0.7000 + 1 -204.7134125183 -0.000000027977 0.00001198 0.00000028 0.0000644 0.7000 + ***Turning on DIIS*** + 2 -204.7134125417 -0.000000023377 0.00002937 0.00000076 0.0000500 0.0000 + 3 -204.7134241793 -0.000011637688 0.00001137 0.00000033 0.0000131 0.0000 + 4 -204.7134076644 0.000016514894 0.00000404 0.00000011 0.0000039 0.0000 + 5 -204.7134079058 -0.000000241318 0.00000163 0.00000004 0.0000016 0.0000 + 6 -204.7134157129 -0.000007807158 0.00000081 0.00000002 0.0000011 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71341297 Eh -5570.53517 eV + +Components: +Nuclear Repulsion : 68.86634741 Eh 1873.94858 eV +Electronic Energy : -273.57976037 Eh -7444.48375 eV +One Electron Energy: -417.44954027 Eh -11359.37949 eV +Two Electron Energy: 143.86977990 Eh 3914.89574 eV + +Virial components: +Potential Energy : -408.95142129 Eh -11128.13392 eV +Kinetic Energy : 204.23800833 Eh 5557.59875 eV +Virial Ratio : 2.00232770 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.7467e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.7651e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.5049e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.6832e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.681104 -562.7615 + 1 1.0000 -20.625809 -561.2568 + 2 1.0000 -15.801683 -429.9856 + 3 1.0000 -1.611266 -43.8448 + 4 1.0000 -1.384549 -37.6755 + 5 1.0000 -0.950608 -25.8674 + 6 1.0000 -0.775245 -21.0955 + 7 1.0000 -0.729171 -19.8417 + 8 1.0000 -0.693930 -18.8828 + 9 1.0000 -0.612549 -16.6683 + 10 1.0000 -0.529508 -14.4087 + 11 1.0000 -0.459564 -12.5054 + 12 0.0000 0.029616 0.8059 + 13 0.0000 0.073520 2.0006 + 14 0.0000 0.092385 2.5139 + 15 0.0000 0.100016 2.7216 + 16 0.0000 0.118483 3.2241 + 17 0.0000 0.151632 4.1261 + 18 0.0000 0.157224 4.2783 + 19 0.0000 0.172808 4.7024 + 20 0.0000 0.186171 5.0660 + 21 0.0000 0.191437 5.2093 + 22 0.0000 0.202962 5.5229 + 23 0.0000 0.236676 6.4403 + 24 0.0000 0.269845 7.3428 + 25 0.0000 0.283612 7.7175 + 26 0.0000 0.309893 8.4326 + 27 0.0000 0.328897 8.9498 + 28 0.0000 0.345679 9.4064 + 29 0.0000 0.361991 9.8503 + 30 0.0000 0.423958 11.5365 + 31 0.0000 0.513696 13.9784 + 32 0.0000 0.518438 14.1074 + 33 0.0000 0.545485 14.8434 + 34 0.0000 0.570939 15.5360 + 35 0.0000 0.610124 16.6023 + 36 0.0000 0.632507 17.2114 + 37 0.0000 0.648345 17.6424 + 38 0.0000 0.700693 19.0668 + 39 0.0000 0.722716 19.6661 + 40 0.0000 0.734528 19.9875 + 41 0.0000 0.742283 20.1985 + 42 0.0000 0.779137 21.2014 + 43 0.0000 0.793857 21.6019 + 44 0.0000 0.801297 21.8044 + 45 0.0000 0.824863 22.4457 + 46 0.0000 0.846276 23.0283 + 47 0.0000 0.861226 23.4351 + 48 0.0000 0.921343 25.0710 + 49 0.0000 0.946889 25.7662 + 50 0.0000 0.960908 26.1476 + 51 0.0000 1.005564 27.3628 + 52 0.0000 1.013517 27.5792 + 53 0.0000 1.024636 27.8818 + 54 0.0000 1.046798 28.4848 + 55 0.0000 1.093010 29.7423 + 56 0.0000 1.147687 31.2302 + 57 0.0000 1.213403 33.0184 + 58 0.0000 1.255749 34.1707 + 59 0.0000 1.306084 35.5404 + 60 0.0000 1.365367 37.1535 + 61 0.0000 1.411763 38.4160 + 62 0.0000 1.445460 39.3330 + 63 0.0000 1.510759 41.1098 + 64 0.0000 1.538693 41.8700 + 65 0.0000 1.550161 42.1820 + 66 0.0000 1.560965 42.4760 + 67 0.0000 1.635781 44.5119 + 68 0.0000 1.665678 45.3254 + 69 0.0000 1.709037 46.5053 + 70 0.0000 1.780833 48.4589 + 71 0.0000 1.796537 48.8862 + 72 0.0000 1.883368 51.2491 + 73 0.0000 1.932552 52.5874 + 74 0.0000 1.960945 53.3600 + 75 0.0000 2.031207 55.2719 + 76 0.0000 2.054833 55.9148 + 77 0.0000 2.095976 57.0344 + 78 0.0000 2.159697 58.7683 + 79 0.0000 2.193423 59.6861 + 80 0.0000 2.272202 61.8298 + 81 0.0000 2.286622 62.2222 + 82 0.0000 2.310782 62.8796 + 83 0.0000 2.376526 64.6686 + 84 0.0000 2.429544 66.1113 + 85 0.0000 2.463700 67.0407 + 86 0.0000 2.477712 67.4220 + 87 0.0000 2.486675 67.6659 + 88 0.0000 2.511278 68.3354 + 89 0.0000 2.536144 69.0120 + 90 0.0000 2.568408 69.8899 + 91 0.0000 2.604369 70.8685 + 92 0.0000 2.667249 72.5795 + 93 0.0000 2.697839 73.4119 + 94 0.0000 2.734528 74.4103 + 95 0.0000 2.802529 76.2607 + 96 0.0000 2.819131 76.7125 + 97 0.0000 2.895945 78.8027 + 98 0.0000 2.961568 80.5884 + 99 0.0000 3.053474 83.0893 + 100 0.0000 3.103956 84.4629 + 101 0.0000 3.166694 86.1701 + 102 0.0000 3.259350 88.6914 + 103 0.0000 3.480319 94.7043 + 104 0.0000 3.735573 101.6501 + 105 0.0000 3.866752 105.2197 + 106 0.0000 4.040647 109.9516 + 107 0.0000 4.159949 113.1980 + 108 0.0000 4.203037 114.3704 + 109 0.0000 4.306998 117.1994 + 110 0.0000 4.361998 118.6960 + 111 0.0000 4.388488 119.4168 + 112 0.0000 4.556806 123.9970 + 113 0.0000 4.624661 125.8434 + 114 0.0000 4.730651 128.7276 + 115 0.0000 4.742136 129.0401 + 116 0.0000 4.783489 130.1654 + 117 0.0000 4.883302 132.8814 + 118 0.0000 4.947098 134.6174 + 119 0.0000 4.983738 135.6144 + 120 0.0000 5.070378 137.9720 + 121 0.0000 5.093436 138.5994 + 122 0.0000 5.172597 140.7535 + 123 0.0000 5.201438 141.5383 + 124 0.0000 5.248574 142.8210 + 125 0.0000 5.331641 145.0813 + 126 0.0000 5.381643 146.4419 + 127 0.0000 5.402499 147.0095 + 128 0.0000 5.540890 150.7753 + 129 0.0000 5.705815 155.2631 + 130 0.0000 5.789000 157.5267 + 131 0.0000 5.978428 162.6813 + 132 0.0000 6.140916 167.1028 + 133 0.0000 6.402530 174.2217 + 134 0.0000 6.493318 176.6922 + 135 0.0000 6.507048 177.0658 + 136 0.0000 6.699825 182.3115 + 137 0.0000 6.706206 182.4851 + 138 0.0000 6.754338 183.7949 + 139 0.0000 6.828677 185.8178 + 140 0.0000 6.878553 187.1749 + 141 0.0000 7.066571 192.2912 + 142 0.0000 7.118509 193.7045 + 143 0.0000 7.142458 194.3562 + 144 0.0000 7.193846 195.7545 + 145 0.0000 7.243123 197.0954 + 146 0.0000 7.272419 197.8926 + 147 0.0000 7.357798 200.2159 + 148 0.0000 7.402966 201.4449 + 149 0.0000 7.446941 202.6416 + 150 0.0000 7.476838 203.4551 + 151 0.0000 7.546653 205.3549 + 152 0.0000 7.614285 207.1952 + 153 0.0000 7.627001 207.5412 + 154 0.0000 7.863254 213.9700 + 155 0.0000 7.902522 215.0386 + 156 0.0000 7.993264 217.5078 + 157 0.0000 8.381929 228.0839 + 158 0.0000 14.078142 383.0857 + 159 0.0000 14.860097 404.3638 + 160 0.0000 16.152880 439.5422 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.681104 -562.7615 + 1 1.0000 -20.625809 -561.2568 + 2 1.0000 -15.801683 -429.9856 + 3 1.0000 -1.611266 -43.8448 + 4 1.0000 -1.384549 -37.6755 + 5 1.0000 -0.950608 -25.8674 + 6 1.0000 -0.775245 -21.0955 + 7 1.0000 -0.729171 -19.8417 + 8 1.0000 -0.693930 -18.8828 + 9 1.0000 -0.612549 -16.6683 + 10 1.0000 -0.529508 -14.4087 + 11 1.0000 -0.459564 -12.5054 + 12 0.0000 0.029616 0.8059 + 13 0.0000 0.073520 2.0006 + 14 0.0000 0.092385 2.5139 + 15 0.0000 0.100016 2.7216 + 16 0.0000 0.118483 3.2241 + 17 0.0000 0.151632 4.1261 + 18 0.0000 0.157224 4.2783 + 19 0.0000 0.172808 4.7024 + 20 0.0000 0.186171 5.0660 + 21 0.0000 0.191437 5.2093 + 22 0.0000 0.202962 5.5229 + 23 0.0000 0.236676 6.4403 + 24 0.0000 0.269845 7.3428 + 25 0.0000 0.283612 7.7175 + 26 0.0000 0.309893 8.4326 + 27 0.0000 0.328897 8.9498 + 28 0.0000 0.345679 9.4064 + 29 0.0000 0.361991 9.8503 + 30 0.0000 0.423958 11.5365 + 31 0.0000 0.513696 13.9784 + 32 0.0000 0.518438 14.1074 + 33 0.0000 0.545485 14.8434 + 34 0.0000 0.570939 15.5360 + 35 0.0000 0.610124 16.6023 + 36 0.0000 0.632507 17.2114 + 37 0.0000 0.648345 17.6424 + 38 0.0000 0.700693 19.0668 + 39 0.0000 0.722716 19.6661 + 40 0.0000 0.734528 19.9875 + 41 0.0000 0.742283 20.1985 + 42 0.0000 0.779137 21.2014 + 43 0.0000 0.793857 21.6019 + 44 0.0000 0.801297 21.8044 + 45 0.0000 0.824863 22.4457 + 46 0.0000 0.846276 23.0283 + 47 0.0000 0.861226 23.4351 + 48 0.0000 0.921343 25.0710 + 49 0.0000 0.946889 25.7662 + 50 0.0000 0.960908 26.1476 + 51 0.0000 1.005564 27.3628 + 52 0.0000 1.013517 27.5792 + 53 0.0000 1.024636 27.8818 + 54 0.0000 1.046798 28.4848 + 55 0.0000 1.093010 29.7423 + 56 0.0000 1.147687 31.2302 + 57 0.0000 1.213403 33.0184 + 58 0.0000 1.255749 34.1707 + 59 0.0000 1.306084 35.5404 + 60 0.0000 1.365367 37.1535 + 61 0.0000 1.411763 38.4160 + 62 0.0000 1.445460 39.3330 + 63 0.0000 1.510759 41.1098 + 64 0.0000 1.538693 41.8700 + 65 0.0000 1.550161 42.1820 + 66 0.0000 1.560965 42.4760 + 67 0.0000 1.635781 44.5119 + 68 0.0000 1.665678 45.3254 + 69 0.0000 1.709037 46.5053 + 70 0.0000 1.780833 48.4589 + 71 0.0000 1.796537 48.8862 + 72 0.0000 1.883368 51.2491 + 73 0.0000 1.932552 52.5874 + 74 0.0000 1.960945 53.3600 + 75 0.0000 2.031207 55.2719 + 76 0.0000 2.054833 55.9148 + 77 0.0000 2.095976 57.0344 + 78 0.0000 2.159697 58.7683 + 79 0.0000 2.193423 59.6861 + 80 0.0000 2.272202 61.8298 + 81 0.0000 2.286622 62.2222 + 82 0.0000 2.310782 62.8796 + 83 0.0000 2.376526 64.6686 + 84 0.0000 2.429544 66.1113 + 85 0.0000 2.463700 67.0407 + 86 0.0000 2.477712 67.4220 + 87 0.0000 2.486675 67.6659 + 88 0.0000 2.511278 68.3354 + 89 0.0000 2.536144 69.0120 + 90 0.0000 2.568408 69.8899 + 91 0.0000 2.604369 70.8685 + 92 0.0000 2.667249 72.5795 + 93 0.0000 2.697839 73.4119 + 94 0.0000 2.734528 74.4103 + 95 0.0000 2.802529 76.2607 + 96 0.0000 2.819131 76.7125 + 97 0.0000 2.895945 78.8027 + 98 0.0000 2.961568 80.5884 + 99 0.0000 3.053474 83.0893 + 100 0.0000 3.103956 84.4629 + 101 0.0000 3.166694 86.1701 + 102 0.0000 3.259350 88.6914 + 103 0.0000 3.480319 94.7043 + 104 0.0000 3.735573 101.6501 + 105 0.0000 3.866752 105.2197 + 106 0.0000 4.040647 109.9516 + 107 0.0000 4.159949 113.1980 + 108 0.0000 4.203037 114.3704 + 109 0.0000 4.306998 117.1994 + 110 0.0000 4.361998 118.6960 + 111 0.0000 4.388488 119.4168 + 112 0.0000 4.556806 123.9970 + 113 0.0000 4.624661 125.8434 + 114 0.0000 4.730651 128.7276 + 115 0.0000 4.742136 129.0401 + 116 0.0000 4.783489 130.1654 + 117 0.0000 4.883302 132.8814 + 118 0.0000 4.947098 134.6174 + 119 0.0000 4.983738 135.6144 + 120 0.0000 5.070378 137.9720 + 121 0.0000 5.093436 138.5994 + 122 0.0000 5.172597 140.7535 + 123 0.0000 5.201438 141.5383 + 124 0.0000 5.248574 142.8210 + 125 0.0000 5.331641 145.0813 + 126 0.0000 5.381643 146.4419 + 127 0.0000 5.402499 147.0095 + 128 0.0000 5.540890 150.7753 + 129 0.0000 5.705815 155.2631 + 130 0.0000 5.789000 157.5267 + 131 0.0000 5.978428 162.6813 + 132 0.0000 6.140916 167.1028 + 133 0.0000 6.402530 174.2217 + 134 0.0000 6.493318 176.6922 + 135 0.0000 6.507048 177.0658 + 136 0.0000 6.699825 182.3115 + 137 0.0000 6.706206 182.4851 + 138 0.0000 6.754338 183.7949 + 139 0.0000 6.828677 185.8178 + 140 0.0000 6.878553 187.1749 + 141 0.0000 7.066571 192.2912 + 142 0.0000 7.118509 193.7045 + 143 0.0000 7.142458 194.3562 + 144 0.0000 7.193846 195.7545 + 145 0.0000 7.243123 197.0954 + 146 0.0000 7.272419 197.8926 + 147 0.0000 7.357798 200.2159 + 148 0.0000 7.402966 201.4449 + 149 0.0000 7.446941 202.6416 + 150 0.0000 7.476838 203.4551 + 151 0.0000 7.546653 205.3549 + 152 0.0000 7.614285 207.1952 + 153 0.0000 7.627001 207.5412 + 154 0.0000 7.863254 213.9700 + 155 0.0000 7.902522 215.0386 + 156 0.0000 7.993264 217.5078 + 157 0.0000 8.381929 228.0839 + 158 0.0000 14.078142 383.0857 + 159 0.0000 14.860097 404.3638 + 160 0.0000 16.152880 439.5422 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.362519 0.000000 + 1 N : 0.351112 0.000000 + 2 O : -0.251615 0.000000 + 3 H : 0.263023 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.869756 s : 3.869756 + pz : 1.280033 p : 4.465509 + px : 1.411072 + py : 1.774404 + dz2 : 0.010064 d : 0.022722 + dxz : 0.005774 + dyz : 0.005479 + dx2y2 : 0.001125 + dxy : 0.000279 + f0 : 0.001906 f : 0.004533 + f+1 : 0.000530 + f-1 : 0.001013 + f+2 : 0.000113 + f-2 : 0.000226 + f+3 : 0.000146 + f-3 : 0.000599 + 1 N s : 3.826346 s : 3.826346 + pz : 0.875786 p : 2.656554 + px : 0.952381 + py : 0.828388 + dz2 : 0.029843 d : 0.135676 + dxz : 0.042747 + dyz : 0.018054 + dx2y2 : 0.019419 + dxy : 0.025613 + f0 : 0.008991 f : 0.030312 + f+1 : 0.004057 + f-1 : 0.005831 + f+2 : 0.002928 + f-2 : 0.003040 + f+3 : 0.003463 + f-3 : 0.002001 + 2 O s : 3.878745 s : 3.878745 + pz : 1.827070 p : 4.301474 + px : 1.187962 + py : 1.286443 + dz2 : 0.004922 d : 0.063762 + dxz : 0.014118 + dyz : 0.002695 + dx2y2 : 0.020605 + dxy : 0.021422 + f0 : 0.001172 f : 0.007634 + f+1 : 0.000947 + f-1 : 0.000441 + f+2 : 0.000601 + f-2 : 0.000589 + f+3 : 0.002454 + f-3 : 0.001430 + 3 H s : 0.632220 s : 0.632220 + pz : 0.019139 p : 0.083289 + px : 0.024376 + py : 0.039774 + dz2 : 0.000636 d : 0.021468 + dxz : 0.007620 + dyz : 0.001763 + dx2y2 : 0.006687 + dxy : 0.004763 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.587221 0.000000 + 1 N : -0.249113 0.000000 + 2 O : 0.244131 0.000000 + 3 H : -0.582238 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.126128 s : 3.126128 + pz : 1.214561 p : 3.933911 + px : 1.281692 + py : 1.437657 + dz2 : 0.110089 d : 0.271893 + dxz : 0.065703 + dyz : 0.047426 + dx2y2 : 0.025667 + dxy : 0.023008 + f0 : 0.026904 f : 0.080847 + f+1 : 0.018760 + f-1 : 0.014616 + f+2 : 0.009023 + f-2 : 0.006631 + f+3 : 0.000978 + f-3 : 0.003936 + 1 N s : 3.021427 s : 3.021427 + pz : 0.916064 p : 2.838108 + px : 1.111127 + py : 0.810917 + dz2 : 0.213018 d : 0.942863 + dxz : 0.301243 + dyz : 0.109917 + dx2y2 : 0.149988 + dxy : 0.168697 + f0 : 0.113965 f : 0.446716 + f+1 : 0.066090 + f-1 : 0.058224 + f+2 : 0.055222 + f-2 : 0.044586 + f+3 : 0.056020 + f-3 : 0.052608 + 2 O s : 3.316244 s : 3.316244 + pz : 1.486014 p : 3.992464 + px : 1.355771 + py : 1.150679 + dz2 : 0.048308 d : 0.328902 + dxz : 0.101448 + dyz : 0.012778 + dx2y2 : 0.077669 + dxy : 0.088699 + f0 : 0.015027 f : 0.118259 + f+1 : 0.020459 + f-1 : 0.005202 + f+2 : 0.018547 + f-2 : 0.010331 + f+3 : 0.022313 + f-3 : 0.026381 + 3 H s : 0.624764 s : 0.624764 + pz : 0.140823 p : 0.564468 + px : 0.242856 + py : 0.180790 + dz2 : 0.034530 d : 0.393006 + dxz : 0.114633 + dyz : 0.028283 + dx2y2 : 0.108085 + dxy : 0.107476 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3625 8.0000 -0.3625 1.8720 1.8720 0.0000 + 1 N 6.6489 7.0000 0.3511 2.5607 2.5607 -0.0000 + 2 O 8.2516 8.0000 -0.2516 1.7709 1.7709 -0.0000 + 3 H 0.7370 1.0000 0.2630 0.9640 0.9640 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8542 B( 0-O , 3-H ) : 0.9615 B( 1-N , 2-O ) : 1.7092 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.415 sec +Sum of individual times .... 1.081 sec ( 76.4%) + +Fock matrix formation .... 0.809 sec ( 57.2%) +Diagonalization .... 0.087 sec ( 6.1%) +Density matrix formation .... 0.007 sec ( 0.5%) +Population analysis .... 0.100 sec ( 7.1%) +Initial guess .... 0.009 sec ( 0.6%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.3%) +DIIS solution .... 0.069 sec ( 4.9%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.204 sec +Reference energy ... -204.713412618 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.409 sec +AO-integral generation ... 0.140 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.420 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.025 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.038 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.357 sec +AO-integral generation ... 0.242 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.053 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.151 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.252 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090271827 +EMP2(bb)= -0.090271827 +EMP2(ab)= -0.516963352 + +Initial guess performed in 0.133 sec +E(0) ... -204.713412618 +E(MP2) ... -0.697507006 +Initial E(tot) ... -205.410919624 + ... 0.188804850 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.410919624 -0.697507006 -0.000000000 0.021510145 2.74 0.000001613 + *** Turning on DIIS *** + 1 -205.382245979 -0.668833361 0.028673645 0.009165351 2.73 0.056815224 + 2 -205.401754579 -0.688341961 -0.019508600 0.004453628 2.81 0.059740988 + 3 -205.405537533 -0.692124915 -0.003782955 0.001923781 2.86 0.073642483 + 4 -205.407096501 -0.693683884 -0.001558968 0.001636353 2.84 0.080138238 + 5 -205.407637571 -0.694224953 -0.000541069 0.000972845 2.87 0.085532973 + 6 -205.407745001 -0.694332383 -0.000107430 0.000609716 2.86 0.088322617 + 7 -205.407791716 -0.694379098 -0.000046715 0.000283927 2.93 0.089711124 + 8 -205.407804707 -0.694392089 -0.000012991 0.000148448 3.02 0.090286616 + 9 -205.407800473 -0.694387855 0.000004234 0.000046294 2.98 0.090471794 + 10 -205.407806118 -0.694393500 -0.000005645 0.000031911 2.80 0.090539938 + 11 -205.407802886 -0.694390268 0.000003232 0.000024356 2.95 0.090532630 + 12 -205.407804521 -0.694391903 -0.000001635 0.000017469 2.91 0.090548756 + 13 -205.407804283 -0.694391665 0.000000238 0.000010857 2.84 0.090543263 + 14 -205.407804664 -0.694392046 -0.000000380 0.000006123 2.91 0.090548444 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.713412618 +E(CORR) ... -0.694392046 +E(TOT) ... -205.407804664 +Singles norm **1/2 ... 0.090548444 ( 0.045274222, 0.045274222) +T1 diagnostic ... 0.021342473 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.053467 + 9a-> 13a 9b-> 13b 0.042233 + 9a-> 13a 8b-> 13b 0.039323 + 8a-> 13a 9b-> 13b 0.039323 + 10a-> 13a -1a-> -1a 0.033189 + 10b-> 13b -1b-> -1b 0.033189 + 8b-> 13b -1b-> -1b 0.032995 + 8a-> 13a -1a-> -1a 0.032995 + 5a-> 13a 5b-> 13b 0.028153 + 11a-> 13a 11b-> 13b 0.027917 + 11a-> 25a 11b-> 25b 0.027579 + 10a-> 13a 10b-> 13b 0.026589 + 10a-> 13a 9b-> 13b 0.026443 + 9a-> 13a 10b-> 13b 0.026443 + 11a-> 25a -1a-> -1a 0.024326 + 11b-> 25b -1b-> -1b 0.024326 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034627723 + alpha-alpha-alpha ... -0.000881728 ( 2.5%) + alpha-alpha-beta ... -0.016432133 ( 47.5%) + alpha-beta -beta ... -0.016432133 ( 47.5%) + beta -beta -beta ... -0.000881728 ( 2.5%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034627723 + +Final correlation energy ... -0.729019769 +E(CCSD) ... -205.407804664 +E(CCSD(T)) ... -205.442432387 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210908925 sqrt= 1.100413070 +W(HF) = 0.825825939 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.287781 -0.000000 + 1 N : 0.168355 -0.000000 + 2 O : -0.131039 0.000000 + 3 H : 0.250465 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.846453 s : 3.846453 + pz : 1.268609 p : 4.378529 + px : 1.397194 + py : 1.712726 + dz2 : 0.014740 d : 0.054492 + dxz : 0.011457 + dyz : 0.012854 + dx2y2 : 0.008284 + dxy : 0.007157 + f0 : 0.002129 f : 0.008308 + f+1 : 0.000980 + f-1 : 0.001551 + f+2 : 0.000766 + f-2 : 0.000875 + f+3 : 0.000788 + f-3 : 0.001220 + 1 N s : 3.879890 s : 3.879890 + pz : 0.913572 p : 2.756019 + px : 0.950008 + py : 0.892439 + dz2 : 0.035964 d : 0.166174 + dxz : 0.052886 + dyz : 0.026799 + dx2y2 : 0.021628 + dxy : 0.028896 + f0 : 0.008643 f : 0.029562 + f+1 : 0.003778 + f-1 : 0.005833 + f+2 : 0.003309 + f-2 : 0.003305 + f+3 : 0.002665 + f-3 : 0.002029 + 2 O s : 3.865528 s : 3.865528 + pz : 1.740486 p : 4.170578 + px : 1.174971 + py : 1.255121 + dz2 : 0.010076 d : 0.084843 + dxz : 0.021764 + dyz : 0.009016 + dx2y2 : 0.021245 + dxy : 0.022742 + f0 : 0.001655 f : 0.010091 + f+1 : 0.001417 + f-1 : 0.000901 + f+2 : 0.001153 + f-2 : 0.001121 + f+3 : 0.002265 + f-3 : 0.001579 + 3 H s : 0.642019 s : 0.642019 + pz : 0.022704 p : 0.089081 + px : 0.020713 + py : 0.045664 + dz2 : 0.000835 d : 0.018436 + dxz : 0.006801 + dyz : 0.001604 + dx2y2 : 0.005412 + dxy : 0.003784 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.598874 0.000000 + 1 N : -0.296363 -0.000000 + 2 O : 0.281629 -0.000000 + 3 H : -0.584140 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.131780 s : 3.131780 + pz : 1.215394 p : 3.878763 + px : 1.273254 + py : 1.390115 + dz2 : 0.116396 d : 0.302839 + dxz : 0.071644 + dyz : 0.052970 + dx2y2 : 0.032440 + dxy : 0.029390 + f0 : 0.028116 f : 0.087744 + f+1 : 0.020414 + f-1 : 0.015674 + f+2 : 0.009610 + f-2 : 0.007444 + f+3 : 0.001629 + f-3 : 0.004858 + 1 N s : 3.026432 s : 3.026432 + pz : 0.930230 p : 2.881512 + px : 1.103301 + py : 0.847981 + dz2 : 0.219958 d : 0.952282 + dxz : 0.299777 + dyz : 0.111856 + dx2y2 : 0.150482 + dxy : 0.170209 + f0 : 0.111483 f : 0.436138 + f+1 : 0.066096 + f-1 : 0.056274 + f+2 : 0.051472 + f-2 : 0.042342 + f+3 : 0.055622 + f-3 : 0.052848 + 2 O s : 3.318484 s : 3.318484 + pz : 1.430200 p : 3.914885 + px : 1.348190 + py : 1.136494 + dz2 : 0.054077 d : 0.358290 + dxz : 0.103646 + dyz : 0.019133 + dx2y2 : 0.085224 + dxy : 0.096210 + f0 : 0.015629 f : 0.126712 + f+1 : 0.021091 + f-1 : 0.005786 + f+2 : 0.018565 + f-2 : 0.011563 + f+3 : 0.026359 + f-3 : 0.027721 + 3 H s : 0.625673 s : 0.625673 + pz : 0.141974 p : 0.575765 + px : 0.246846 + py : 0.186945 + dz2 : 0.035956 d : 0.382701 + dxz : 0.110745 + dyz : 0.027213 + dx2y2 : 0.104630 + dxy : 0.104157 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2878 8.0000 -0.2878 2.2310 1.7690 0.4620 + 1 N 6.8316 7.0000 0.1684 2.8387 2.3530 0.4857 + 2 O 8.1310 8.0000 -0.1310 2.1644 1.6663 0.4981 + 3 H 0.7495 1.0000 0.2505 0.9862 0.9136 0.0725 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7798 B( 0-O , 3-H ) : 0.8946 B( 1-N , 2-O ) : 1.5629 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 58.241 sec + +Fock Matrix Formation ... 0.204 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 2.063 sec ( 3.5%) +State Vector Update ... 0.093 sec ( 0.2%) +Sigma-vector construction ... 40.908 sec ( 70.2%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (0-ext) ... 0.073 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.027 sec ( 0.1% of sigma) + (2-ext) ... 0.991 sec ( 2.4% of sigma) + (4-ext) ... 22.904 sec ( 56.0% of sigma) + ... 1.557 sec ( 3.8% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.009 sec ( 0.0% of sigma) + (1-ext) ... 0.116 sec ( 0.3% of sigma) + Fock-dressing ... 2.220 sec ( 5.4% of sigma) + (ik|jl)-dressing ... 0.079 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 10.127 sec ( 24.8% of sigma) + Pair energies ... 0.006 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.672 sec ( 11.5% of ALL) + I/O of integral and amplitudes ... 0.662 sec ( 9.9% of (T)) + External N**7 contributions ... 3.911 sec ( 58.6% of (T)) + Internal N**7 contributions ... 0.307 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.608 sec ( 24.1% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.442432386691 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.039.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.039.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.689662, -0.154384 -0.311518) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.73351 -0.15387 -0.87363 +Nuclear contribution : -1.43735 0.35731 0.71924 + ----------------------------------------- +Total Dipole Moment : -0.70384 0.20344 -0.15439 + ----------------------------------------- +Magnitude (a.u.) : 0.74874 +Magnitude (Debye) : 1.90315 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.890623 0.407592 0.364430 +Rotational constants in MHz : 86658.710035 12219.307251 10925.347243 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.385747 -0.448353 0.459121 +x,y,z [Debye]: -0.980491 -1.139624 1.166994 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.689662, -0.154384 -0.311518) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.90334 -0.12377 -0.85641 +Nuclear contribution : -1.43735 0.35731 0.71924 + ----------------------------------------- +Total Dipole Moment : -0.53401 0.23354 -0.13717 + ----------------------------------------- +Magnitude (a.u.) : 0.59877 +Magnitude (Debye) : 1.52196 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.890623 0.407592 0.364430 +Rotational constants in MHz : 86658.710035 12219.307251 10925.347243 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.274373 -0.319909 0.425330 +x,y,z [Debye]: -0.697401 -0.813144 1.081103 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 40 * + * * + * Dihedral ( 2, 1, 0, 3) : 139.09090909 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0399451794 RMS(Int)= 0.0001996301 + Iter 1: RMS(Cart)= 0.0000558423 RMS(Int)= 0.0000009180 + Iter 2: RMS(Cart)= 0.0000002568 RMS(Int)= 0.0000000042 + Iter 3: RMS(Cart)= 0.0000000012 RMS(Int)= 0.0000000000 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4721 0.000000 + 2. B(O 2,N 1) 1.1705 0.000000 + 3. B(H 3,O 0) 0.9720 0.000000 + 4. A(N 1,O 0,H 3) 102.0676 0.000000 + 5. A(O 0,N 1,O 2) 110.3970 0.000000 + 6. D(O 2,N 1,O 0,H 3) 139.0909 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.287011 -0.062435 0.752784 + N 0.184454 -0.278679 -0.624952 + O 1.293898 0.077328 -0.737092 + H -1.191340 0.263786 0.609260 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.542371 -0.117984 1.422556 + 1 N 7.0000 0 14.007 0.348567 -0.526627 -1.180988 + 2 O 8.0000 0 15.999 2.445112 0.146128 -1.392902 + 3 H 1.0000 0 1.008 -2.251306 0.498483 1.151334 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.472020279738 0.00000000 0.00000000 + O 2 1 0 1.168438782730 110.46007613 0.00000000 + H 1 2 3 0.969243714746 102.11712370 130.90909107 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.781715192283 0.00000000 0.00000000 + O 2 1 0 2.208029303611 110.46007613 0.00000000 + H 1 2 3 1.831605177895 102.11712370 130.90909107 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2223 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2687 + la=0 lb=0: 547 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.777133962015 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.7771339620 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.982e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7101106813 0.000000000000 0.00170051 0.00005407 0.0199244 0.7000 + 1 -204.7110232081 -0.000912526809 0.00164441 0.00004892 0.0164824 0.7000 + ***Turning on DIIS*** + 2 -204.7118030280 -0.000779819911 0.00453389 0.00013263 0.0133860 0.0000 + 3 -204.7149544251 -0.003151397114 0.00182320 0.00005498 0.0051824 0.0000 + 4 -204.7137632407 0.001191184420 0.00085941 0.00002618 0.0020137 0.0000 + 5 -204.7153221566 -0.001558915933 0.00059846 0.00002109 0.0010770 0.0000 + 6 -204.7144680102 0.000854146399 0.00068775 0.00002503 0.0006366 0.0000 + 7 -204.7142860679 0.000181942344 0.00033176 0.00001246 0.0002910 0.0000 + 8 -204.7149265227 -0.000640454858 0.00017391 0.00000733 0.0002098 0.0000 + 9 -204.7145301254 0.000396397310 0.00015072 0.00000550 0.0001324 0.0000 + 10 -204.7147387339 -0.000208608483 0.00006662 0.00000228 0.0000557 0.0000 + 11 -204.7147185486 0.000020185267 0.00001538 0.00000050 0.0000245 0.0000 + 12 -204.7146714893 0.000047059306 0.00000580 0.00000021 0.0000102 0.0000 + 13 -204.7146937172 -0.000022227874 0.00000232 0.00000007 0.0000025 0.0000 + 14 -204.7146879121 0.000005805049 0.00000108 0.00000003 0.0000018 0.0000 + 15 -204.7146892300 -0.000001317906 0.00000062 0.00000002 0.0000013 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 16 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71469110 Eh -5570.56995 eV + +Components: +Nuclear Repulsion : 68.77713396 Eh 1871.52096 eV +Electronic Energy : -273.49182506 Eh -7442.09091 eV +One Electron Energy: -417.27987279 Eh -11354.76260 eV +Two Electron Energy: 143.78804774 Eh 3912.67170 eV + +Virial components: +Potential Energy : -408.92960029 Eh -11127.54014 eV +Kinetic Energy : 204.21490920 Eh 5556.97019 eV +Virial Ratio : 2.00244733 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.8671e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.6988e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.5908e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.4779e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.679571 -562.7197 + 1 1.0000 -20.628291 -561.3243 + 2 1.0000 -15.802516 -430.0083 + 3 1.0000 -1.608655 -43.7737 + 4 1.0000 -1.384822 -37.6829 + 5 1.0000 -0.950191 -25.8560 + 6 1.0000 -0.775212 -21.0946 + 7 1.0000 -0.728502 -19.8235 + 8 1.0000 -0.690005 -18.7760 + 9 1.0000 -0.615373 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2.5164 + 15 0.0000 0.099357 2.7037 + 16 0.0000 0.120741 3.2855 + 17 0.0000 0.150196 4.0870 + 18 0.0000 0.157078 4.2743 + 19 0.0000 0.172833 4.7030 + 20 0.0000 0.186653 5.0791 + 21 0.0000 0.192641 5.2420 + 22 0.0000 0.203248 5.5306 + 23 0.0000 0.235671 6.4129 + 24 0.0000 0.266792 7.2598 + 25 0.0000 0.283105 7.7037 + 26 0.0000 0.308041 8.3822 + 27 0.0000 0.328619 8.9422 + 28 0.0000 0.351319 9.5599 + 29 0.0000 0.364633 9.9222 + 30 0.0000 0.423505 11.5241 + 31 0.0000 0.512981 13.9589 + 32 0.0000 0.520318 14.1586 + 33 0.0000 0.545659 14.8481 + 34 0.0000 0.570013 15.5108 + 35 0.0000 0.611306 16.6345 + 36 0.0000 0.632399 17.2084 + 37 0.0000 0.647081 17.6080 + 38 0.0000 0.701120 19.0785 + 39 0.0000 0.719404 19.5760 + 40 0.0000 0.731889 19.9157 + 41 0.0000 0.743255 20.2250 + 42 0.0000 0.775904 21.1134 + 43 0.0000 0.794531 21.6203 + 44 0.0000 0.801386 21.8068 + 45 0.0000 0.822948 22.3935 + 46 0.0000 0.847414 23.0593 + 47 0.0000 0.859594 23.3907 + 48 0.0000 0.924233 25.1497 + 49 0.0000 0.946202 25.7475 + 50 0.0000 0.961060 26.1518 + 51 0.0000 1.010762 27.5042 + 52 0.0000 1.020316 27.7642 + 53 0.0000 1.030775 28.0488 + 54 0.0000 1.046715 28.4826 + 55 0.0000 1.086553 29.5666 + 56 0.0000 1.151995 31.3474 + 57 0.0000 1.204857 32.7858 + 58 0.0000 1.253236 34.1023 + 59 0.0000 1.309908 35.6444 + 60 0.0000 1.373371 37.3713 + 61 0.0000 1.405345 38.2414 + 62 0.0000 1.461621 39.7727 + 63 0.0000 1.510667 41.1073 + 64 0.0000 1.530348 41.6429 + 65 0.0000 1.541872 41.9565 + 66 0.0000 1.566402 42.6240 + 67 0.0000 1.625809 44.2405 + 68 0.0000 1.667211 45.3671 + 69 0.0000 1.714009 46.6405 + 70 0.0000 1.781941 48.4891 + 71 0.0000 1.794423 48.8287 + 72 0.0000 1.877669 51.0940 + 73 0.0000 1.928743 52.4838 + 74 0.0000 1.958851 53.3030 + 75 0.0000 2.029960 55.2380 + 76 0.0000 2.048292 55.7369 + 77 0.0000 2.098729 57.1093 + 78 0.0000 2.157703 58.7141 + 79 0.0000 2.193359 59.6843 + 80 0.0000 2.279200 62.0202 + 81 0.0000 2.282363 62.1062 + 82 0.0000 2.310209 62.8640 + 83 0.0000 2.376257 64.6612 + 84 0.0000 2.437617 66.3309 + 85 0.0000 2.461735 66.9872 + 86 0.0000 2.482582 67.5545 + 87 0.0000 2.494286 67.8730 + 88 0.0000 2.507587 68.2349 + 89 0.0000 2.529245 68.8243 + 90 0.0000 2.573246 70.0216 + 91 0.0000 2.605043 70.8868 + 92 0.0000 2.658740 72.3480 + 93 0.0000 2.704529 73.5940 + 94 0.0000 2.733038 74.3697 + 95 0.0000 2.782624 75.7191 + 96 0.0000 2.810733 76.4839 + 97 0.0000 2.891383 78.6785 + 98 0.0000 2.950370 80.2837 + 99 0.0000 3.062773 83.3423 + 100 0.0000 3.121840 84.9496 + 101 0.0000 3.171791 86.3088 + 102 0.0000 3.259364 88.6918 + 103 0.0000 3.471199 94.4561 + 104 0.0000 3.737194 101.6942 + 105 0.0000 3.876645 105.4889 + 106 0.0000 4.035381 109.8083 + 107 0.0000 4.155349 113.0728 + 108 0.0000 4.194992 114.1515 + 109 0.0000 4.288498 116.6960 + 110 0.0000 4.366750 118.8253 + 111 0.0000 4.388657 119.4214 + 112 0.0000 4.545776 123.6969 + 113 0.0000 4.626776 125.9010 + 114 0.0000 4.743771 129.0846 + 115 0.0000 4.753412 129.3469 + 116 0.0000 4.782060 130.1265 + 117 0.0000 4.885189 132.9327 + 118 0.0000 4.950451 134.7086 + 119 0.0000 4.989753 135.7781 + 120 0.0000 5.066500 137.8665 + 121 0.0000 5.095029 138.6428 + 122 0.0000 5.173235 140.7709 + 123 0.0000 5.206226 141.6686 + 124 0.0000 5.250954 142.8857 + 125 0.0000 5.322684 144.8376 + 126 0.0000 5.354611 145.7064 + 127 0.0000 5.395231 146.8117 + 128 0.0000 5.541641 150.7957 + 129 0.0000 5.695243 154.9754 + 130 0.0000 5.786956 157.4711 + 131 0.0000 5.982084 162.7808 + 132 0.0000 6.125774 166.6908 + 133 0.0000 6.399053 174.1271 + 134 0.0000 6.494040 176.7118 + 135 0.0000 6.506557 177.0524 + 136 0.0000 6.698545 182.2767 + 137 0.0000 6.702392 182.3814 + 138 0.0000 6.746727 183.5878 + 139 0.0000 6.831151 185.8851 + 140 0.0000 6.888447 187.4442 + 141 0.0000 7.058426 192.0695 + 142 0.0000 7.118067 193.6925 + 143 0.0000 7.154169 194.6748 + 144 0.0000 7.185601 195.5301 + 145 0.0000 7.232511 196.8066 + 146 0.0000 7.265033 197.6916 + 147 0.0000 7.350200 200.0091 + 148 0.0000 7.396928 201.2806 + 149 0.0000 7.436431 202.3556 + 150 0.0000 7.476333 203.4414 + 151 0.0000 7.564824 205.8493 + 152 0.0000 7.608525 207.0385 + 153 0.0000 7.639575 207.8834 + 154 0.0000 7.877908 214.3688 + 155 0.0000 7.879759 214.4192 + 156 0.0000 7.991644 217.4637 + 157 0.0000 8.372331 227.8227 + 158 0.0000 14.048616 382.2823 + 159 0.0000 14.821275 403.3074 + 160 0.0000 16.091774 437.8794 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.365493 0.000000 + 1 N : 0.352017 0.000000 + 2 O : -0.255474 0.000000 + 3 H : 0.268950 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.870771 s : 3.870771 + pz : 1.282133 p : 4.467300 + px : 1.388424 + py : 1.796742 + dz2 : 0.009856 d : 0.022913 + dxz : 0.005282 + dyz : 0.005960 + dx2y2 : 0.001581 + dxy : 0.000233 + f0 : 0.001936 f : 0.004510 + f+1 : 0.000465 + f-1 : 0.001067 + f+2 : 0.000145 + f-2 : 0.000182 + f+3 : 0.000206 + f-3 : 0.000507 + 1 N s : 3.827684 s : 3.827684 + pz : 0.879697 p : 2.653873 + px : 0.969109 + py : 0.805067 + dz2 : 0.030403 d : 0.136393 + dxz : 0.043796 + dyz : 0.017359 + dx2y2 : 0.016748 + dxy : 0.028087 + f0 : 0.008955 f : 0.030032 + f+1 : 0.004112 + f-1 : 0.005841 + f+2 : 0.003178 + f-2 : 0.002505 + f+3 : 0.003106 + f-3 : 0.002335 + 2 O s : 3.879313 s : 3.879313 + pz : 1.836641 p : 4.304528 + px : 1.182781 + py : 1.285107 + dz2 : 0.004960 d : 0.063935 + dxz : 0.014865 + dyz : 0.001891 + dx2y2 : 0.018109 + dxy : 0.024109 + f0 : 0.001173 f : 0.007699 + f+1 : 0.000980 + f-1 : 0.000415 + f+2 : 0.000788 + f-2 : 0.000429 + f+3 : 0.002170 + f-3 : 0.001745 + 3 H s : 0.628209 s : 0.628209 + pz : 0.018973 p : 0.081375 + px : 0.021901 + py : 0.040501 + dz2 : 0.000491 d : 0.021465 + dxz : 0.008287 + dyz : 0.001243 + dx2y2 : 0.005172 + dxy : 0.006271 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.585643 0.000000 + 1 N : -0.248101 0.000000 + 2 O : 0.240778 0.000000 + 3 H : -0.578320 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.127997 s : 3.127997 + pz : 1.215341 p : 3.932471 + px : 1.273143 + py : 1.443987 + dz2 : 0.112989 d : 0.272959 + dxz : 0.065077 + dyz : 0.045840 + dx2y2 : 0.029521 + dxy : 0.019531 + f0 : 0.027817 f : 0.080931 + f+1 : 0.019255 + f-1 : 0.014019 + f+2 : 0.008755 + f-2 : 0.006310 + f+3 : 0.001457 + f-3 : 0.003318 + 1 N s : 3.021973 s : 3.021973 + pz : 0.920675 p : 2.836360 + px : 1.135491 + py : 0.780193 + dz2 : 0.213444 d : 0.943444 + dxz : 0.307969 + dyz : 0.105079 + dx2y2 : 0.155064 + dxy : 0.161888 + f0 : 0.115315 f : 0.446325 + f+1 : 0.067234 + f-1 : 0.058038 + f+2 : 0.062168 + f-2 : 0.036228 + f+3 : 0.054513 + f-3 : 0.052830 + 2 O s : 3.317542 s : 3.317542 + pz : 1.493601 p : 3.995953 + px : 1.367454 + py : 1.134898 + dz2 : 0.047707 d : 0.327938 + dxz : 0.104966 + dyz : 0.010003 + dx2y2 : 0.084634 + dxy : 0.080629 + f0 : 0.015233 f : 0.117788 + f+1 : 0.021005 + f-1 : 0.004229 + f+2 : 0.021153 + f-2 : 0.007909 + f+3 : 0.022269 + f-3 : 0.025990 + 3 H s : 0.624196 s : 0.624196 + pz : 0.138891 p : 0.560994 + px : 0.248353 + py : 0.173749 + dz2 : 0.035219 d : 0.393130 + dxz : 0.120310 + dyz : 0.021337 + dx2y2 : 0.104203 + dxy : 0.112061 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3655 8.0000 -0.3655 1.8895 1.8895 -0.0000 + 1 N 6.6480 7.0000 0.3520 2.5579 2.5579 0.0000 + 2 O 8.2555 8.0000 -0.2555 1.7653 1.7653 0.0000 + 3 H 0.7310 1.0000 0.2690 0.9563 0.9563 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8704 B( 0-O , 3-H ) : 0.9609 B( 1-N , 2-O ) : 1.6996 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.590 sec +Sum of individual times .... 2.243 sec ( 86.6%) + +Fock matrix formation .... 1.775 sec ( 68.5%) +Diagonalization .... 0.185 sec ( 7.1%) +Density matrix formation .... 0.014 sec ( 0.5%) +Population analysis .... 0.102 sec ( 3.9%) +Initial guess .... 0.009 sec ( 0.3%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.2%) +DIIS solution .... 0.158 sec ( 6.1%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.202 sec +Reference energy ... -204.714690625 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.358 sec +AO-integral generation ... 0.142 sec +Half transformation ... 0.079 sec +K-integral sorting ... 5.366 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.024 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.022 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.028 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.045 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.345 sec +AO-integral generation ... 0.243 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.048 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.154 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.250 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090509513 +EMP2(bb)= -0.090509513 +EMP2(ab)= -0.517797626 + +Initial guess performed in 0.133 sec +E(0) ... -204.714690625 +E(MP2) ... -0.698816652 +Initial E(tot) ... -205.413507277 + ... 0.189784316 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.413507277 -0.698816652 -0.000000000 0.022685572 2.71 0.000002156 + *** Turning on DIIS *** + 1 -205.384092347 -0.669401722 0.029414930 0.009651803 2.71 0.057751200 + 2 -205.403806897 -0.689116272 -0.019714550 0.004770562 2.79 0.060606769 + 3 -205.407607520 -0.692916896 -0.003800623 0.002074970 2.82 0.074898363 + 4 -205.409196366 -0.694505741 -0.001588845 0.001762280 2.79 0.081650437 + 5 -205.409763741 -0.695073117 -0.000567376 0.001014287 2.90 0.087397601 + 6 -205.409879318 -0.695188694 -0.000115577 0.000625567 2.83 0.090394230 + 7 -205.409929719 -0.695239095 -0.000050401 0.000270998 2.90 0.091884423 + 8 -205.409944032 -0.695253408 -0.000014313 0.000140891 2.89 0.092478017 + 9 -205.409939521 -0.695248897 0.000004511 0.000041082 2.81 0.092662154 + 10 -205.409945294 -0.695254670 -0.000005773 0.000026591 2.78 0.092724808 + 11 -205.409942036 -0.695251411 0.000003259 0.000020656 3.25 0.092716454 + 12 -205.409943546 -0.695252921 -0.000001510 0.000015278 2.82 0.092731612 + 13 -205.409943265 -0.695252640 0.000000281 0.000009859 3.02 0.092725990 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.714690625 +E(CORR) ... -0.695252640 +E(TOT) ... -205.409943265 +Singles norm **1/2 ... 0.092725990 ( 0.046362995, 0.046362995) +T1 diagnostic ... 0.021855725 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.056584 + 9a-> 13a 8b-> 13b 0.036255 + 8a-> 13a 9b-> 13b 0.036255 + 10a-> 13a -1a-> -1a 0.036011 + 10b-> 13b -1b-> -1b 0.036011 + 8b-> 13b -1b-> -1b 0.035491 + 8a-> 13a -1a-> -1a 0.035491 + 9a-> 13a 9b-> 13b 0.034372 + 10a-> 13a 10b-> 13b 0.033087 + 11a-> 25a 11b-> 25b 0.028190 + 5a-> 13a 5b-> 13b 0.027959 + 11a-> 13a 11b-> 13b 0.027726 + 10a-> 13a 9b-> 13b 0.026088 + 9a-> 13a 10b-> 13b 0.026088 + 10a-> 13a 8b-> 13b 0.025836 + 8a-> 13a 10b-> 13b 0.025836 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034939343 + alpha-alpha-alpha ... -0.000891194 ( 2.6%) + alpha-alpha-beta ... -0.016578478 ( 47.4%) + alpha-beta -beta ... -0.016578478 ( 47.4%) + beta -beta -beta ... -0.000891194 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034939343 + +Final correlation energy ... -0.730191984 +E(CCSD) ... -205.409943265 +E(CCSD(T)) ... -205.444882608 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.212309629 sqrt= 1.101049331 +W(HF) = 0.824871779 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.285772 -0.000000 + 1 N : 0.165866 0.000000 + 2 O : -0.135774 0.000000 + 3 H : 0.255680 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.848152 s : 3.848152 + pz : 1.271670 p : 4.374471 + px : 1.374889 + py : 1.727912 + dz2 : 0.014624 d : 0.054840 + dxz : 0.011073 + dyz : 0.013349 + dx2y2 : 0.008593 + dxy : 0.007201 + f0 : 0.002147 f : 0.008308 + f+1 : 0.000938 + f-1 : 0.001607 + f+2 : 0.000806 + f-2 : 0.000832 + f+3 : 0.000851 + f-3 : 0.001127 + 1 N s : 3.880077 s : 3.880077 + pz : 0.916154 p : 2.757888 + px : 0.961728 + py : 0.880005 + dz2 : 0.036329 d : 0.166841 + dxz : 0.054091 + dyz : 0.026212 + dx2y2 : 0.019492 + dxy : 0.030717 + f0 : 0.008629 f : 0.029328 + f+1 : 0.003825 + f-1 : 0.005829 + f+2 : 0.003521 + f-2 : 0.002869 + f+3 : 0.002455 + f-3 : 0.002199 + 2 O s : 3.866314 s : 3.866314 + pz : 1.749577 p : 4.174245 + px : 1.171057 + py : 1.253611 + dz2 : 0.010058 d : 0.085049 + dxz : 0.022661 + dyz : 0.008245 + dx2y2 : 0.019115 + dxy : 0.024971 + f0 : 0.001658 f : 0.010166 + f+1 : 0.001447 + f-1 : 0.000879 + f+2 : 0.001318 + f-2 : 0.000995 + f+3 : 0.002064 + f-3 : 0.001806 + 3 H s : 0.639130 s : 0.639130 + pz : 0.022639 p : 0.086804 + px : 0.017483 + py : 0.046682 + dz2 : 0.000731 d : 0.018386 + dxz : 0.007393 + dyz : 0.001163 + dx2y2 : 0.003959 + dxy : 0.005141 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.599259 -0.000000 + 1 N : -0.297125 0.000000 + 2 O : 0.277353 0.000000 + 3 H : -0.579487 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.134064 s : 3.134064 + pz : 1.217376 p : 3.874687 + px : 1.265373 + py : 1.391939 + dz2 : 0.119340 d : 0.304116 + dxz : 0.070877 + dyz : 0.051617 + dx2y2 : 0.036576 + dxy : 0.025707 + f0 : 0.028953 f : 0.087873 + f+1 : 0.020867 + f-1 : 0.015257 + f+2 : 0.009372 + f-2 : 0.007072 + f+3 : 0.002170 + f-3 : 0.004183 + 1 N s : 3.026945 s : 3.026945 + pz : 0.933777 p : 2.881969 + px : 1.123728 + py : 0.824464 + dz2 : 0.220397 d : 0.952766 + dxz : 0.305786 + dyz : 0.107192 + dx2y2 : 0.157063 + dxy : 0.162328 + f0 : 0.112938 f : 0.435445 + f+1 : 0.067257 + f-1 : 0.055856 + f+2 : 0.057647 + f-2 : 0.034552 + f+3 : 0.054359 + f-3 : 0.052837 + 2 O s : 3.319631 s : 3.319631 + pz : 1.437325 p : 3.918780 + px : 1.360112 + py : 1.121343 + dz2 : 0.053472 d : 0.357877 + dxz : 0.107036 + dyz : 0.016419 + dx2y2 : 0.091685 + dxy : 0.089265 + f0 : 0.015784 f : 0.126358 + f+1 : 0.021645 + f-1 : 0.004855 + f+2 : 0.021112 + f-2 : 0.009122 + f+3 : 0.025849 + f-3 : 0.027992 + 3 H s : 0.625385 s : 0.625385 + pz : 0.140108 p : 0.571492 + px : 0.251894 + py : 0.179490 + dz2 : 0.036657 d : 0.382610 + dxz : 0.116204 + dyz : 0.020492 + dx2y2 : 0.101506 + dxy : 0.107751 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2858 8.0000 -0.2858 2.2550 1.7896 0.4654 + 1 N 6.8341 7.0000 0.1659 2.8410 2.3551 0.4858 + 2 O 8.1358 8.0000 -0.1358 2.1627 1.6637 0.4989 + 3 H 0.7443 1.0000 0.2557 0.9789 0.9064 0.0725 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.7983 B( 0-O , 3-H ) : 0.8926 B( 1-N , 2-O ) : 1.5541 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 55.601 sec + +Fock Matrix Formation ... 0.202 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 1.808 sec ( 3.3%) +State Vector Update ... 0.084 sec ( 0.2%) +Sigma-vector construction ... 38.134 sec ( 68.6%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.023 sec ( 0.1% of sigma) + (0-ext) ... 0.072 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (2-ext) ... 0.941 sec ( 2.5% of sigma) + (4-ext) ... 21.421 sec ( 56.2% of sigma) + ... 1.293 sec ( 3.4% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.107 sec ( 0.3% of sigma) + Fock-dressing ... 2.102 sec ( 5.5% of sigma) + (ik|jl)-dressing ... 0.077 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.469 sec ( 24.8% of sigma) + Pair energies ... 0.008 sec ( 0.0% of sigma) +Total Time for computing (T) ... 7.189 sec ( 12.9% of ALL) + I/O of integral and amplitudes ... 0.966 sec ( 13.4% of (T)) + External N**7 contributions ... 3.973 sec ( 55.3% of (T)) + Internal N**7 contributions ... 0.346 sec ( 4.8% of (T)) + N**6 triples energy contributions ... 1.826 sec ( 25.4% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.444882608188 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.003233075 -0.008388218 0.002671478 + 2 N : 0.001865461 -0.009769720 0.000236325 + 3 O : 0.000722745 0.008433315 -0.002599225 + 4 H : 0.000644868 0.009724623 -0.000308578 + +Norm of the cartesian gradient ... 0.018984559 +RMS gradient ... 0.005480370 +MAX gradient ... 0.009769720 + +------- +TIMINGS +------- + +Total numerical gradient time ... 372.766 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 309.24 cm**-1 + 7: 571.87 cm**-1 + 8: 783.11 cm**-1 + 9: 1237.36 cm**-1 + 10: 1691.76 cm**-1 + 11: 3737.30 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 0.045361 -0.324557 -0.081606 -0.059050 -0.004213 -0.059175 + 1 0.045663 0.004373 -0.122504 0.000535 -0.015781 0.020684 + 2 -0.051771 0.405182 -0.175241 -0.055934 -0.094510 -0.007371 + 3 -0.040564 0.209287 -0.005388 0.020645 0.678379 -0.002045 + 4 0.074454 0.104671 0.132407 -0.015639 0.236621 -0.001521 + 5 0.038909 -0.100592 0.509157 0.038622 0.044057 -0.001022 + 6 0.009700 0.167984 0.076168 0.052395 -0.590475 0.002198 + 7 -0.051631 -0.062316 -0.013569 0.007260 -0.193721 0.001204 + 8 0.014982 -0.299426 -0.226635 -0.039136 0.037729 -0.000542 + 9 -0.310251 -0.423081 0.161169 -0.181244 0.012253 0.932744 + 10 -0.939875 -0.534813 0.319840 0.093598 0.037182 -0.326266 + 11 0.043230 -0.280739 -0.696563 0.972256 0.289012 0.139792 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 309.24 0.035055 177.15 0.035375 (-0.111119 -0.125626 0.085120) + 7: 571.87 0.021696 109.64 0.011839 ( 0.064991 -0.022268 -0.084377) + 8: 783.11 0.019030 96.17 0.007583 (-0.049067 0.020697 0.068902) + 9: 1237.36 0.021113 106.70 0.005325 (-0.032935 0.015160 0.063327) + 10: 1691.76 0.031491 159.14 0.005809 ( 0.058580 0.005201 -0.048480) + 11: 3737.30 0.013782 69.65 0.001151 ( 0.030727 -0.010556 -0.009760) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 309.24 E(vib) ... 0.26 +freq. 571.87 E(vib) ... 0.11 +freq. 783.11 E(vib) ... 0.05 +freq. 1237.36 E(vib) ... 0.01 +freq. 1691.76 E(vib) ... 0.00 +freq. 3737.30 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.44488261 Eh +Zero point energy ... 0.01897862 Eh 11.91 kcal/mol +Thermal vibrational correction ... 0.00068492 Eh 0.43 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42238652 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00351747 Eh 2.21 kcal/mol +Non-thermal (ZPE) correction 0.01897862 Eh 11.91 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02249609 Eh 14.12 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42238652 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.42144231 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.914438 0.407033 0.362499 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00101390 Eh 0.64 kcal/mol +Rotational entropy ... 0.00990922 Eh 6.22 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02872544 Eh 18.03 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00990922 Eh 6.22 kcal/mol| +| sn= 2 | S(rot)= 0.00925476 Eh 5.81 kcal/mol| +| sn= 3 | S(rot)= 0.00887193 Eh 5.57 kcal/mol| +| sn= 4 | S(rot)= 0.00860030 Eh 5.40 kcal/mol| +| sn= 5 | S(rot)= 0.00838962 Eh 5.26 kcal/mol| +| sn= 6 | S(rot)= 0.00821747 Eh 5.16 kcal/mol| +| sn= 7 | S(rot)= 0.00807193 Eh 5.07 kcal/mol| +| sn= 8 | S(rot)= 0.00794585 Eh 4.99 kcal/mol| +| sn= 9 | S(rot)= 0.00783464 Eh 4.92 kcal/mol| +| sn=10 | S(rot)= 0.00773516 Eh 4.85 kcal/mol| +| sn=11 | S(rot)= 0.00764517 Eh 4.80 kcal/mol| +| sn=12 | S(rot)= 0.00756302 Eh 4.75 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.42144231 Eh +Total entropy correction ... -0.02872544 Eh -18.03 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.45016775 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00528514 Eh -3.32 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.444882609 Eh +Current gradient norm .... 0.018984559 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.008092146 0.113996950 0.172620101 0.481997280 0.506994327 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999745228 +Lowest eigenvalues of augmented Hessian: + -0.000089031 0.111487387 0.171598857 0.481981712 0.506978529 +Length of the computed step .... 0.022577411 +The final length of the internal step .... 0.022577411 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0092171893 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0060728576 RMS(Int)= 0.0092159643 + Iter 1: RMS(Cart)= 0.0000028157 RMS(Int)= 0.0000055920 + Iter 2: RMS(Cart)= 0.0000000219 RMS(Int)= 0.0000000245 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0022652741 0.0001000000 NO + MAX gradient 0.0034968798 0.0003000000 NO + RMS step 0.0092171893 0.0020000000 NO + MAX step 0.0217296221 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0115 Max(Angles) 0.12 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4721 0.003241 -0.0115 1.4606 + 2. B(O 2,N 1) 1.1705 0.003497 -0.0006 1.1699 + 3. B(H 3,O 0) 0.9720 0.002704 -0.0030 0.9690 + 4. A(N 1,O 0,H 3) 102.07 0.000708 -0.01 102.06 + 5. A(O 0,N 1,O 2) 110.40 0.000489 0.12 110.52 + 6. D(O 2,N 1,O 0,H 3) 139.09 -0.016837 0.00 139.09 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.284959 -0.062933 0.748183 + N 0.181286 -0.277244 -0.619355 + O 1.290151 0.077418 -0.734795 + H -1.186477 0.262759 0.605966 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.538494 -0.118925 1.413861 + 1 N 7.0000 0 14.007 0.342582 -0.523915 -1.170410 + 2 O 8.0000 0 15.999 2.438032 0.146298 -1.388561 + 3 H 1.0000 0 1.008 -2.242117 0.496542 1.145110 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.460641205068 0.00000000 0.00000000 + O 2 1 0 1.169911031801 110.51510479 0.00000000 + H 1 2 3 0.969038827467 102.05626343 139.09090891 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.760211857500 0.00000000 0.00000000 + O 2 1 0 2.210811451157 110.51510479 0.00000000 + H 1 2 3 1.831217997048 102.05626343 139.09090891 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2224 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2689 + la=0 lb=0: 547 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 391 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.044256445130 Eh + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.960e-04 +Time for diagonalization ... 0.005 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.004 sec +Total time needed ... 0.010 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7159702832 0.000000000000 0.00045374 0.00000916 0.0020765 0.7000 + 1 -204.7159853197 -0.000015036493 0.00033781 0.00000758 0.0015936 0.7000 + ***Turning on DIIS*** + 2 -204.7159977334 -0.000012413716 0.00078523 0.00001941 0.0012093 0.0000 + 3 -204.7153024635 0.000695269843 0.00029716 0.00000797 0.0002911 0.0000 + 4 -204.7160717318 -0.000769268258 0.00009782 0.00000252 0.0001229 0.0000 + 5 -204.7163981223 -0.000326390560 0.00002952 0.00000098 0.0000593 0.0000 + 6 -204.7158915025 0.000506619803 0.00001581 0.00000056 0.0000273 0.0000 + 7 -204.7160282603 -0.000136757743 0.00000803 0.00000033 0.0000129 0.0000 + 8 -204.7160431294 -0.000014869117 0.00000749 0.00000028 0.0000084 0.0000 + 9 -204.7160109160 0.000032213402 0.00000564 0.00000025 0.0000053 0.0000 + 10 -204.7160471138 -0.000036197771 0.00000333 0.00000013 0.0000030 0.0000 + 11 -204.7160366987 0.000010415052 0.00000145 0.00000005 0.0000014 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + +Total Energy : -204.71603657 Eh -5570.60656 eV + Last Energy change ... 1.2697e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.6128e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 5 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.603 sec +Reference energy ... -204.716038170 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 10.466 sec +AO-integral generation ... 0.344 sec +Half transformation ... 0.173 sec +K-integral sorting ... 8.074 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.076 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.064 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.067 s ( 0.000 ms/b) + 151164 b 0 skpd 0.118 s ( 0.001 ms/b) +: 159120 b 0 skpd 0.047 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.106 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.077 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.063 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.105 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.063 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.896 sec +AO-integral generation ... 0.698 sec +Half transformation ... 0.091 sec +J-integral sorting ... 0.079 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.259 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.392 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090354638 +EMP2(bb)= -0.090354638 +EMP2(ab)= -0.516776027 + +Initial guess performed in 0.186 sec +E(0) ... -204.716038170 +E(MP2) ... -0.697485302 +Initial E(tot) ... -205.413523472 + ... 0.188514600 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.413523472 -0.697485302 -0.000000000 0.022687126 6.56 0.000001048 + *** Turning on DIIS *** + 1 -205.384724119 -0.668685949 0.028799354 0.009368008 6.16 0.057182418 + 2 -205.404220272 -0.688182102 -0.019496153 0.004785564 7.02 0.060136343 + 3 -205.407981213 -0.691943043 -0.003760941 0.002015646 6.94 0.074251201 + 4 -205.409544734 -0.693506564 -0.001563521 0.001703525 6.18 0.080911850 + 5 -205.410096671 -0.694058500 -0.000551937 0.000980318 6.67 0.086517100 + 6 -205.410208841 -0.694170671 -0.000112171 0.000600528 7.32 0.089412475 + 7 -205.410256671 -0.694218501 -0.000047830 0.000261551 6.15 0.090817460 + 8 -205.410269906 -0.694231736 -0.000013235 0.000135102 6.08 0.091374014 + 9 -205.410265527 -0.694227356 0.000004380 0.000039369 7.15 0.091544540 + 10 -205.410270902 -0.694232732 -0.000005376 0.000025721 6.21 0.091602410 + 11 -205.410267848 -0.694229677 0.000003055 0.000020020 5.84 0.091594497 + 12 -205.410269271 -0.694231101 -0.000001423 0.000014791 5.67 0.091608143 + 13 -205.410269008 -0.694230837 0.000000263 0.000009439 6.85 0.091603014 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.716038170 +E(CORR) ... -0.694230837 +E(TOT) ... -205.410269008 +Singles norm **1/2 ... 0.091603014 ( 0.045801507, 0.045801507) +T1 diagnostic ... 0.021591038 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.054789 + 8a-> 13a -1a-> -1a 0.035569 + 8b-> 13b -1b-> -1b 0.035569 + 8a-> 13a 9b-> 13b 0.035456 + 9a-> 13a 8b-> 13b 0.035456 + 10b-> 13b -1b-> -1b 0.034661 + 10a-> 13a -1a-> -1a 0.034661 + 9a-> 13a 9b-> 13b 0.034420 + 10a-> 13a 10b-> 13b 0.034212 + 11a-> 13a 11b-> 13b 0.028025 + 5a-> 13a 5b-> 13b 0.027413 + 10a-> 13a 9b-> 13b 0.026635 + 9a-> 13a 10b-> 13b 0.026635 + 8a-> 13a 10b-> 13b 0.025887 + 10a-> 13a 8b-> 13b 0.025887 + 11a-> 26a 11b-> 26b 0.023095 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034657806 + alpha-alpha-alpha ... -0.000887650 ( 2.6%) + alpha-alpha-beta ... -0.016441253 ( 47.4%) + alpha-beta -beta ... -0.016441253 ( 47.4%) + beta -beta -beta ... -0.000887650 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034657806 + +Final correlation energy ... -0.728888643 +E(CCSD) ... -205.410269008 +E(CCSD(T)) ... -205.444926813 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210692285 sqrt= 1.100314630 +W(HF) = 0.825973711 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 121.784 sec + +Fock Matrix Formation ... 0.603 sec ( 0.5%) +Initial Guess ... 0.186 sec ( 0.2%) +DIIS Solver ... 5.902 sec ( 4.8%) +State Vector Update ... 0.329 sec ( 0.3%) +Sigma-vector construction ... 84.575 sec ( 69.4%) + <0|H|D> ... 0.007 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.048 sec ( 0.1% of sigma) + (0-ext) ... 0.164 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.057 sec ( 0.1% of sigma) + (2-ext) ... 2.054 sec ( 2.4% of sigma) + (4-ext) ... 47.928 sec ( 56.7% of sigma) + ... 4.687 sec ( 5.5% of sigma) + ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.020 sec ( 0.0% of sigma) + (1-ext) ... 0.245 sec ( 0.3% of sigma) + Fock-dressing ... 5.804 sec ( 6.9% of sigma) + (ik|jl)-dressing ... 0.198 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 19.093 sec ( 22.6% of sigma) + Pair energies ... 0.028 sec ( 0.0% of sigma) +Total Time for computing (T) ... 15.817 sec ( 13.0% of ALL) + I/O of integral and amplitudes ... 1.136 sec ( 7.2% of (T)) + External N**7 contributions ... 5.949 sec ( 37.6% of (T)) + Internal N**7 contributions ... 0.474 sec ( 3.0% of (T)) + N**6 triples energy contributions ... 2.340 sec ( 14.8% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.444926813238 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.004646327 -0.008151442 -0.000353252 + 2 N : 0.003978576 -0.008394073 0.002817793 + 3 O : -0.002745455 0.007553341 -0.002176819 + 4 H : 0.003413206 0.008992174 -0.000287721 + +Norm of the cartesian gradient ... 0.018555582 +RMS gradient ... 0.005356535 +MAX gradient ... 0.008992174 + +------- +TIMINGS +------- + +Total numerical gradient time ... 809.669 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.444926813 Eh +Current gradient norm .... 0.018555582 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999611 +Lowest eigenvalues of augmented Hessian: + -0.000000197 0.112668556 0.173879714 0.488718947 0.504941550 +Length of the computed step .... 0.000882284 +The final length of the internal step .... 0.000882284 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0003601909 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0002547229 RMS(Int)= 0.0003602003 + Iter 1: RMS(Cart)= 0.0000000638 RMS(Int)= 0.0000000945 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000442042 0.0000050000 NO + RMS gradient 0.0001093582 0.0001000000 NO + MAX gradient 0.0002052942 0.0003000000 YES + RMS step 0.0003601909 0.0020000000 YES + MAX step 0.0006422979 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0003 Max(Angles) 0.03 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4606 -0.000083 0.0003 1.4610 + 2. B(O 2,N 1) 1.1699 -0.000097 0.0000 1.1699 + 3. B(H 3,O 0) 0.9690 -0.000111 0.0001 0.9692 + 4. A(N 1,O 0,H 3) 102.06 -0.000029 0.01 102.07 + 5. A(O 0,N 1,O 2) 110.52 0.000205 -0.03 110.49 + 6. D(O 2,N 1,O 0,H 3) 139.09 -0.017234 -0.00 139.09 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.284929 -0.062864 0.748183 + N 0.181332 -0.277413 -0.619675 + O 1.290208 0.077468 -0.734670 + H -1.186610 0.262809 0.606161 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.538437 -0.118796 1.413862 + 1 N 7.0000 0 14.007 0.342669 -0.524234 -1.171015 + 2 O 8.0000 0 15.999 2.438139 0.146393 -1.388325 + 3 H 1.0000 0 1.008 -2.242368 0.496637 1.145479 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.460981094503 0.00000000 0.00000000 + O 2 1 0 1.169943814589 110.48518899 0.00000000 + H 1 2 3 0.969155460257 102.06784278 139.09090891 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.760854155447 0.00000000 0.00000000 + O 2 1 0 2.210873401648 110.48518899 0.00000000 + H 1 2 3 1.831438401080 102.06784278 139.09090891 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.1 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.1 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2224 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2689 + la=0 lb=0: 547 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 391 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.038152022953 Eh + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.0381520230 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.961e-04 +Time for diagonalization ... 0.006 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.004 sec +Total time needed ... 0.011 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7159985993 0.000000000000 0.00001931 0.00000044 0.0001061 0.7000 + 1 -204.7159986445 -0.000000045251 0.00001212 0.00000037 0.0000857 0.7000 + ***Turning on DIIS*** + 2 -204.7159986821 -0.000000037622 0.00002330 0.00000097 0.0000678 0.0000 + 3 -204.7160322276 -0.000033545449 0.00000995 0.00000041 0.0000196 0.0000 + 4 -204.7159972788 0.000034948805 0.00000371 0.00000013 0.0000054 0.0000 + 5 -204.7159744309 0.000022847881 0.00000226 0.00000007 0.0000037 0.0000 + 6 -204.7160068986 -0.000032467656 0.00000155 0.00000006 0.0000018 0.0000 + 7 -204.7159977516 0.000009146922 0.00000114 0.00000004 0.0000013 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71599684 Eh -5570.60548 eV + +Components: +Nuclear Repulsion : 69.03815202 Eh 1878.62362 eV +Electronic Energy : -273.75414886 Eh -7449.22910 eV +One Electron Energy: -417.79053619 Eh -11368.65846 eV +Two Electron Energy: 144.03638733 Eh 3919.42936 eV + +Virial components: +Potential Energy : -408.95681484 Eh -11128.28068 eV +Kinetic Energy : 204.24081800 Eh 5557.67520 eV +Virial Ratio : 2.00232656 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 9.1278e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.4898e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.0791e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.8709e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.677306 -562.6581 + 1 1.0000 -20.629540 -561.3583 + 2 1.0000 -15.800829 -429.9624 + 3 1.0000 -1.609298 -43.7912 + 4 1.0000 -1.389089 -37.7990 + 5 1.0000 -0.949877 -25.8475 + 6 1.0000 -0.777540 -21.1580 + 7 1.0000 -0.729121 -19.8404 + 8 1.0000 -0.691441 -18.8151 + 9 1.0000 -0.615161 -16.7394 + 10 1.0000 -0.529557 -14.4100 + 11 1.0000 -0.460123 -12.5206 + 12 0.0000 0.029250 0.7959 + 13 0.0000 0.075395 2.0516 + 14 0.0000 0.092746 2.5238 + 15 0.0000 0.099448 2.7061 + 16 0.0000 0.120552 3.2804 + 17 0.0000 0.150067 4.0835 + 18 0.0000 0.157216 4.2781 + 19 0.0000 0.172762 4.7011 + 20 0.0000 0.186486 5.0745 + 21 0.0000 0.192771 5.2456 + 22 0.0000 0.203548 5.5388 + 23 0.0000 0.236188 6.4270 + 24 0.0000 0.267031 7.2663 + 25 0.0000 0.286279 7.7901 + 26 0.0000 0.310444 8.4476 + 27 0.0000 0.329060 8.9542 + 28 0.0000 0.351326 9.5601 + 29 0.0000 0.365472 9.9450 + 30 0.0000 0.423796 11.5321 + 31 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83.5391 + 100 0.0000 3.128300 85.1254 + 101 0.0000 3.171090 86.2897 + 102 0.0000 3.263161 88.7951 + 103 0.0000 3.474751 94.5528 + 104 0.0000 3.741859 101.8211 + 105 0.0000 3.883339 105.6710 + 106 0.0000 4.035530 109.8123 + 107 0.0000 4.158333 113.1540 + 108 0.0000 4.198934 114.2588 + 109 0.0000 4.293362 116.8283 + 110 0.0000 4.371210 118.9467 + 111 0.0000 4.390947 119.4837 + 112 0.0000 4.549915 123.8095 + 113 0.0000 4.629671 125.9798 + 114 0.0000 4.748666 129.2178 + 115 0.0000 4.757825 129.4670 + 116 0.0000 4.788538 130.3027 + 117 0.0000 4.885398 132.9384 + 118 0.0000 4.953855 134.8012 + 119 0.0000 4.992254 135.8462 + 120 0.0000 5.070894 137.9860 + 121 0.0000 5.096730 138.6891 + 122 0.0000 5.177783 140.8946 + 123 0.0000 5.208900 141.7414 + 124 0.0000 5.255261 143.0029 + 125 0.0000 5.328781 145.0035 + 126 0.0000 5.360739 145.8731 + 127 0.0000 5.405671 147.0958 + 128 0.0000 5.548511 150.9827 + 129 0.0000 5.698827 155.0730 + 130 0.0000 5.793090 157.6380 + 131 0.0000 5.992746 163.0709 + 132 0.0000 6.127189 166.7293 + 133 0.0000 6.404401 174.2726 + 134 0.0000 6.495759 176.7586 + 135 0.0000 6.508990 177.1186 + 136 0.0000 6.699500 182.3027 + 137 0.0000 6.702324 182.3795 + 138 0.0000 6.746592 183.5841 + 139 0.0000 6.837539 186.0589 + 140 0.0000 6.895289 187.6304 + 141 0.0000 7.067851 192.3260 + 142 0.0000 7.121723 193.7919 + 143 0.0000 7.159733 194.8262 + 144 0.0000 7.189833 195.6453 + 145 0.0000 7.234313 196.8557 + 146 0.0000 7.268830 197.7949 + 147 0.0000 7.355079 200.1419 + 148 0.0000 7.400651 201.3820 + 149 0.0000 7.443734 202.5543 + 150 0.0000 7.480546 203.5560 + 151 0.0000 7.566658 205.8992 + 152 0.0000 7.619835 207.3463 + 153 0.0000 7.649847 208.1629 + 154 0.0000 7.881957 214.4790 + 155 0.0000 7.896656 214.8789 + 156 0.0000 8.012099 218.0203 + 157 0.0000 8.381397 228.0694 + 158 0.0000 14.083783 383.2392 + 159 0.0000 14.905388 405.5962 + 160 0.0000 16.139631 439.1817 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.677306 -562.6581 + 1 1.0000 -20.629540 -561.3583 + 2 1.0000 -15.800829 -429.9624 + 3 1.0000 -1.609298 -43.7912 + 4 1.0000 -1.389089 -37.7990 + 5 1.0000 -0.949877 -25.8475 + 6 1.0000 -0.777540 -21.1580 + 7 1.0000 -0.729121 -19.8404 + 8 1.0000 -0.691441 -18.8151 + 9 1.0000 -0.615161 -16.7394 + 10 1.0000 -0.529557 -14.4100 + 11 1.0000 -0.460123 -12.5206 + 12 0.0000 0.029250 0.7959 + 13 0.0000 0.075395 2.0516 + 14 0.0000 0.092746 2.5238 + 15 0.0000 0.099448 2.7061 + 16 0.0000 0.120552 3.2804 + 17 0.0000 0.150067 4.0835 + 18 0.0000 0.157216 4.2781 + 19 0.0000 0.172762 4.7011 + 20 0.0000 0.186486 5.0745 + 21 0.0000 0.192771 5.2456 + 22 0.0000 0.203548 5.5388 + 23 0.0000 0.236188 6.4270 + 24 0.0000 0.267031 7.2663 + 25 0.0000 0.286279 7.7901 + 26 0.0000 0.310444 8.4476 + 27 0.0000 0.329060 8.9542 + 28 0.0000 0.351326 9.5601 + 29 0.0000 0.365472 9.9450 + 30 0.0000 0.423796 11.5321 + 31 0.0000 0.513287 13.9673 + 32 0.0000 0.520819 14.1722 + 33 0.0000 0.546521 14.8716 + 34 0.0000 0.570238 15.5170 + 35 0.0000 0.611646 16.6437 + 36 0.0000 0.633348 17.2343 + 37 0.0000 0.647140 17.6096 + 38 0.0000 0.701295 19.0832 + 39 0.0000 0.719902 19.5895 + 40 0.0000 0.731971 19.9179 + 41 0.0000 0.743264 20.2252 + 42 0.0000 0.776419 21.1274 + 43 0.0000 0.794066 21.6076 + 44 0.0000 0.801489 21.8096 + 45 0.0000 0.823205 22.4005 + 46 0.0000 0.848303 23.0835 + 47 0.0000 0.860778 23.4230 + 48 0.0000 0.923984 25.1429 + 49 0.0000 0.946425 25.7535 + 50 0.0000 0.961073 26.1521 + 51 0.0000 1.010575 27.4991 + 52 0.0000 1.020936 27.7811 + 53 0.0000 1.031953 28.0809 + 54 0.0000 1.047829 28.5129 + 55 0.0000 1.088150 29.6101 + 56 0.0000 1.152953 31.3735 + 57 0.0000 1.206487 32.8302 + 58 0.0000 1.255012 34.1506 + 59 0.0000 1.310434 35.6587 + 60 0.0000 1.373264 37.3684 + 61 0.0000 1.406176 38.2640 + 62 0.0000 1.461410 39.7670 + 63 0.0000 1.511303 41.1246 + 64 0.0000 1.529625 41.6232 + 65 0.0000 1.543996 42.0143 + 66 0.0000 1.567142 42.6441 + 67 0.0000 1.627359 44.2827 + 68 0.0000 1.668878 45.4125 + 69 0.0000 1.716636 46.7120 + 70 0.0000 1.783675 48.5363 + 71 0.0000 1.796440 48.8836 + 72 0.0000 1.880745 51.1777 + 73 0.0000 1.930239 52.5245 + 74 0.0000 1.960475 53.3472 + 75 0.0000 2.032763 55.3143 + 76 0.0000 2.051918 55.8355 + 77 0.0000 2.102335 57.2074 + 78 0.0000 2.158676 58.7406 + 79 0.0000 2.193077 59.6767 + 80 0.0000 2.280675 62.0603 + 81 0.0000 2.285588 62.1940 + 82 0.0000 2.311558 62.9007 + 83 0.0000 2.375234 64.6334 + 84 0.0000 2.439558 66.3837 + 85 0.0000 2.463410 67.0328 + 86 0.0000 2.483193 67.5711 + 87 0.0000 2.497295 67.9548 + 88 0.0000 2.509395 68.2841 + 89 0.0000 2.532023 68.8998 + 90 0.0000 2.572800 70.0094 + 91 0.0000 2.604886 70.8825 + 92 0.0000 2.659493 72.3685 + 93 0.0000 2.707095 73.6638 + 94 0.0000 2.733937 74.3942 + 95 0.0000 2.788002 75.8654 + 96 0.0000 2.814239 76.5793 + 97 0.0000 2.902039 78.9685 + 98 0.0000 2.956317 80.4455 + 99 0.0000 3.070006 83.5391 + 100 0.0000 3.128300 85.1254 + 101 0.0000 3.171090 86.2897 + 102 0.0000 3.263161 88.7951 + 103 0.0000 3.474751 94.5528 + 104 0.0000 3.741859 101.8211 + 105 0.0000 3.883339 105.6710 + 106 0.0000 4.035530 109.8123 + 107 0.0000 4.158333 113.1540 + 108 0.0000 4.198934 114.2588 + 109 0.0000 4.293362 116.8283 + 110 0.0000 4.371210 118.9467 + 111 0.0000 4.390947 119.4837 + 112 0.0000 4.549915 123.8095 + 113 0.0000 4.629671 125.9798 + 114 0.0000 4.748666 129.2178 + 115 0.0000 4.757825 129.4670 + 116 0.0000 4.788538 130.3027 + 117 0.0000 4.885398 132.9384 + 118 0.0000 4.953855 134.8012 + 119 0.0000 4.992254 135.8462 + 120 0.0000 5.070894 137.9860 + 121 0.0000 5.096730 138.6891 + 122 0.0000 5.177783 140.8946 + 123 0.0000 5.208900 141.7414 + 124 0.0000 5.255261 143.0029 + 125 0.0000 5.328781 145.0035 + 126 0.0000 5.360739 145.8731 + 127 0.0000 5.405671 147.0958 + 128 0.0000 5.548511 150.9827 + 129 0.0000 5.698827 155.0730 + 130 0.0000 5.793090 157.6380 + 131 0.0000 5.992746 163.0709 + 132 0.0000 6.127189 166.7293 + 133 0.0000 6.404401 174.2726 + 134 0.0000 6.495759 176.7586 + 135 0.0000 6.508990 177.1186 + 136 0.0000 6.699500 182.3027 + 137 0.0000 6.702324 182.3795 + 138 0.0000 6.746592 183.5841 + 139 0.0000 6.837539 186.0589 + 140 0.0000 6.895289 187.6304 + 141 0.0000 7.067851 192.3260 + 142 0.0000 7.121723 193.7919 + 143 0.0000 7.159733 194.8262 + 144 0.0000 7.189833 195.6453 + 145 0.0000 7.234313 196.8557 + 146 0.0000 7.268830 197.7949 + 147 0.0000 7.355079 200.1419 + 148 0.0000 7.400651 201.3820 + 149 0.0000 7.443734 202.5543 + 150 0.0000 7.480546 203.5560 + 151 0.0000 7.566658 205.8992 + 152 0.0000 7.619835 207.3463 + 153 0.0000 7.649847 208.1629 + 154 0.0000 7.881957 214.4790 + 155 0.0000 7.896656 214.8789 + 156 0.0000 8.012099 218.0203 + 157 0.0000 8.381397 228.0694 + 158 0.0000 14.083783 383.2392 + 159 0.0000 14.905388 405.5962 + 160 0.0000 16.139631 439.1817 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.357135 0.000000 + 1 N : 0.348820 0.000000 + 2 O : -0.258881 0.000000 + 3 H : 0.267197 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.868876 s : 3.868876 + pz : 1.280179 p : 4.460815 + px : 1.387010 + py : 1.793626 + dz2 : 0.009831 d : 0.022879 + dxz : 0.005240 + dyz : 0.006151 + dx2y2 : 0.001500 + dxy : 0.000157 + f0 : 0.001981 f : 0.004566 + f+1 : 0.000464 + f-1 : 0.001094 + f+2 : 0.000142 + f-2 : 0.000186 + f+3 : 0.000200 + f-3 : 0.000498 + 1 N s : 3.827950 s : 3.827950 + pz : 0.880430 p : 2.655780 + px : 0.969931 + py : 0.805419 + dz2 : 0.030719 d : 0.137236 + dxz : 0.043692 + dyz : 0.017816 + dx2y2 : 0.016708 + dxy : 0.028300 + f0 : 0.009015 f : 0.030215 + f+1 : 0.004119 + f-1 : 0.005943 + f+2 : 0.003219 + f-2 : 0.002480 + f+3 : 0.003104 + f-3 : 0.002335 + 2 O s : 3.879015 s : 3.879015 + pz : 1.839738 p : 4.308420 + px : 1.182775 + py : 1.285906 + dz2 : 0.004987 d : 0.063767 + dxz : 0.014741 + dyz : 0.001870 + dx2y2 : 0.018044 + dxy : 0.024126 + f0 : 0.001158 f : 0.007680 + f+1 : 0.000993 + f-1 : 0.000414 + f+2 : 0.000784 + f-2 : 0.000422 + f+3 : 0.002164 + f-3 : 0.001745 + 3 H s : 0.628963 s : 0.628963 + pz : 0.019248 p : 0.082003 + px : 0.022002 + py : 0.040753 + dz2 : 0.000479 d : 0.021838 + dxz : 0.008458 + dyz : 0.001267 + dx2y2 : 0.005280 + dxy : 0.006352 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.591791 0.000000 + 1 N : -0.254683 0.000000 + 2 O : 0.241865 0.000000 + 3 H : -0.578973 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.122433 s : 3.122433 + pz : 1.216124 p : 3.925163 + px : 1.270529 + py : 1.438511 + dz2 : 0.114633 d : 0.277588 + dxz : 0.066183 + dyz : 0.046952 + dx2y2 : 0.029945 + dxy : 0.019875 + f0 : 0.028457 f : 0.083025 + f+1 : 0.019729 + f-1 : 0.014445 + f+2 : 0.009071 + f-2 : 0.006507 + f+3 : 0.001471 + f-3 : 0.003345 + 1 N s : 3.016045 s : 3.016045 + pz : 0.924443 p : 2.837121 + px : 1.133824 + py : 0.778854 + dz2 : 0.215920 d : 0.951195 + dxz : 0.309861 + dyz : 0.107138 + dx2y2 : 0.155484 + dxy : 0.162791 + f0 : 0.116381 f : 0.450322 + f+1 : 0.068081 + f-1 : 0.059138 + f+2 : 0.062871 + f-2 : 0.036346 + f+3 : 0.054579 + f-3 : 0.052926 + 2 O s : 3.316147 s : 3.316147 + pz : 1.494718 p : 3.995929 + px : 1.366843 + py : 1.134369 + dz2 : 0.047754 d : 0.327828 + dxz : 0.105160 + dyz : 0.010090 + dx2y2 : 0.084408 + dxy : 0.080416 + f0 : 0.015285 f : 0.118231 + f+1 : 0.021186 + f-1 : 0.004233 + f+2 : 0.021383 + f-2 : 0.007972 + f+3 : 0.022231 + f-3 : 0.025941 + 3 H s : 0.623727 s : 0.623727 + pz : 0.139261 p : 0.561570 + px : 0.248423 + py : 0.173886 + dz2 : 0.035392 d : 0.393676 + dxz : 0.120666 + dyz : 0.021536 + dx2y2 : 0.104080 + dxy : 0.112003 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3571 8.0000 -0.3571 1.8901 1.8901 -0.0000 + 1 N 6.6512 7.0000 0.3488 2.5516 2.5516 0.0000 + 2 O 8.2589 8.0000 -0.2589 1.7579 1.7579 -0.0000 + 3 H 0.7328 1.0000 0.2672 0.9569 0.9569 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8712 B( 0-O , 3-H ) : 0.9624 B( 1-N , 2-O ) : 1.6937 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 4 sec + +Total time .... 4.080 sec +Sum of individual times .... 3.330 sec ( 81.6%) + +Fock matrix formation .... 2.680 sec ( 65.7%) +Diagonalization .... 0.212 sec ( 5.2%) +Density matrix formation .... 0.014 sec ( 0.4%) +Population analysis .... 0.231 sec ( 5.7%) +Initial guess .... 0.021 sec ( 0.5%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.013 sec ( 0.3%) +DIIS solution .... 0.172 sec ( 4.2%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.618 sec +Reference energy ... -204.715998806 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 10.510 sec +AO-integral generation ... 0.428 sec +Half transformation ... 0.215 sec +K-integral sorting ... 8.171 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: + 251940 b 0 skpd 0.053 s ( 0.000 ms/b) +: : 377910 b 0 skpd 0.056 s ( 0.000 ms/b) + 277134 b 0 skpd 0.078 s ( 0.000 ms/b) +: : 151164 b 0 skpd 0.124 s ( 0.001 ms/b) + 159120 b 0 skpd 0.038 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.080 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.084 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.060 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.100 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.062 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.855 sec +AO-integral generation ... 0.651 sec +Half transformation ... 0.091 sec +J-integral sorting ... 0.086 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.244 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.378 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090359045 +EMP2(bb)= -0.090359045 +EMP2(ab)= -0.516806963 + +Initial guess performed in 0.179 sec +E(0) ... -204.715998806 +E(MP2) ... -0.697525053 +Initial E(tot) ... -205.413523859 + ... 0.188552391 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.413523859 -0.697525053 -0.000000000 0.022684685 6.27 0.000001648 + *** Turning on DIIS *** + 1 -205.384707825 -0.668709018 0.028816034 0.009377641 5.55 0.057195932 + 2 -205.404209985 -0.688211179 -0.019502161 0.004784671 6.73 0.060147687 + 3 -205.407972179 -0.691973373 -0.003762194 0.002017275 6.33 0.074267035 + 4 -205.409536336 -0.693537529 -0.001564156 0.001705225 5.79 0.080929810 + 5 -205.410088654 -0.694089848 -0.000552319 0.000981356 7.10 0.086538782 + 6 -205.410200922 -0.694202116 -0.000112268 0.000601343 8.37 0.089437064 + 7 -205.410248824 -0.694250017 -0.000047902 0.000261882 7.13 0.090844725 + 8 -205.410262095 -0.694263289 -0.000013272 0.000135301 5.77 0.091402575 + 9 -205.410257712 -0.694258906 0.000004383 0.000039416 6.04 0.091573641 + 10 -205.410263101 -0.694264295 -0.000005389 0.000025876 6.09 0.091631713 + 11 -205.410260038 -0.694261232 0.000003063 0.000020130 5.83 0.091623802 + 12 -205.410261467 -0.694262660 -0.000001428 0.000014860 6.46 0.091637526 + 13 -205.410261202 -0.694262395 0.000000265 0.000009472 5.49 0.091632373 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.715998806 +E(CORR) ... -0.694262395 +E(TOT) ... -205.410261202 +Singles norm **1/2 ... 0.091632373 ( 0.045816186, 0.045816186) +T1 diagnostic ... 0.021597957 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.054853 + 8b-> 13b -1b-> -1b 0.035563 + 8a-> 13a -1a-> -1a 0.035563 + 9a-> 13a 8b-> 13b 0.035482 + 8a-> 13a 9b-> 13b 0.035482 + 10b-> 13b -1b-> -1b 0.034700 + 10a-> 13a -1a-> -1a 0.034700 + 9a-> 13a 9b-> 13b 0.034414 + 10a-> 13a 10b-> 13b 0.034177 + 11a-> 13a 11b-> 13b 0.028009 + 5a-> 13a 5b-> 13b 0.027430 + 9a-> 13a 10b-> 13b 0.026618 + 10a-> 13a 9b-> 13b 0.026618 + 10a-> 13a 8b-> 13b 0.025894 + 8a-> 13a 10b-> 13b 0.025894 + 11a-> 26a 11b-> 26b 0.022994 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034665706 + alpha-alpha-alpha ... -0.000887733 ( 2.6%) + alpha-alpha-beta ... -0.016445120 ( 47.4%) + alpha-beta -beta ... -0.016445120 ( 47.4%) + beta -beta -beta ... -0.000887733 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034665706 + +Final correlation energy ... -0.728928101 +E(CCSD) ... -205.410261202 +E(CCSD(T)) ... -205.444926907 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210740322 sqrt= 1.100336459 +W(HF) = 0.825940940 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.277892 0.000000 + 1 N : 0.163314 -0.000000 + 2 O : -0.140000 0.000000 + 3 H : 0.254578 -0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.846307 s : 3.846307 + pz : 1.269821 p : 4.368412 + px : 1.373475 + py : 1.725116 + dz2 : 0.014577 d : 0.054819 + dxz : 0.011052 + dyz : 0.013522 + dx2y2 : 0.008528 + dxy : 0.007140 + f0 : 0.002183 f : 0.008354 + f+1 : 0.000943 + f-1 : 0.001627 + f+2 : 0.000803 + f-2 : 0.000834 + f+3 : 0.000845 + f-3 : 0.001118 + 1 N s : 3.880800 s : 3.880800 + pz : 0.915184 p : 2.758604 + px : 0.962593 + py : 0.880826 + dz2 : 0.036647 d : 0.167770 + dxz : 0.054122 + dyz : 0.026600 + dx2y2 : 0.019473 + dxy : 0.030928 + f0 : 0.008689 f : 0.029513 + f+1 : 0.003829 + f-1 : 0.005918 + f+2 : 0.003568 + f-2 : 0.002854 + f+3 : 0.002455 + f-3 : 0.002201 + 2 O s : 3.865973 s : 3.865973 + pz : 1.754071 p : 4.178878 + px : 1.170749 + py : 1.254059 + dz2 : 0.010098 d : 0.084980 + dxz : 0.022550 + dyz : 0.008231 + dx2y2 : 0.019087 + dxy : 0.025014 + f0 : 0.001648 f : 0.010169 + f+1 : 0.001462 + f-1 : 0.000880 + f+2 : 0.001316 + f-2 : 0.000990 + f+3 : 0.002065 + f-3 : 0.001808 + 3 H s : 0.639460 s : 0.639460 + pz : 0.022876 p : 0.087200 + px : 0.017541 + py : 0.046783 + dz2 : 0.000738 d : 0.018762 + dxz : 0.007557 + dyz : 0.001188 + dx2y2 : 0.004059 + dxy : 0.005220 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.605229 0.000000 + 1 N : -0.302898 -0.000000 + 2 O : 0.277901 -0.000000 + 3 H : -0.580233 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.128603 s : 3.128603 + pz : 1.217882 p : 3.867628 + px : 1.262688 + py : 1.387057 + dz2 : 0.120907 d : 0.308597 + dxz : 0.071932 + dyz : 0.052744 + dx2y2 : 0.036985 + dxy : 0.026029 + f0 : 0.029589 f : 0.089943 + f+1 : 0.021300 + f-1 : 0.015714 + f+2 : 0.009676 + f-2 : 0.007272 + f+3 : 0.002184 + f-3 : 0.004207 + 1 N s : 3.021113 s : 3.021113 + pz : 0.936229 p : 2.881834 + px : 1.122189 + py : 0.823416 + dz2 : 0.222941 d : 0.960617 + dxz : 0.308033 + dyz : 0.109071 + dx2y2 : 0.157489 + dxy : 0.163084 + f0 : 0.114021 f : 0.439334 + f+1 : 0.068025 + f-1 : 0.056879 + f+2 : 0.058382 + f-2 : 0.034699 + f+3 : 0.054409 + f-3 : 0.052918 + 2 O s : 3.318228 s : 3.318228 + pz : 1.439460 p : 3.919295 + px : 1.359282 + py : 1.120553 + dz2 : 0.053527 d : 0.357835 + dxz : 0.107271 + dyz : 0.016505 + dx2y2 : 0.091467 + dxy : 0.089065 + f0 : 0.015810 f : 0.126741 + f+1 : 0.021824 + f-1 : 0.004859 + f+2 : 0.021317 + f-2 : 0.009171 + f+3 : 0.025807 + f-3 : 0.027952 + 3 H s : 0.624988 s : 0.624988 + pz : 0.140591 p : 0.571930 + px : 0.251919 + py : 0.179420 + dz2 : 0.036834 d : 0.383314 + dxz : 0.116636 + dyz : 0.020699 + dx2y2 : 0.101414 + dxy : 0.107732 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2779 8.0000 -0.2779 2.2526 1.7911 0.4615 + 1 N 6.8367 7.0000 0.1633 2.8338 2.3510 0.4828 + 2 O 8.1400 8.0000 -0.1400 2.1540 1.6563 0.4978 + 3 H 0.7454 1.0000 0.2546 0.9788 0.9069 0.0719 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8007 B( 0-O , 3-H ) : 0.8938 B( 1-N , 2-O ) : 1.5485 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 118.658 sec + +Fock Matrix Formation ... 0.618 sec ( 0.5%) +Initial Guess ... 0.179 sec ( 0.2%) +DIIS Solver ... 5.073 sec ( 4.3%) +State Vector Update ... 0.261 sec ( 0.2%) +Sigma-vector construction ... 83.624 sec ( 70.5%) + <0|H|D> ... 0.007 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.042 sec ( 0.0% of sigma) + (0-ext) ... 0.142 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.054 sec ( 0.1% of sigma) + (2-ext) ... 1.881 sec ( 2.2% of sigma) + (4-ext) ... 48.716 sec ( 58.3% of sigma) + ... 4.539 sec ( 5.4% of sigma) + ... 0.005 sec ( 0.0% of sigma) + (1-ext) ... 0.019 sec ( 0.0% of sigma) + (1-ext) ... 0.212 sec ( 0.3% of sigma) + Fock-dressing ... 5.879 sec ( 7.0% of sigma) + (ik|jl)-dressing ... 0.154 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 17.918 sec ( 21.4% of sigma) + Pair energies ... 0.021 sec ( 0.0% of sigma) +Total Time for computing (T) ... 14.685 sec ( 12.4% of ALL) + I/O of integral and amplitudes ... 1.152 sec ( 7.8% of (T)) + External N**7 contributions ... 5.852 sec ( 39.9% of (T)) + Internal N**7 contributions ... 0.483 sec ( 3.3% of (T)) + N**6 triples energy contributions ... 2.366 sec ( 16.1% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.444926907461 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.040.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.040.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.700504, -0.136150 -0.315640) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.70355 -0.14911 -0.84660 +Nuclear contribution : -1.45816 0.31537 0.72804 + ----------------------------------------- +Total Dipole Moment : -0.75461 0.16626 -0.11857 + ----------------------------------------- +Magnitude (a.u.) : 0.78175 +Magnitude (Debye) : 1.98706 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.939720 0.410620 0.365704 +Rotational constants in MHz : 88130.598209 12310.072625 10963.534826 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.456307 -0.499904 -0.391174 +x,y,z [Debye]: 1.159840 -1.270655 -0.994285 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.700504, -0.136150 -0.315640) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.87250 -0.12265 -0.81903 +Nuclear contribution : -1.45816 0.31537 0.72804 + ----------------------------------------- +Total Dipole Moment : -0.58566 0.19272 -0.09099 + ----------------------------------------- +Magnitude (a.u.) : 0.62323 +Magnitude (Debye) : 1.58414 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.939720 0.410620 0.365704 +Rotational constants in MHz : 88130.598209 12310.072625 10963.534826 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.352780 -0.364006 -0.362584 +x,y,z [Debye]: 0.896694 -0.925230 -0.921616 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 41 * + * * + * Dihedral ( 2, 1, 0, 3) : 147.27272727 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0398873768 RMS(Int)= 0.0002204494 + Iter 1: RMS(Cart)= 0.0000615768 RMS(Int)= 0.0000010728 + Iter 2: RMS(Cart)= 0.0000002997 RMS(Int)= 0.0000000052 + Iter 3: RMS(Cart)= 0.0000000015 RMS(Int)= 0.0000000000 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4611 0.000000 + 2. B(O 2,N 1) 1.1721 0.000000 + 3. B(H 3,O 0) 0.9719 0.000000 + 4. A(N 1,O 0,H 3) 102.0255 0.000000 + 5. A(O 0,N 1,O 2) 110.4269 0.000000 + 6. D(O 2,N 1,O 0,H 3) 147.2727 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.276676 -0.030461 0.745922 + N 0.175204 -0.242687 -0.627202 + O 1.306173 0.045549 -0.734826 + H -1.204700 0.227599 0.616105 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.522841 -0.057562 1.409589 + 1 N 7.0000 0 14.007 0.331088 -0.458612 -1.185239 + 2 O 8.0000 0 15.999 2.468308 0.086076 -1.388620 + 3 H 1.0000 0 1.008 -2.276554 0.430099 1.164271 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.460981094503 0.00000000 0.00000000 + O 2 1 0 1.169943814589 110.48518899 0.00000000 + H 1 2 3 0.969155460257 102.06784278 139.09090891 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.760854155447 0.00000000 0.00000000 + O 2 1 0 2.210873401648 110.48518899 0.00000000 + H 1 2 3 1.831438401080 102.06784278 139.09090891 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.1 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2223 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2688 + la=0 lb=0: 547 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.952000292071 Eh + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 68.9520002921 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.987e-04 +Time for diagonalization ... 0.020 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.010 sec +Total time needed ... 0.033 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7126782635 0.000000000000 0.00176469 0.00005452 0.0199219 0.7000 + 1 -204.7135885586 -0.000910295066 0.00169397 0.00004916 0.0164769 0.7000 + ***Turning on DIIS*** + 2 -204.7143657093 -0.000777150698 0.00464822 0.00013287 0.0133773 0.0000 + 3 -204.7175261471 -0.003160437876 0.00181175 0.00005405 0.0052092 0.0000 + 4 -204.7163240483 0.001202098828 0.00086808 0.00002516 0.0020208 0.0000 + 5 -204.7178266500 -0.001502601657 0.00052472 0.00001998 0.0010535 0.0000 + 6 -204.7169943359 0.000832314036 0.00066932 0.00002373 0.0006109 0.0000 + 7 -204.7168258240 0.000168511887 0.00033006 0.00001197 0.0002862 0.0000 + 8 -204.7174510182 -0.000625194178 0.00017657 0.00000710 0.0002069 0.0000 + 9 -204.7170611220 0.000389896239 0.00015195 0.00000528 0.0001299 0.0000 + 10 -204.7172666910 -0.000205569024 0.00006712 0.00000219 0.0000546 0.0000 + 11 -204.7172522900 0.000014401020 0.00001546 0.00000049 0.0000237 0.0000 + 12 -204.7172032091 0.000049080835 0.00000576 0.00000020 0.0000097 0.0000 + 13 -204.7172247749 -0.000021565791 0.00000214 0.00000007 0.0000024 0.0000 + 14 -204.7172189851 0.000005789832 0.00000099 0.00000003 0.0000016 0.0000 + 15 -204.7172203235 -0.000001338364 0.00000056 0.00000002 0.0000012 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 16 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71722211 Eh -5570.63882 eV + +Components: +Nuclear Repulsion : 68.95200029 Eh 1876.27932 eV +Electronic Energy : -273.66922240 Eh -7446.91814 eV +One Electron Energy: -417.62634894 Eh -11364.19070 eV +Two Electron Energy: 143.95712654 Eh 3917.27256 eV + +Virial components: +Potential Energy : -408.93544133 Eh -11127.69908 eV +Kinetic Energy : 204.21821922 Eh 5557.06026 eV +Virial Ratio : 2.00244348 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.7852e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.3306e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.4226e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.8928e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.675808 -562.6173 + 1 1.0000 -20.632005 -561.4254 + 2 1.0000 -15.801669 -429.9853 + 3 1.0000 -1.606784 -43.7228 + 4 1.0000 -1.389318 -37.8053 + 5 1.0000 -0.949544 -25.8384 + 6 1.0000 -0.777461 -21.1558 + 7 1.0000 -0.728578 -19.8256 + 8 1.0000 -0.687392 -18.7049 + 9 1.0000 -0.618130 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2.5268 + 15 0.0000 0.098822 2.6891 + 16 0.0000 0.122939 3.3453 + 17 0.0000 0.148545 4.0421 + 18 0.0000 0.157034 4.2731 + 19 0.0000 0.172771 4.7013 + 20 0.0000 0.186866 5.0849 + 21 0.0000 0.194044 5.2802 + 22 0.0000 0.203761 5.5446 + 23 0.0000 0.235041 6.3958 + 24 0.0000 0.263970 7.1830 + 25 0.0000 0.286760 7.8031 + 26 0.0000 0.307790 8.3754 + 27 0.0000 0.328872 8.9491 + 28 0.0000 0.356253 9.6941 + 29 0.0000 0.368842 10.0367 + 30 0.0000 0.423447 11.5226 + 31 0.0000 0.512071 13.9342 + 32 0.0000 0.524352 14.2683 + 33 0.0000 0.546788 14.8789 + 34 0.0000 0.569491 15.4966 + 35 0.0000 0.612635 16.6706 + 36 0.0000 0.632646 17.2152 + 37 0.0000 0.646576 17.5942 + 38 0.0000 0.698374 19.0037 + 39 0.0000 0.717132 19.5142 + 40 0.0000 0.729371 19.8472 + 41 0.0000 0.744688 20.2640 + 42 0.0000 0.772219 21.0132 + 43 0.0000 0.792872 21.5752 + 44 0.0000 0.803782 21.8720 + 45 0.0000 0.819812 22.3082 + 46 0.0000 0.852010 23.1844 + 47 0.0000 0.861514 23.4430 + 48 0.0000 0.925777 25.1917 + 49 0.0000 0.944102 25.6903 + 50 0.0000 0.958358 26.0782 + 51 0.0000 1.009015 27.4567 + 52 0.0000 1.030295 28.0357 + 53 0.0000 1.042675 28.3726 + 54 0.0000 1.050280 28.5796 + 55 0.0000 1.085983 29.5511 + 56 0.0000 1.156509 31.4702 + 57 0.0000 1.199839 32.6493 + 58 0.0000 1.251413 34.0527 + 59 0.0000 1.307355 35.5749 + 60 0.0000 1.375874 37.4394 + 61 0.0000 1.405544 38.2468 + 62 0.0000 1.478667 40.2366 + 63 0.0000 1.511321 41.1251 + 64 0.0000 1.519567 41.3495 + 65 0.0000 1.539537 41.8929 + 66 0.0000 1.572644 42.7938 + 67 0.0000 1.615195 43.9517 + 68 0.0000 1.668146 45.3926 + 69 0.0000 1.721501 46.8444 + 70 0.0000 1.778468 48.3946 + 71 0.0000 1.798628 48.9432 + 72 0.0000 1.873016 50.9674 + 73 0.0000 1.931741 52.5654 + 74 0.0000 1.959065 53.3089 + 75 0.0000 2.027059 55.1591 + 76 0.0000 2.053707 55.8842 + 77 0.0000 2.100712 57.1633 + 78 0.0000 2.157739 58.7151 + 79 0.0000 2.189653 59.5835 + 80 0.0000 2.279155 62.0190 + 81 0.0000 2.294891 62.4472 + 82 0.0000 2.309015 62.8315 + 83 0.0000 2.376061 64.6559 + 84 0.0000 2.442063 66.4519 + 85 0.0000 2.464252 67.0557 + 86 0.0000 2.487037 67.6757 + 87 0.0000 2.500383 68.0389 + 88 0.0000 2.512228 68.3612 + 89 0.0000 2.527479 68.7762 + 90 0.0000 2.574302 70.0503 + 91 0.0000 2.603381 70.8416 + 92 0.0000 2.653287 72.1996 + 93 0.0000 2.716498 73.9197 + 94 0.0000 2.730031 74.2879 + 95 0.0000 2.755939 74.9929 + 96 0.0000 2.832299 77.0708 + 97 0.0000 2.895246 78.7836 + 98 0.0000 2.941086 80.0310 + 99 0.0000 3.077713 83.7488 + 100 0.0000 3.139542 85.4313 + 101 0.0000 3.177248 86.4573 + 102 0.0000 3.259038 88.6829 + 103 0.0000 3.465431 94.2992 + 104 0.0000 3.749730 102.0353 + 105 0.0000 3.886195 105.7487 + 106 0.0000 4.031045 109.6903 + 107 0.0000 4.156248 113.0973 + 108 0.0000 4.186431 113.9186 + 109 0.0000 4.274150 116.3055 + 110 0.0000 4.361131 118.6724 + 111 0.0000 4.398674 119.6940 + 112 0.0000 4.543590 123.6374 + 113 0.0000 4.627107 125.9100 + 114 0.0000 4.747347 129.1819 + 115 0.0000 4.781338 130.1068 + 116 0.0000 4.795188 130.4837 + 117 0.0000 4.888719 133.0288 + 118 0.0000 4.957113 134.8899 + 119 0.0000 4.995448 135.9330 + 120 0.0000 5.066311 137.8613 + 121 0.0000 5.098599 138.7399 + 122 0.0000 5.172256 140.7442 + 123 0.0000 5.222304 142.1061 + 124 0.0000 5.253791 142.9629 + 125 0.0000 5.320197 144.7699 + 126 0.0000 5.338444 145.2664 + 127 0.0000 5.399541 146.9290 + 128 0.0000 5.549927 151.0212 + 129 0.0000 5.688621 154.7953 + 130 0.0000 5.790932 157.5793 + 131 0.0000 5.993881 163.1018 + 132 0.0000 6.114412 166.3816 + 133 0.0000 6.403635 174.2518 + 134 0.0000 6.497623 176.8093 + 135 0.0000 6.507410 177.0756 + 136 0.0000 6.691736 182.0914 + 137 0.0000 6.705223 182.4584 + 138 0.0000 6.741685 183.4506 + 139 0.0000 6.838261 186.0785 + 140 0.0000 6.901127 187.7892 + 141 0.0000 7.059985 192.1120 + 142 0.0000 7.121675 193.7906 + 143 0.0000 7.171735 195.1528 + 144 0.0000 7.183278 195.4669 + 145 0.0000 7.228427 196.6955 + 146 0.0000 7.262325 197.6179 + 147 0.0000 7.346104 199.8976 + 148 0.0000 7.393110 201.1767 + 149 0.0000 7.434231 202.2957 + 150 0.0000 7.477665 203.4776 + 151 0.0000 7.585489 206.4117 + 152 0.0000 7.615958 207.2407 + 153 0.0000 7.661510 208.4803 + 154 0.0000 7.849136 213.5858 + 155 0.0000 7.904188 215.0839 + 156 0.0000 8.016686 218.1451 + 157 0.0000 8.378226 227.9831 + 158 0.0000 14.065712 382.7475 + 159 0.0000 14.879123 404.8815 + 160 0.0000 16.065606 437.1674 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.360251 0.000000 + 1 N : 0.349622 0.000000 + 2 O : -0.262253 0.000000 + 3 H : 0.272883 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.869738 s : 3.869738 + pz : 1.282881 p : 4.462786 + px : 1.368543 + py : 1.811361 + dz2 : 0.009672 d : 0.023180 + dxz : 0.004749 + dyz : 0.006626 + dx2y2 : 0.001933 + dxy : 0.000200 + f0 : 0.002009 f : 0.004547 + f+1 : 0.000407 + f-1 : 0.001144 + f+2 : 0.000186 + f-2 : 0.000143 + f+3 : 0.000279 + f-3 : 0.000378 + 1 N s : 3.828823 s : 3.828823 + pz : 0.883598 p : 2.653130 + px : 0.984235 + py : 0.785297 + dz2 : 0.031344 d : 0.138495 + dxz : 0.044729 + dyz : 0.017156 + dx2y2 : 0.014469 + dxy : 0.030796 + f0 : 0.008951 f : 0.029930 + f+1 : 0.004142 + f-1 : 0.005940 + f+2 : 0.003462 + f-2 : 0.001975 + f+3 : 0.002702 + f-3 : 0.002759 + 2 O s : 3.879121 s : 3.879121 + pz : 1.848585 p : 4.311525 + px : 1.177476 + py : 1.285464 + dz2 : 0.005035 d : 0.063860 + dxz : 0.015305 + dyz : 0.001270 + dx2y2 : 0.015617 + dxy : 0.026633 + f0 : 0.001161 f : 0.007747 + f+1 : 0.001018 + f-1 : 0.000394 + f+2 : 0.000954 + f-2 : 0.000283 + f+3 : 0.001847 + f-3 : 0.002091 + 3 H s : 0.625294 s : 0.625294 + pz : 0.019109 p : 0.080038 + px : 0.019836 + py : 0.041093 + dz2 : 0.000372 d : 0.021785 + dxz : 0.009073 + dyz : 0.000767 + dx2y2 : 0.003784 + dxy : 0.007789 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.590216 0.000000 + 1 N : -0.253735 0.000000 + 2 O : 0.238577 0.000000 + 3 H : -0.575058 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.124279 s : 3.124279 + pz : 1.217126 p : 3.923793 + px : 1.263152 + py : 1.443515 + dz2 : 0.117219 d : 0.278629 + dxz : 0.065739 + dyz : 0.045451 + dx2y2 : 0.033649 + dxy : 0.016573 + f0 : 0.029236 f : 0.083083 + f+1 : 0.020233 + f-1 : 0.013831 + f+2 : 0.008777 + f-2 : 0.006281 + f+3 : 0.002194 + f-3 : 0.002530 + 1 N s : 3.016583 s : 3.016583 + pz : 0.928628 p : 2.835406 + px : 1.154313 + py : 0.752465 + dz2 : 0.216052 d : 0.951659 + dxz : 0.315638 + dyz : 0.102831 + dx2y2 : 0.160881 + dxy : 0.156256 + f0 : 0.117560 f : 0.450087 + f+1 : 0.069097 + f-1 : 0.058951 + f+2 : 0.069423 + f-2 : 0.028656 + f+3 : 0.053273 + f-3 : 0.053127 + 2 O s : 3.317334 s : 3.317334 + pz : 1.501697 p : 3.999447 + px : 1.375761 + py : 1.121989 + dz2 : 0.047105 d : 0.326882 + dxz : 0.108166 + dyz : 0.007748 + dx2y2 : 0.091224 + dxy : 0.072639 + f0 : 0.015492 f : 0.117760 + f+1 : 0.021528 + f-1 : 0.003414 + f+2 : 0.023762 + f-2 : 0.005770 + f+3 : 0.022554 + f-3 : 0.025239 + 3 H s : 0.623133 s : 0.623133 + pz : 0.137439 p : 0.558211 + px : 0.253051 + py : 0.167721 + dz2 : 0.036149 d : 0.393713 + dxz : 0.125406 + dyz : 0.015409 + dx2y2 : 0.100529 + dxy : 0.116220 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3603 8.0000 -0.3603 1.9068 1.9068 -0.0000 + 1 N 6.6504 7.0000 0.3496 2.5504 2.5504 0.0000 + 2 O 8.2623 8.0000 -0.2623 1.7532 1.7532 0.0000 + 3 H 0.7271 1.0000 0.2729 0.9497 0.9497 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8873 B( 0-O , 3-H ) : 0.9614 B( 1-N , 2-O ) : 1.6850 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 6 sec + +Total time .... 6.927 sec +Sum of individual times .... 6.096 sec ( 88.0%) + +Fock matrix formation .... 5.184 sec ( 74.8%) +Diagonalization .... 0.369 sec ( 5.3%) +Density matrix formation .... 0.028 sec ( 0.4%) +Population analysis .... 0.202 sec ( 2.9%) +Initial guess .... 0.021 sec ( 0.3%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.011 sec ( 0.2%) +DIIS solution .... 0.293 sec ( 4.2%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.529 sec +Reference energy ... -204.717221628 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 11.119 sec +AO-integral generation ... 0.366 sec +Half transformation ... 0.183 sec +K-integral sorting ... 8.846 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.061 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.063 s ( 0.000 ms/b) + 277134 b 0 skpd 0.096 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.105 s ( 0.001 ms/b) +: 159120 b 0 skpd 0.050 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.104 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.083 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.064 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.110 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.063 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.915 sec +AO-integral generation ... 0.742 sec +Half transformation ... 0.062 sec +J-integral sorting ... 0.083 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.292 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.432 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090583594 +EMP2(bb)= -0.090583594 +EMP2(ab)= -0.517606289 + +Initial guess performed in 0.219 sec +E(0) ... -204.717221628 +E(MP2) ... -0.698773477 +Initial E(tot) ... -205.415995105 + ... 0.189486016 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.415995105 -0.698773477 -0.000000000 0.023934973 6.07 0.000001969 + *** Turning on DIIS *** + 1 -205.386473298 -0.669251670 0.029521806 0.009956386 5.92 0.058044643 + 2 -205.406171093 -0.688949465 -0.019697795 0.005121565 6.21 0.060912379 + 3 -205.409948287 -0.692726659 -0.003777193 0.002097490 5.38 0.075352051 + 4 -205.411539144 -0.694317516 -0.001590858 0.001771369 5.73 0.082216780 + 5 -205.412112563 -0.694890935 -0.000573419 0.000990351 6.50 0.088086163 + 6 -205.412230265 -0.695008637 -0.000117702 0.000600075 6.89 0.091110572 + 7 -205.412280246 -0.695058618 -0.000049982 0.000246704 5.87 0.092564458 + 8 -205.412294260 -0.695072632 -0.000014013 0.000127516 6.60 0.093122008 + 9 -205.412289745 -0.695068117 0.000004515 0.000035261 6.60 0.093289169 + 10 -205.412295129 -0.695073501 -0.000005384 0.000020698 6.90 0.093341998 + 11 -205.412292120 -0.695070492 0.000003009 0.000016356 8.01 0.093333806 + 12 -205.412293419 -0.695071791 -0.000001299 0.000012417 6.22 0.093346332 + 13 -205.412293157 -0.695071529 0.000000262 0.000008278 6.81 0.093341578 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.717221628 +E(CORR) ... -0.695071529 +E(TOT) ... -205.412293157 +Singles norm **1/2 ... 0.093341578 ( 0.046670789, 0.046670789) +T1 diagnostic ... 0.022000821 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.058649 + 10a-> 13a 10b-> 13b 0.040078 + 8b-> 13b -1b-> -1b 0.038241 + 8a-> 13a -1a-> -1a 0.038241 + 10a-> 13a -1a-> -1a 0.036299 + 10b-> 13b -1b-> -1b 0.036299 + 8a-> 13a 9b-> 13b 0.031552 + 9a-> 13a 8b-> 13b 0.031552 + 10a-> 13a 8b-> 13b 0.029252 + 8a-> 13a 10b-> 13b 0.029252 + 11a-> 13a 11b-> 13b 0.027834 + 5a-> 13a 5b-> 13b 0.027265 + 9a-> 13a 9b-> 13b 0.026452 + 10a-> 13a 9b-> 13b 0.024324 + 9a-> 13a 10b-> 13b 0.024324 + 11a-> 25a -1a-> -1a 0.023070 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034954186 + alpha-alpha-alpha ... -0.000896182 ( 2.6%) + alpha-alpha-beta ... -0.016580911 ( 47.4%) + alpha-beta -beta ... -0.016580911 ( 47.4%) + beta -beta -beta ... -0.000896182 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034954186 + +Final correlation energy ... -0.730025715 +E(CCSD) ... -205.412293157 +E(CCSD(T)) ... -205.447247343 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.211927646 sqrt= 1.100875854 +W(HF) = 0.825131767 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.276721 -0.000000 + 1 N : 0.161422 0.000000 + 2 O : -0.144284 0.000000 + 3 H : 0.259583 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.847922 s : 3.847922 + pz : 1.273193 p : 4.365193 + px : 1.355345 + py : 1.736654 + dz2 : 0.014507 d : 0.055252 + dxz : 0.010672 + dyz : 0.013996 + dx2y2 : 0.008819 + dxy : 0.007258 + f0 : 0.002201 f : 0.008355 + f+1 : 0.000905 + f-1 : 0.001678 + f+2 : 0.000853 + f-2 : 0.000791 + f+3 : 0.000926 + f-3 : 0.001001 + 1 N s : 3.880441 s : 3.880441 + pz : 0.916852 p : 2.759948 + px : 0.972365 + py : 0.870731 + dz2 : 0.037084 d : 0.168917 + dxz : 0.055320 + dyz : 0.026020 + dx2y2 : 0.017754 + dxy : 0.032740 + f0 : 0.008647 f : 0.029271 + f+1 : 0.003846 + f-1 : 0.005904 + f+2 : 0.003779 + f-2 : 0.002440 + f+3 : 0.002239 + f-3 : 0.002416 + 2 O s : 3.866600 s : 3.866600 + pz : 1.762503 p : 4.182307 + px : 1.166659 + py : 1.253146 + dz2 : 0.010092 d : 0.085131 + dxz : 0.023274 + dyz : 0.007637 + dx2y2 : 0.017028 + dxy : 0.027100 + f0 : 0.001652 f : 0.010246 + f+1 : 0.001485 + f-1 : 0.000863 + f+2 : 0.001467 + f-2 : 0.000880 + f+3 : 0.001840 + f-3 : 0.002059 + 3 H s : 0.636798 s : 0.636798 + pz : 0.022846 p : 0.084950 + px : 0.014754 + py : 0.047351 + dz2 : 0.000658 d : 0.018668 + dxz : 0.008100 + dyz : 0.000762 + dx2y2 : 0.002643 + dxy : 0.006506 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.605320 -0.000000 + 1 N : -0.303534 -0.000000 + 2 O : 0.273913 0.000000 + 3 H : -0.575699 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.130820 s : 3.130820 + pz : 1.219811 p : 3.863989 + px : 1.255945 + py : 1.388233 + dz2 : 0.123500 d : 0.309831 + dxz : 0.071347 + dyz : 0.051509 + dx2y2 : 0.040958 + dxy : 0.022517 + f0 : 0.030279 f : 0.090040 + f+1 : 0.021759 + f-1 : 0.015288 + f+2 : 0.009413 + f-2 : 0.006997 + f+3 : 0.002989 + f-3 : 0.003315 + 1 N s : 3.021627 s : 3.021627 + pz : 0.939248 p : 2.882189 + px : 1.139154 + py : 0.803787 + dz2 : 0.223092 d : 0.960912 + dxz : 0.313124 + dyz : 0.104847 + dx2y2 : 0.164325 + dxy : 0.155524 + f0 : 0.115276 f : 0.438806 + f+1 : 0.069100 + f-1 : 0.056479 + f+2 : 0.064241 + f-2 : 0.027538 + f+3 : 0.053322 + f-3 : 0.052849 + 2 O s : 3.319295 s : 3.319295 + pz : 1.446088 p : 3.923017 + px : 1.368395 + py : 1.108534 + dz2 : 0.052884 d : 0.357396 + dxz : 0.110187 + dyz : 0.014180 + dx2y2 : 0.097654 + dxy : 0.082490 + f0 : 0.015965 f : 0.126378 + f+1 : 0.022185 + f-1 : 0.004081 + f+2 : 0.023648 + f-2 : 0.006933 + f+3 : 0.025484 + f-3 : 0.028084 + 3 H s : 0.624665 s : 0.624665 + pz : 0.138808 p : 0.567868 + px : 0.256157 + py : 0.172903 + dz2 : 0.037569 d : 0.383166 + dxz : 0.121164 + dyz : 0.014819 + dx2y2 : 0.098629 + dxy : 0.110985 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2767 8.0000 -0.2767 2.2745 1.8098 0.4647 + 1 N 6.8386 7.0000 0.1614 2.8369 2.3540 0.4829 + 2 O 8.1443 8.0000 -0.1443 2.1527 1.6542 0.4985 + 3 H 0.7404 1.0000 0.2596 0.9720 0.9003 0.0718 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8183 B( 0-O , 3-H ) : 0.8916 B( 1-N , 2-O ) : 1.5407 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 123.200 sec + +Fock Matrix Formation ... 0.529 sec ( 0.4%) +Initial Guess ... 0.219 sec ( 0.2%) +DIIS Solver ... 5.253 sec ( 4.3%) +State Vector Update ... 0.245 sec ( 0.2%) +Sigma-vector construction ... 84.213 sec ( 68.4%) + <0|H|D> ... 0.009 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.054 sec ( 0.1% of sigma) + (0-ext) ... 0.174 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.056 sec ( 0.1% of sigma) + (2-ext) ... 2.056 sec ( 2.4% of sigma) + (4-ext) ... 48.866 sec ( 58.0% of sigma) + ... 4.710 sec ( 5.6% of sigma) + ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.020 sec ( 0.0% of sigma) + (1-ext) ... 0.256 sec ( 0.3% of sigma) + Fock-dressing ... 5.428 sec ( 6.4% of sigma) + (ik|jl)-dressing ... 0.187 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 18.254 sec ( 21.7% of sigma) + Pair energies ... 0.028 sec ( 0.0% of sigma) +Total Time for computing (T) ... 17.835 sec ( 14.5% of ALL) + I/O of integral and amplitudes ... 1.903 sec ( 10.7% of (T)) + External N**7 contributions ... 8.100 sec ( 45.4% of (T)) + Internal N**7 contributions ... 0.777 sec ( 4.4% of (T)) + N**6 triples energy contributions ... 2.994 sec ( 16.8% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.447247342719 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.001869252 -0.007657325 0.002945459 + 2 N : 0.000679565 -0.008998743 -0.000220933 + 3 O : 0.001472575 0.007734913 -0.002192851 + 4 H : -0.000282888 0.008921155 -0.000531674 + +Norm of the cartesian gradient ... 0.017293008 +RMS gradient ... 0.004992061 +MAX gradient ... 0.008998743 + +------- +TIMINGS +------- + +Total numerical gradient time ... 815.619 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 412.27 cm**-1 + 7: 594.49 cm**-1 + 8: 794.85 cm**-1 + 9: 1258.71 cm**-1 + 10: 1704.56 cm**-1 + 11: 3735.96 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 0.054536 -0.284672 -0.075041 -0.058638 -0.014181 -0.059927 + 1 0.047177 0.027563 -0.102890 -0.002893 -0.015671 0.016226 + 2 -0.070163 0.341774 -0.159565 -0.062967 -0.104378 -0.007578 + 3 -0.047074 0.184446 -0.000596 0.005182 0.652463 -0.001495 + 4 0.072530 0.094744 0.111092 -0.015285 0.183380 -0.000986 + 5 0.043617 -0.077417 0.478488 0.046537 0.059371 -0.000301 + 6 0.001354 0.148776 0.068508 0.064328 -0.554532 0.000983 + 7 -0.050318 -0.067548 -0.012580 0.008937 -0.147768 0.000810 + 8 0.027445 -0.263797 -0.211728 -0.039007 0.024782 -0.000034 + 9 -0.232963 -0.406095 0.111976 -0.162316 -0.039884 0.956328 + 10 -0.958001 -0.681908 0.289030 0.116480 0.045881 -0.256700 + 11 0.071935 -0.161883 -0.755825 0.971859 0.438344 0.124995 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 412.27 0.035597 179.89 0.026945 (-0.093492 -0.106639 0.082659) + 7: 594.49 0.018856 95.29 0.009898 ( 0.057423 -0.032043 -0.074658) + 8: 794.85 0.018936 95.69 0.007434 (-0.051123 0.020321 0.066392) + 9: 1258.71 0.027427 138.60 0.006800 (-0.039219 0.014871 0.070996) + 10: 1704.56 0.027187 137.39 0.004977 ( 0.055449 0.003727 -0.043460) + 11: 3735.96 0.014038 70.94 0.001173 ( 0.031560 -0.008951 -0.009823) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 412.27 E(vib) ... 0.19 +freq. 594.49 E(vib) ... 0.10 +freq. 794.85 E(vib) ... 0.05 +freq. 1258.71 E(vib) ... 0.01 +freq. 1704.56 E(vib) ... 0.00 +freq. 3735.96 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.44724734 Eh +Zero point energy ... 0.01936634 Eh 12.15 kcal/mol +Thermal vibrational correction ... 0.00055588 Eh 0.35 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42449258 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00338842 Eh 2.13 kcal/mol +Non-thermal (ZPE) correction 0.01936634 Eh 12.15 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02275476 Eh 14.28 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42449258 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.42354837 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 2.961098 0.410139 0.363888 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00077413 Eh 0.49 kcal/mol +Rotational entropy ... 0.00989632 Eh 6.21 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02847277 Eh 17.87 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00989632 Eh 6.21 kcal/mol| +| sn= 2 | S(rot)= 0.00924187 Eh 5.80 kcal/mol| +| sn= 3 | S(rot)= 0.00885903 Eh 5.56 kcal/mol| +| sn= 4 | S(rot)= 0.00858741 Eh 5.39 kcal/mol| +| sn= 5 | S(rot)= 0.00837672 Eh 5.26 kcal/mol| +| sn= 6 | S(rot)= 0.00820458 Eh 5.15 kcal/mol| +| sn= 7 | S(rot)= 0.00805903 Eh 5.06 kcal/mol| +| sn= 8 | S(rot)= 0.00793295 Eh 4.98 kcal/mol| +| sn= 9 | S(rot)= 0.00782175 Eh 4.91 kcal/mol| +| sn=10 | S(rot)= 0.00772227 Eh 4.85 kcal/mol| +| sn=11 | S(rot)= 0.00763228 Eh 4.79 kcal/mol| +| sn=12 | S(rot)= 0.00755012 Eh 4.74 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.42354837 Eh +Total entropy correction ... -0.02847277 Eh -17.87 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.45202114 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00477380 Eh -3.00 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.447247344 Eh +Current gradient norm .... 0.017293008 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.017366785 0.117746007 0.171577484 0.487750767 0.517868671 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999791841 +Lowest eigenvalues of augmented Hessian: + -0.000079906 0.115907878 0.171049696 0.487736677 0.517829464 +Length of the computed step .... 0.020407082 +The final length of the internal step .... 0.020407082 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0083311565 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0054967450 RMS(Int)= 0.0083301512 + Iter 1: RMS(Cart)= 0.0000019212 RMS(Int)= 0.0000038129 + Iter 2: RMS(Cart)= 0.0000000136 RMS(Int)= 0.0000000152 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0022357693 0.0001000000 NO + MAX gradient 0.0035245554 0.0003000000 NO + RMS step 0.0083311565 0.0020000000 NO + MAX step 0.0195579020 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0103 Max(Angles) 0.09 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4611 0.003118 -0.0103 1.4507 + 2. B(O 2,N 1) 1.1721 0.003525 -0.0008 1.1713 + 3. B(H 3,O 0) 0.9719 0.002710 -0.0029 0.9691 + 4. A(N 1,O 0,H 3) 102.03 0.000600 0.01 102.04 + 5. A(O 0,N 1,O 2) 110.43 0.000383 0.09 110.52 + 6. D(O 2,N 1,O 0,H 3) 147.27 -0.015299 0.00 147.27 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.274887 -0.030879 0.741594 + N 0.172468 -0.241558 -0.622245 + O 1.302651 0.045667 -0.732608 + H -1.200231 0.226770 0.613260 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.519461 -0.058352 1.401409 + 1 N 7.0000 0 14.007 0.325917 -0.456479 -1.175874 + 2 O 8.0000 0 15.999 2.461654 0.086299 -1.384429 + 3 H 1.0000 0 1.008 -2.268108 0.428532 1.158893 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.450713613593 0.00000000 0.00000000 + O 2 1 0 1.171321303746 110.51825029 0.00000000 + H 1 2 3 0.969078874612 102.03822523 147.27272731 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.741451428443 0.00000000 0.00000000 + O 2 1 0 2.213476478908 110.51825029 0.00000000 + H 1 2 3 1.831293675186 102.03822523 147.27272731 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2225 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2690 + la=0 lb=0: 549 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.201777424325 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.967e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7184192157 0.000000000000 0.00041913 0.00000845 0.0019251 0.7000 + 1 -204.7184316950 -0.000012479356 0.00031281 0.00000698 0.0014760 0.7000 + ***Turning on DIIS*** + 2 -204.7184419734 -0.000010278347 0.00072807 0.00001784 0.0011192 0.0000 + 3 -204.7177666626 0.000675310797 0.00027661 0.00000717 0.0002644 0.0000 + 4 -204.7184792846 -0.000712621977 0.00009319 0.00000225 0.0001180 0.0000 + 5 -204.7188257556 -0.000346470993 0.00002725 0.00000084 0.0000570 0.0000 + 6 -204.7183541697 0.000471585864 0.00001491 0.00000043 0.0000238 0.0000 + 7 -204.7184599667 -0.000105797027 0.00000559 0.00000022 0.0000099 0.0000 + 8 -204.7184810809 -0.000021114222 0.00000457 0.00000017 0.0000059 0.0000 + 9 -204.7184546773 0.000026403626 0.00000400 0.00000016 0.0000038 0.0000 + 10 -204.7184817516 -0.000027074271 0.00000278 0.00000011 0.0000024 0.0000 + 11 -204.7184738041 0.000007947523 0.00000121 0.00000004 0.0000011 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + +Total Energy : -204.71847361 Eh -5570.67287 eV + Last Energy change ... 1.9269e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.0641e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 2 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.206 sec +Reference energy ... -204.718475293 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.393 sec +AO-integral generation ... 0.145 sec +Half transformation ... 0.081 sec +K-integral sorting ... 5.374 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.027 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.034 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.046 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.023 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.358 sec +AO-integral generation ... 0.254 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.049 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.152 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.256 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090440277 +EMP2(bb)= -0.090440277 +EMP2(ab)= -0.516661827 + +Initial guess performed in 0.133 sec +E(0) ... -204.718475293 +E(MP2) ... -0.697542381 +Initial E(tot) ... -205.416017674 + ... 0.188312616 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.416017674 -0.697542381 -0.000000000 0.023948037 2.83 0.000000860 + *** Turning on DIIS *** + 1 -205.387062144 -0.668586851 0.028955530 0.009701588 2.87 0.057508076 + 2 -205.406556516 -0.688081223 -0.019494372 0.005134840 2.89 0.060462912 + 3 -205.410296018 -0.691820725 -0.003739502 0.002058974 3.00 0.074727457 + 4 -205.411862667 -0.693387374 -0.001566650 0.001709573 3.10 0.081498388 + 5 -205.412420670 -0.693945377 -0.000558002 0.000955584 3.00 0.087220849 + 6 -205.412534728 -0.694059435 -0.000114058 0.000575464 3.00 0.090140865 + 7 -205.412582159 -0.694106866 -0.000047431 0.000238087 3.25 0.091512443 + 8 -205.412595135 -0.694119842 -0.000012976 0.000122496 3.04 0.092035559 + 9 -205.412590745 -0.694115452 0.000004390 0.000033924 2.92 0.092190869 + 10 -205.412595785 -0.694120492 -0.000005040 0.000020134 3.29 0.092239828 + 11 -205.412592955 -0.694117662 0.000002830 0.000015929 3.07 0.092232129 + 12 -205.412594180 -0.694118887 -0.000001224 0.000012072 3.04 0.092243449 + 13 -205.412593933 -0.694118640 0.000000246 0.000007960 2.97 0.092239081 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.718475293 +E(CORR) ... -0.694118640 +E(TOT) ... -205.412593933 +Singles norm **1/2 ... 0.092239081 ( 0.046119540, 0.046119540) +T1 diagnostic ... 0.021740960 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.057058 + 10a-> 13a 10b-> 13b 0.041108 + 8b-> 13b -1b-> -1b 0.038298 + 8a-> 13a -1a-> -1a 0.038298 + 10a-> 13a -1a-> -1a 0.034908 + 10b-> 13b -1b-> -1b 0.034908 + 9a-> 13a 8b-> 13b 0.030802 + 8a-> 13a 9b-> 13b 0.030802 + 8a-> 13a 10b-> 13b 0.029202 + 10a-> 13a 8b-> 13b 0.029202 + 11a-> 13a 11b-> 13b 0.028047 + 5a-> 13a 5b-> 13b 0.026730 + 9a-> 13a 9b-> 13b 0.026324 + 9a-> 13a 10b-> 13b 0.024611 + 10a-> 13a 9b-> 13b 0.024611 + 11a-> 26a 11b-> 26b 0.024449 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034692744 + alpha-alpha-alpha ... -0.000892700 ( 2.6%) + alpha-alpha-beta ... -0.016453672 ( 47.4%) + alpha-beta -beta ... -0.016453672 ( 47.4%) + beta -beta -beta ... -0.000892700 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034692744 + +Final correlation energy ... -0.728811384 +E(CCSD) ... -205.412593933 +E(CCSD(T)) ... -205.447286677 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210399523 sqrt= 1.100181586 +W(HF) = 0.826173492 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 57.812 sec + +Fock Matrix Formation ... 0.206 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 2.233 sec ( 3.9%) +State Vector Update ... 0.097 sec ( 0.2%) +Sigma-vector construction ... 39.935 sec ( 69.1%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.023 sec ( 0.1% of sigma) + (0-ext) ... 0.068 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (2-ext) ... 0.930 sec ( 2.3% of sigma) + (4-ext) ... 22.633 sec ( 56.7% of sigma) + ... 1.505 sec ( 3.8% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.109 sec ( 0.3% of sigma) + Fock-dressing ... 2.211 sec ( 5.5% of sigma) + (ik|jl)-dressing ... 0.075 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.754 sec ( 24.4% of sigma) + Pair energies ... 0.007 sec ( 0.0% of sigma) +Total Time for computing (T) ... 7.094 sec ( 12.3% of ALL) + I/O of integral and amplitudes ... 0.697 sec ( 9.8% of (T)) + External N**7 contributions ... 3.891 sec ( 54.8% of (T)) + Internal N**7 contributions ... 0.308 sec ( 4.3% of (T)) + N**6 triples energy contributions ... 1.628 sec ( 23.0% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.447286676808 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.003240186 -0.007555925 -0.000002338 + 2 N : 0.002878544 -0.007880605 0.002236205 + 3 O : -0.002039061 0.007059300 -0.001716407 + 4 H : 0.002400703 0.008377229 -0.000517460 + +Norm of the cartesian gradient ... 0.016617101 +RMS gradient ... 0.004796944 +MAX gradient ... 0.008377229 + +------- +TIMINGS +------- + +Total numerical gradient time ... 364.099 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.447286677 Eh +Current gradient norm .... 0.016617101 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999743 +Lowest eigenvalues of augmented Hessian: + -0.000000077 0.118360584 0.172198603 0.485006833 0.517778013 +Length of the computed step .... 0.000717134 +The final length of the internal step .... 0.000717134 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0002927687 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001793025 RMS(Int)= 0.0002927715 + Iter 1: RMS(Cart)= 0.0000000073 RMS(Int)= 0.0000000114 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000393333 0.0000050000 NO + RMS gradient 0.0000568006 0.0001000000 YES + MAX gradient 0.0001104907 0.0003000000 YES + RMS step 0.0002927687 0.0020000000 YES + MAX step 0.0007162536 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0004 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4507 -0.000110 0.0004 1.4511 + 2. B(O 2,N 1) 1.1713 -0.000075 -0.0000 1.1713 + 3. B(H 3,O 0) 0.9691 0.000003 -0.0000 0.9691 + 4. A(N 1,O 0,H 3) 102.04 -0.000019 -0.00 102.04 + 5. A(O 0,N 1,O 2) 110.52 -0.000035 -0.00 110.52 + 6. D(O 2,N 1,O 0,H 3) 147.27 -0.015638 -0.00 147.27 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.274994 -0.030854 0.741759 + N 0.172572 -0.241582 -0.622407 + O 1.302748 0.045656 -0.732689 + H -1.200325 0.226780 0.613338 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.519664 -0.058305 1.401721 + 1 N 7.0000 0 14.007 0.326114 -0.456523 -1.176179 + 2 O 8.0000 0 15.999 2.461838 0.086276 -1.384582 + 3 H 1.0000 0 1.008 -2.268286 0.428552 1.159041 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.451092638658 0.00000000 0.00000000 + O 2 1 0 1.171309639152 110.51812271 0.00000000 + H 1 2 3 0.969073736954 102.03673458 147.27272731 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.742167682012 0.00000000 0.00000000 + O 2 1 0 2.213454436020 110.51812271 0.00000000 + H 1 2 3 1.831283966419 102.03673458 147.27272731 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2225 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2690 + la=0 lb=0: 549 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.193985173575 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.1939851736 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.968e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7184419701 0.000000000000 0.00001229 0.00000026 0.0000656 0.7000 + 1 -204.7184419868 -0.000000016680 0.00000927 0.00000022 0.0000514 0.7000 + ***Turning on DIIS*** + 2 -204.7184420007 -0.000000013912 0.00002308 0.00000059 0.0000399 0.0000 + 3 -204.7184531222 -0.000011121492 0.00000887 0.00000024 0.0000105 0.0000 + 4 -204.7184382273 0.000014894926 0.00000342 0.00000008 0.0000030 0.0000 + 5 -204.7184373396 0.000000887667 0.00000112 0.00000002 0.0000010 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 6 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71844417 Eh -5570.67207 eV + +Components: +Nuclear Repulsion : 69.19398517 Eh 1882.86406 eV +Electronic Energy : -273.91242934 Eh -7453.53613 eV +One Electron Energy: -418.09890132 Eh -11377.04950 eV +Two Electron Energy: 144.18647197 Eh 3923.51337 eV + +Virial components: +Potential Energy : -408.96176543 Eh -11128.41540 eV +Kinetic Energy : 204.24332126 Eh 5557.74332 eV +Virial Ratio : 2.00232626 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -6.8300e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.3646e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.2822e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.4794e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.673741 -562.5611 + 1 1.0000 -20.633109 -561.4554 + 2 1.0000 -15.800140 -429.9437 + 3 1.0000 -1.607663 -43.7467 + 4 1.0000 -1.393203 -37.9110 + 5 1.0000 -0.949313 -25.8321 + 6 1.0000 -0.779724 -21.2174 + 7 1.0000 -0.729269 -19.8444 + 8 1.0000 -0.688786 -18.7428 + 9 1.0000 -0.618052 -16.8181 + 10 1.0000 -0.529416 -14.4062 + 11 1.0000 -0.460565 -12.5326 + 12 0.0000 0.028904 0.7865 + 13 0.0000 0.077139 2.0990 + 14 0.0000 0.093095 2.5332 + 15 0.0000 0.098888 2.6909 + 16 0.0000 0.122785 3.3411 + 17 0.0000 0.148429 4.0389 + 18 0.0000 0.157156 4.2764 + 19 0.0000 0.172682 4.6989 + 20 0.0000 0.186666 5.0794 + 21 0.0000 0.194166 5.2835 + 22 0.0000 0.204033 5.5520 + 23 0.0000 0.235507 6.4085 + 24 0.0000 0.264224 7.1899 + 25 0.0000 0.289088 7.8665 + 26 0.0000 0.310316 8.4441 + 27 0.0000 0.329268 8.9599 + 28 0.0000 0.356336 9.6964 + 29 0.0000 0.369774 10.0620 + 30 0.0000 0.423846 11.5334 + 31 0.0000 0.512484 13.9454 + 32 0.0000 0.524791 14.2803 + 33 0.0000 0.547614 14.9013 + 34 0.0000 0.569737 15.5033 + 35 0.0000 0.612902 16.6779 + 36 0.0000 0.633685 17.2435 + 37 0.0000 0.646657 17.5964 + 38 0.0000 0.698424 19.0051 + 39 0.0000 0.717719 19.5301 + 40 0.0000 0.729334 19.8462 + 41 0.0000 0.744388 20.2558 + 42 0.0000 0.772950 21.0330 + 43 0.0000 0.791972 21.5507 + 44 0.0000 0.804102 21.8807 + 45 0.0000 0.820211 22.3191 + 46 0.0000 0.852871 23.2078 + 47 0.0000 0.862632 23.4734 + 48 0.0000 0.925598 25.1868 + 49 0.0000 0.944234 25.6939 + 50 0.0000 0.958250 26.0753 + 51 0.0000 1.008898 27.4535 + 52 0.0000 1.031180 28.0598 + 53 0.0000 1.043834 28.4042 + 54 0.0000 1.051420 28.6106 + 55 0.0000 1.087403 29.5897 + 56 0.0000 1.157197 31.4889 + 57 0.0000 1.201481 32.6940 + 58 0.0000 1.252838 34.0915 + 59 0.0000 1.308018 35.5930 + 60 0.0000 1.375900 37.4401 + 61 0.0000 1.405946 38.2577 + 62 0.0000 1.478976 40.2450 + 63 0.0000 1.511850 41.1395 + 64 0.0000 1.519058 41.3357 + 65 0.0000 1.541517 41.9468 + 66 0.0000 1.573412 42.8147 + 67 0.0000 1.616531 43.9880 + 68 0.0000 1.669460 45.4283 + 69 0.0000 1.723881 46.9092 + 70 0.0000 1.779956 48.4351 + 71 0.0000 1.800584 48.9964 + 72 0.0000 1.875826 51.0438 + 73 0.0000 1.933047 52.6009 + 74 0.0000 1.960615 53.3511 + 75 0.0000 2.028475 55.1976 + 76 0.0000 2.057656 55.9917 + 77 0.0000 2.103580 57.2413 + 78 0.0000 2.158860 58.7456 + 79 0.0000 2.189602 59.5821 + 80 0.0000 2.280208 62.0476 + 81 0.0000 2.297728 62.5244 + 82 0.0000 2.310936 62.8838 + 83 0.0000 2.374949 64.6257 + 84 0.0000 2.444164 66.5091 + 85 0.0000 2.465380 67.0864 + 86 0.0000 2.487605 67.6912 + 87 0.0000 2.502090 68.0853 + 88 0.0000 2.515402 68.4476 + 89 0.0000 2.528977 68.8170 + 90 0.0000 2.574377 70.0524 + 91 0.0000 2.603794 70.8528 + 92 0.0000 2.653502 72.2055 + 93 0.0000 2.719319 73.9964 + 94 0.0000 2.731248 74.3210 + 95 0.0000 2.760257 75.1104 + 96 0.0000 2.835747 77.1646 + 97 0.0000 2.903436 79.0065 + 98 0.0000 2.948352 80.2287 + 99 0.0000 3.083957 83.9187 + 100 0.0000 3.144785 85.5740 + 101 0.0000 3.176569 86.4388 + 102 0.0000 3.263175 88.7955 + 103 0.0000 3.469179 94.4012 + 104 0.0000 3.754454 102.1639 + 105 0.0000 3.892545 105.9215 + 106 0.0000 4.031551 109.7041 + 107 0.0000 4.159377 113.1824 + 108 0.0000 4.190161 114.0201 + 109 0.0000 4.278647 116.4279 + 110 0.0000 4.364981 118.7772 + 111 0.0000 4.401069 119.7592 + 112 0.0000 4.548282 123.7651 + 113 0.0000 4.630427 126.0003 + 114 0.0000 4.750899 129.2785 + 115 0.0000 4.787172 130.2656 + 116 0.0000 4.800058 130.6162 + 117 0.0000 4.888947 133.0350 + 118 0.0000 4.960201 134.9739 + 119 0.0000 4.998188 136.0076 + 120 0.0000 5.070640 137.9791 + 121 0.0000 5.100145 138.7820 + 122 0.0000 5.177096 140.8760 + 123 0.0000 5.224820 142.1746 + 124 0.0000 5.257455 143.0626 + 125 0.0000 5.326716 144.9473 + 126 0.0000 5.343934 145.4158 + 127 0.0000 5.409955 147.2123 + 128 0.0000 5.555610 151.1758 + 129 0.0000 5.691940 154.8856 + 130 0.0000 5.795476 157.7029 + 131 0.0000 6.000651 163.2860 + 132 0.0000 6.117611 166.4687 + 133 0.0000 6.409186 174.4028 + 134 0.0000 6.499172 176.8515 + 135 0.0000 6.509698 177.1379 + 136 0.0000 6.693278 182.1334 + 137 0.0000 6.705111 182.4553 + 138 0.0000 6.742097 183.4618 + 139 0.0000 6.844286 186.2425 + 140 0.0000 6.907148 187.9531 + 141 0.0000 7.068139 192.3339 + 142 0.0000 7.125034 193.8820 + 143 0.0000 7.177588 195.3121 + 144 0.0000 7.188331 195.6044 + 145 0.0000 7.229956 196.7371 + 146 0.0000 7.265696 197.7096 + 147 0.0000 7.350826 200.0262 + 148 0.0000 7.396214 201.2612 + 149 0.0000 7.440819 202.4750 + 150 0.0000 7.480659 203.5591 + 151 0.0000 7.589377 206.5175 + 152 0.0000 7.626059 207.5156 + 153 0.0000 7.670970 208.7377 + 154 0.0000 7.855516 213.7595 + 155 0.0000 7.921352 215.5510 + 156 0.0000 8.032960 218.5880 + 157 0.0000 8.386630 228.2118 + 158 0.0000 14.103229 383.7684 + 159 0.0000 14.960897 407.1067 + 160 0.0000 16.114676 438.5026 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.673741 -562.5611 + 1 1.0000 -20.633109 -561.4554 + 2 1.0000 -15.800140 -429.9437 + 3 1.0000 -1.607663 -43.7467 + 4 1.0000 -1.393203 -37.9110 + 5 1.0000 -0.949313 -25.8321 + 6 1.0000 -0.779724 -21.2174 + 7 1.0000 -0.729269 -19.8444 + 8 1.0000 -0.688786 -18.7428 + 9 1.0000 -0.618052 -16.8181 + 10 1.0000 -0.529416 -14.4062 + 11 1.0000 -0.460565 -12.5326 + 12 0.0000 0.028904 0.7865 + 13 0.0000 0.077139 2.0990 + 14 0.0000 0.093095 2.5332 + 15 0.0000 0.098888 2.6909 + 16 0.0000 0.122785 3.3411 + 17 0.0000 0.148429 4.0389 + 18 0.0000 0.157156 4.2764 + 19 0.0000 0.172682 4.6989 + 20 0.0000 0.186666 5.0794 + 21 0.0000 0.194166 5.2835 + 22 0.0000 0.204033 5.5520 + 23 0.0000 0.235507 6.4085 + 24 0.0000 0.264224 7.1899 + 25 0.0000 0.289088 7.8665 + 26 0.0000 0.310316 8.4441 + 27 0.0000 0.329268 8.9599 + 28 0.0000 0.356336 9.6964 + 29 0.0000 0.369774 10.0620 + 30 0.0000 0.423846 11.5334 + 31 0.0000 0.512484 13.9454 + 32 0.0000 0.524791 14.2803 + 33 0.0000 0.547614 14.9013 + 34 0.0000 0.569737 15.5033 + 35 0.0000 0.612902 16.6779 + 36 0.0000 0.633685 17.2435 + 37 0.0000 0.646657 17.5964 + 38 0.0000 0.698424 19.0051 + 39 0.0000 0.717719 19.5301 + 40 0.0000 0.729334 19.8462 + 41 0.0000 0.744388 20.2558 + 42 0.0000 0.772950 21.0330 + 43 0.0000 0.791972 21.5507 + 44 0.0000 0.804102 21.8807 + 45 0.0000 0.820211 22.3191 + 46 0.0000 0.852871 23.2078 + 47 0.0000 0.862632 23.4734 + 48 0.0000 0.925598 25.1868 + 49 0.0000 0.944234 25.6939 + 50 0.0000 0.958250 26.0753 + 51 0.0000 1.008898 27.4535 + 52 0.0000 1.031180 28.0598 + 53 0.0000 1.043834 28.4042 + 54 0.0000 1.051420 28.6106 + 55 0.0000 1.087403 29.5897 + 56 0.0000 1.157197 31.4889 + 57 0.0000 1.201481 32.6940 + 58 0.0000 1.252838 34.0915 + 59 0.0000 1.308018 35.5930 + 60 0.0000 1.375900 37.4401 + 61 0.0000 1.405946 38.2577 + 62 0.0000 1.478976 40.2450 + 63 0.0000 1.511850 41.1395 + 64 0.0000 1.519058 41.3357 + 65 0.0000 1.541517 41.9468 + 66 0.0000 1.573412 42.8147 + 67 0.0000 1.616531 43.9880 + 68 0.0000 1.669460 45.4283 + 69 0.0000 1.723881 46.9092 + 70 0.0000 1.779956 48.4351 + 71 0.0000 1.800584 48.9964 + 72 0.0000 1.875826 51.0438 + 73 0.0000 1.933047 52.6009 + 74 0.0000 1.960615 53.3511 + 75 0.0000 2.028475 55.1976 + 76 0.0000 2.057656 55.9917 + 77 0.0000 2.103580 57.2413 + 78 0.0000 2.158860 58.7456 + 79 0.0000 2.189602 59.5821 + 80 0.0000 2.280208 62.0476 + 81 0.0000 2.297728 62.5244 + 82 0.0000 2.310936 62.8838 + 83 0.0000 2.374949 64.6257 + 84 0.0000 2.444164 66.5091 + 85 0.0000 2.465380 67.0864 + 86 0.0000 2.487605 67.6912 + 87 0.0000 2.502090 68.0853 + 88 0.0000 2.515402 68.4476 + 89 0.0000 2.528977 68.8170 + 90 0.0000 2.574377 70.0524 + 91 0.0000 2.603794 70.8528 + 92 0.0000 2.653502 72.2055 + 93 0.0000 2.719319 73.9964 + 94 0.0000 2.731248 74.3210 + 95 0.0000 2.760257 75.1104 + 96 0.0000 2.835747 77.1646 + 97 0.0000 2.903436 79.0065 + 98 0.0000 2.948352 80.2287 + 99 0.0000 3.083957 83.9187 + 100 0.0000 3.144785 85.5740 + 101 0.0000 3.176569 86.4388 + 102 0.0000 3.263175 88.7955 + 103 0.0000 3.469179 94.4012 + 104 0.0000 3.754454 102.1639 + 105 0.0000 3.892545 105.9215 + 106 0.0000 4.031551 109.7041 + 107 0.0000 4.159377 113.1824 + 108 0.0000 4.190161 114.0201 + 109 0.0000 4.278647 116.4279 + 110 0.0000 4.364981 118.7772 + 111 0.0000 4.401069 119.7592 + 112 0.0000 4.548282 123.7651 + 113 0.0000 4.630427 126.0003 + 114 0.0000 4.750899 129.2785 + 115 0.0000 4.787172 130.2656 + 116 0.0000 4.800058 130.6162 + 117 0.0000 4.888947 133.0350 + 118 0.0000 4.960201 134.9739 + 119 0.0000 4.998188 136.0076 + 120 0.0000 5.070640 137.9791 + 121 0.0000 5.100145 138.7820 + 122 0.0000 5.177096 140.8760 + 123 0.0000 5.224820 142.1746 + 124 0.0000 5.257455 143.0626 + 125 0.0000 5.326716 144.9473 + 126 0.0000 5.343934 145.4158 + 127 0.0000 5.409955 147.2123 + 128 0.0000 5.555610 151.1758 + 129 0.0000 5.691940 154.8856 + 130 0.0000 5.795476 157.7029 + 131 0.0000 6.000651 163.2860 + 132 0.0000 6.117611 166.4687 + 133 0.0000 6.409186 174.4028 + 134 0.0000 6.499172 176.8515 + 135 0.0000 6.509698 177.1379 + 136 0.0000 6.693278 182.1334 + 137 0.0000 6.705111 182.4553 + 138 0.0000 6.742097 183.4618 + 139 0.0000 6.844286 186.2425 + 140 0.0000 6.907148 187.9531 + 141 0.0000 7.068139 192.3339 + 142 0.0000 7.125034 193.8820 + 143 0.0000 7.177588 195.3121 + 144 0.0000 7.188331 195.6044 + 145 0.0000 7.229956 196.7371 + 146 0.0000 7.265696 197.7096 + 147 0.0000 7.350826 200.0262 + 148 0.0000 7.396214 201.2612 + 149 0.0000 7.440819 202.4750 + 150 0.0000 7.480659 203.5591 + 151 0.0000 7.589377 206.5175 + 152 0.0000 7.626059 207.5156 + 153 0.0000 7.670970 208.7377 + 154 0.0000 7.855516 213.7595 + 155 0.0000 7.921352 215.5510 + 156 0.0000 8.032960 218.5880 + 157 0.0000 8.386630 228.2118 + 158 0.0000 14.103229 383.7684 + 159 0.0000 14.960897 407.1067 + 160 0.0000 16.114676 438.5026 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.352425 0.000000 + 1 N : 0.346748 0.000000 + 2 O : -0.265335 0.000000 + 3 H : 0.271013 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.867966 s : 3.867966 + pz : 1.281300 p : 4.456719 + px : 1.367111 + py : 1.808308 + dz2 : 0.009633 d : 0.023147 + dxz : 0.004708 + dyz : 0.006817 + dx2y2 : 0.001833 + dxy : 0.000156 + f0 : 0.002049 f : 0.004593 + f+1 : 0.000404 + f-1 : 0.001169 + f+2 : 0.000184 + f-2 : 0.000145 + f+3 : 0.000271 + f-3 : 0.000371 + 1 N s : 3.829127 s : 3.829127 + pz : 0.884111 p : 2.654757 + px : 0.985097 + py : 0.785549 + dz2 : 0.031616 d : 0.139284 + dxz : 0.044645 + dyz : 0.017589 + dx2y2 : 0.014432 + dxy : 0.031002 + f0 : 0.008997 f : 0.030084 + f+1 : 0.004140 + f-1 : 0.006035 + f+2 : 0.003498 + f-2 : 0.001954 + f+3 : 0.002700 + f-3 : 0.002761 + 2 O s : 3.878768 s : 3.878768 + pz : 1.851141 p : 4.315105 + px : 1.177419 + py : 1.286545 + dz2 : 0.005060 d : 0.063732 + dxz : 0.015199 + dyz : 0.001258 + dx2y2 : 0.015557 + dxy : 0.026657 + f0 : 0.001147 f : 0.007731 + f+1 : 0.001031 + f-1 : 0.000392 + f+2 : 0.000948 + f-2 : 0.000279 + f+3 : 0.001841 + f-3 : 0.002093 + 3 H s : 0.626174 s : 0.626174 + pz : 0.019402 p : 0.080663 + px : 0.019899 + py : 0.041363 + dz2 : 0.000366 d : 0.022149 + dxz : 0.009242 + dyz : 0.000780 + dx2y2 : 0.003878 + dxy : 0.007884 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.596103 0.000000 + 1 N : -0.259587 0.000000 + 2 O : 0.239637 0.000000 + 3 H : -0.576152 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.119123 s : 3.119123 + pz : 1.217901 p : 3.916994 + px : 1.260838 + py : 1.438255 + dz2 : 0.118684 d : 0.282793 + dxz : 0.066782 + dyz : 0.046409 + dx2y2 : 0.034043 + dxy : 0.016876 + f0 : 0.029812 f : 0.084986 + f+1 : 0.020696 + f-1 : 0.014197 + f+2 : 0.009057 + f-2 : 0.006464 + f+3 : 0.002209 + f-3 : 0.002551 + 1 N s : 3.011144 s : 3.011144 + pz : 0.931906 p : 2.835993 + px : 1.152763 + py : 0.751324 + dz2 : 0.218244 d : 0.958782 + dxz : 0.317434 + dyz : 0.104667 + dx2y2 : 0.161270 + dxy : 0.157167 + f0 : 0.118476 f : 0.453668 + f+1 : 0.069886 + f-1 : 0.059927 + f+2 : 0.070050 + f-2 : 0.028763 + f+3 : 0.053335 + f-3 : 0.053232 + 2 O s : 3.315941 s : 3.315941 + pz : 1.502410 p : 3.999399 + px : 1.375238 + py : 1.121751 + dz2 : 0.047156 d : 0.326834 + dxz : 0.108337 + dyz : 0.007834 + dx2y2 : 0.090991 + dxy : 0.072516 + f0 : 0.015540 f : 0.118190 + f+1 : 0.021700 + f-1 : 0.003415 + f+2 : 0.023975 + f-2 : 0.005830 + f+3 : 0.022520 + f-3 : 0.025211 + 3 H s : 0.622846 s : 0.622846 + pz : 0.137893 p : 0.559023 + px : 0.253193 + py : 0.167937 + dz2 : 0.036334 d : 0.394283 + dxz : 0.125779 + dyz : 0.015550 + dx2y2 : 0.100401 + dxy : 0.116220 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3524 8.0000 -0.3524 1.9080 1.9080 -0.0000 + 1 N 6.6533 7.0000 0.3467 2.5445 2.5445 -0.0000 + 2 O 8.2653 8.0000 -0.2653 1.7465 1.7465 -0.0000 + 3 H 0.7290 1.0000 0.2710 0.9503 0.9503 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8882 B( 0-O , 3-H ) : 0.9632 B( 1-N , 2-O ) : 1.6795 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.318 sec +Sum of individual times .... 0.967 sec ( 73.3%) + +Fock matrix formation .... 0.701 sec ( 53.2%) +Diagonalization .... 0.076 sec ( 5.8%) +Density matrix formation .... 0.006 sec ( 0.5%) +Population analysis .... 0.109 sec ( 8.3%) +Initial guess .... 0.009 sec ( 0.7%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.4%) +DIIS solution .... 0.065 sec ( 4.9%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.204 sec +Reference energy ... -204.718442046 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.385 sec +AO-integral generation ... 0.140 sec +Half transformation ... 0.081 sec +K-integral sorting ... 5.392 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.034 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.045 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.356 sec +AO-integral generation ... 0.252 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.049 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.153 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.251 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090444019 +EMP2(bb)= -0.090444019 +EMP2(ab)= -0.516687678 + +Initial guess performed in 0.131 sec +E(0) ... -204.718442046 +E(MP2) ... -0.697575716 +Initial E(tot) ... -205.416017762 + ... 0.188345207 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.416017762 -0.697575716 -0.000000000 0.023944834 2.79 0.000001104 + *** Turning on DIIS *** + 1 -205.387046238 -0.668604192 0.028971524 0.009709801 2.78 0.057524808 + 2 -205.406546420 -0.688104375 -0.019500183 0.005133583 2.89 0.060476784 + 3 -205.410286952 -0.691844906 -0.003740531 0.002059062 2.88 0.074746893 + 4 -205.411854309 -0.693412263 -0.001567357 0.001711923 2.92 0.081520894 + 5 -205.412412806 -0.693970761 -0.000558498 0.000956849 2.91 0.087248480 + 6 -205.412526993 -0.694084948 -0.000114187 0.000576308 2.91 0.090172293 + 7 -205.412574513 -0.694132467 -0.000047519 0.000238348 2.97 0.091546751 + 8 -205.412587524 -0.694145479 -0.000013011 0.000122647 2.99 0.092071013 + 9 -205.412583130 -0.694141084 0.000004395 0.000033961 3.27 0.092226700 + 10 -205.412588181 -0.694146135 -0.000005051 0.000020167 3.27 0.092275788 + 11 -205.412585345 -0.694143299 0.000002836 0.000015954 3.13 0.092268071 + 12 -205.412586572 -0.694144526 -0.000001227 0.000012090 3.09 0.092279436 + 13 -205.412586325 -0.694144279 0.000000247 0.000007973 3.19 0.092275053 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.718442046 +E(CORR) ... -0.694144279 +E(TOT) ... -205.412586325 +Singles norm **1/2 ... 0.092275053 ( 0.046137526, 0.046137526) +T1 diagnostic ... 0.021749439 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.057113 + 10a-> 13a 10b-> 13b 0.041061 + 8b-> 13b -1b-> -1b 0.038290 + 8a-> 13a -1a-> -1a 0.038290 + 10b-> 13b -1b-> -1b 0.034962 + 10a-> 13a -1a-> -1a 0.034962 + 8a-> 13a 9b-> 13b 0.030829 + 9a-> 13a 8b-> 13b 0.030829 + 8a-> 13a 10b-> 13b 0.029198 + 10a-> 13a 8b-> 13b 0.029198 + 11a-> 13a 11b-> 13b 0.028039 + 5a-> 13a 5b-> 13b 0.026747 + 9a-> 13a 9b-> 13b 0.026328 + 9a-> 13a 10b-> 13b 0.024597 + 10a-> 13a 9b-> 13b 0.024597 + 11a-> 26a 11b-> 26b 0.024355 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034700385 + alpha-alpha-alpha ... -0.000892798 ( 2.6%) + alpha-alpha-beta ... -0.016457394 ( 47.4%) + alpha-beta -beta ... -0.016457394 ( 47.4%) + beta -beta -beta ... -0.000892798 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034700385 + +Final correlation energy ... -0.728844664 +E(CCSD) ... -205.412586325 +E(CCSD(T)) ... -205.447286709 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210443923 sqrt= 1.100201765 +W(HF) = 0.826143187 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.269430 0.000000 + 1 N : 0.159137 0.000000 + 2 O : -0.148059 -0.000000 + 3 H : 0.258352 -0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.846260 s : 3.846260 + pz : 1.271602 p : 4.359542 + px : 1.353945 + py : 1.733995 + dz2 : 0.014453 d : 0.055237 + dxz : 0.010654 + dyz : 0.014168 + dx2y2 : 0.008737 + dxy : 0.007225 + f0 : 0.002234 f : 0.008392 + f+1 : 0.000909 + f-1 : 0.001696 + f+2 : 0.000850 + f-2 : 0.000791 + f+3 : 0.000918 + f-3 : 0.000994 + 1 N s : 3.881139 s : 3.881139 + pz : 0.915924 p : 2.760544 + px : 0.973261 + py : 0.871358 + dz2 : 0.037350 d : 0.169756 + dxz : 0.055348 + dyz : 0.026384 + dx2y2 : 0.017737 + dxy : 0.032938 + f0 : 0.008692 f : 0.029424 + f+1 : 0.003842 + f-1 : 0.005986 + f+2 : 0.003820 + f-2 : 0.002426 + f+3 : 0.002239 + f-3 : 0.002419 + 2 O s : 3.866222 s : 3.866222 + pz : 1.766334 p : 4.186493 + px : 1.166342 + py : 1.253816 + dz2 : 0.010129 d : 0.085094 + dxz : 0.023178 + dyz : 0.007633 + dx2y2 : 0.016999 + dxy : 0.027155 + f0 : 0.001642 f : 0.010250 + f+1 : 0.001499 + f-1 : 0.000863 + f+2 : 0.001466 + f-2 : 0.000878 + f+3 : 0.001839 + f-3 : 0.002063 + 3 H s : 0.637263 s : 0.637263 + pz : 0.023102 p : 0.085356 + px : 0.014778 + py : 0.047476 + dz2 : 0.000668 d : 0.019029 + dxz : 0.008260 + dyz : 0.000775 + dx2y2 : 0.002729 + dxy : 0.006596 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.610996 0.000000 + 1 N : -0.308633 0.000000 + 2 O : 0.274501 -0.000000 + 3 H : -0.576863 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.125749 s : 3.125749 + pz : 1.220263 p : 3.857464 + px : 1.253573 + py : 1.383628 + dz2 : 0.124893 d : 0.313870 + dxz : 0.072343 + dyz : 0.052494 + dx2y2 : 0.041339 + dxy : 0.022801 + f0 : 0.030846 f : 0.091921 + f+1 : 0.022184 + f-1 : 0.015688 + f+2 : 0.009684 + f-2 : 0.007182 + f+3 : 0.003003 + f-3 : 0.003335 + 1 N s : 3.016263 s : 3.016263 + pz : 0.941422 p : 2.882010 + px : 1.137745 + py : 0.802843 + dz2 : 0.225340 d : 0.968076 + dxz : 0.315224 + dyz : 0.106516 + dx2y2 : 0.164713 + dxy : 0.156283 + f0 : 0.116203 f : 0.442284 + f+1 : 0.069818 + f-1 : 0.057386 + f+2 : 0.064909 + f-2 : 0.027663 + f+3 : 0.053370 + f-3 : 0.052934 + 2 O s : 3.317898 s : 3.317898 + pz : 1.447752 p : 3.923433 + px : 1.367682 + py : 1.107999 + dz2 : 0.052940 d : 0.357410 + dxz : 0.110404 + dyz : 0.014267 + dx2y2 : 0.097423 + dxy : 0.082376 + f0 : 0.015992 f : 0.126758 + f+1 : 0.022354 + f-1 : 0.004083 + f+2 : 0.023837 + f-2 : 0.006985 + f+3 : 0.025443 + f-3 : 0.028063 + 3 H s : 0.624440 s : 0.624440 + pz : 0.139356 p : 0.568546 + px : 0.256263 + py : 0.172928 + dz2 : 0.037756 d : 0.383877 + dxz : 0.121602 + dyz : 0.014970 + dx2y2 : 0.098526 + dxy : 0.111023 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2694 8.0000 -0.2694 2.2727 1.8115 0.4612 + 1 N 6.8409 7.0000 0.1591 2.8300 2.3500 0.4800 + 2 O 8.1481 8.0000 -0.1481 2.1449 1.6476 0.4973 + 3 H 0.7416 1.0000 0.2584 0.9721 0.9008 0.0713 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8205 B( 0-O , 3-H ) : 0.8930 B( 1-N , 2-O ) : 1.5356 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 57.542 sec + +Fock Matrix Formation ... 0.204 sec ( 0.4%) +Initial Guess ... 0.131 sec ( 0.2%) +DIIS Solver ... 1.887 sec ( 3.3%) +State Vector Update ... 0.089 sec ( 0.2%) +Sigma-vector construction ... 40.008 sec ( 69.5%) + <0|H|D> ... 0.004 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.025 sec ( 0.1% of sigma) + (0-ext) ... 0.068 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.026 sec ( 0.1% of sigma) + (2-ext) ... 0.933 sec ( 2.3% of sigma) + (4-ext) ... 22.765 sec ( 56.9% of sigma) + ... 1.484 sec ( 3.7% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.119 sec ( 0.3% of sigma) + Fock-dressing ... 2.189 sec ( 5.5% of sigma) + (ik|jl)-dressing ... 0.074 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.720 sec ( 24.3% of sigma) + Pair energies ... 0.010 sec ( 0.0% of sigma) +Total Time for computing (T) ... 7.074 sec ( 12.3% of ALL) + I/O of integral and amplitudes ... 0.772 sec ( 10.9% of (T)) + External N**7 contributions ... 3.919 sec ( 55.4% of (T)) + Internal N**7 contributions ... 0.317 sec ( 4.5% of (T)) + N**6 triples energy contributions ... 1.696 sec ( 24.0% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.447286709395 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.041.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.041.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.709469, -0.117309 -0.319746) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.67559 -0.14273 -0.82141 +Nuclear contribution : -1.47536 0.27207 0.73680 + ----------------------------------------- +Total Dipole Moment : -0.79977 0.12933 -0.08460 + ----------------------------------------- +Magnitude (a.u.) : 0.81457 +Magnitude (Debye) : 2.07046 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.986251 0.413368 0.366788 +Rotational constants in MHz : 89525.557747 12392.462654 10996.033540 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.519960 -0.540457 -0.317910 +x,y,z [Debye]: 1.321634 -1.373733 -0.808062 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.709469, -0.117309 -0.319746) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.84440 -0.11948 -0.78510 +Nuclear contribution : -1.47536 0.27207 0.73680 + ----------------------------------------- +Total Dipole Moment : -0.63096 0.15259 -0.04830 + ----------------------------------------- +Magnitude (a.u.) : 0.65094 +Magnitude (Debye) : 1.65457 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.986251 0.413368 0.366788 +Rotational constants in MHz : 89525.557747 12392.462654 10996.033540 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.422451 -0.397929 -0.294813 +x,y,z [Debye]: 1.073785 -1.011456 -0.749355 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 42 * + * * + * Dihedral ( 2, 1, 0, 3) : 155.45454545 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0398041082 RMS(Int)= 0.0002344420 + Iter 1: RMS(Cart)= 0.0000653486 RMS(Int)= 0.0000011824 + Iter 2: RMS(Cart)= 0.0000003296 RMS(Int)= 0.0000000060 + Iter 3: RMS(Cart)= 0.0000000017 RMS(Int)= 0.0000000000 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4511 0.000000 + 2. B(O 2,N 1) 1.1735 0.000000 + 3. B(H 3,O 0) 0.9719 0.000000 + 4. A(N 1,O 0,H 3) 102.0004 0.000000 + 5. A(O 0,N 1,O 2) 110.4637 0.000000 + 6. D(O 2,N 1,O 0,H 3) 155.4545 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.268550 0.002318 0.738753 + N 0.167623 -0.205972 -0.629527 + O 1.315871 0.013174 -0.731956 + H -1.214944 0.190479 0.622730 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.507485 0.004381 1.396041 + 1 N 7.0000 0 14.007 0.316761 -0.389231 -1.189634 + 2 O 8.0000 0 15.999 2.486636 0.024896 -1.383196 + 3 H 1.0000 0 1.008 -2.295911 0.359954 1.176789 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.451092638658 0.00000000 0.00000000 + O 2 1 0 1.171309639152 110.51812271 0.00000000 + H 1 2 3 0.969073736954 102.03673458 147.27272731 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.742167682012 0.00000000 0.00000000 + O 2 1 0 2.213454436020 110.51812271 0.00000000 + H 1 2 3 1.831283966419 102.03673458 147.27272731 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2225 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2690 + la=0 lb=0: 549 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.111075960165 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.1110759602 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.988e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7149655152 0.000000000000 0.00180464 0.00005457 0.0199011 0.7000 + 1 -204.7158727428 -0.000907227589 0.00172269 0.00004909 0.0164562 0.7000 + ***Turning on DIIS*** + 2 -204.7166465699 -0.000773827067 0.00470938 0.00013242 0.0133565 0.0000 + 3 -204.7198494930 -0.003202923140 0.00182304 0.00005317 0.0052252 0.0000 + 4 -204.7185884885 0.001261004474 0.00087353 0.00002423 0.0020220 0.0000 + 5 -204.7200536726 -0.001465184108 0.00052385 0.00001897 0.0010294 0.0000 + 6 -204.7192450310 0.000808641671 0.00064845 0.00002255 0.0005869 0.0000 + 7 -204.7190765634 0.000168467546 0.00032671 0.00001154 0.0002828 0.0000 + 8 -204.7196981128 -0.000621549336 0.00017870 0.00000692 0.0002044 0.0000 + 9 -204.7193043967 0.000393716048 0.00015069 0.00000503 0.0001271 0.0000 + 10 -204.7195032416 -0.000198844925 0.00006532 0.00000205 0.0000546 0.0000 + 11 -204.7195134898 -0.000010248199 0.00001893 0.00000057 0.0000254 0.0000 + 12 -204.7194535242 0.000059965688 0.00000615 0.00000020 0.0000082 0.0000 + 13 -204.7194737455 -0.000020221325 0.00000198 0.00000006 0.0000024 0.0000 + 14 -204.7194681251 0.000005620375 0.00000090 0.00000003 0.0000015 0.0000 + 15 -204.7194694145 -0.000001289386 0.00000051 0.00000002 0.0000011 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 16 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.71947110 Eh -5570.70002 eV + +Components: +Nuclear Repulsion : 69.11107596 Eh 1880.60799 eV +Electronic Energy : -273.83054706 Eh -7451.30800 eV +One Electron Energy: -417.94077173 Eh -11372.74658 eV +Two Electron Energy: 144.11022467 Eh 3921.43858 eV + +Virial components: +Potential Energy : -408.94121703 Eh -11127.85624 eV +Kinetic Energy : 204.22174594 Eh 5557.15623 eV +Virial Ratio : 2.00243718 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.6852e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.7875e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.2148e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.5811e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.672392 -562.5244 + 1 1.0000 -20.635397 -561.5177 + 2 1.0000 -15.800927 -429.9651 + 3 1.0000 -1.605278 -43.6818 + 4 1.0000 -1.393316 -37.9141 + 5 1.0000 -0.949072 -25.8256 + 6 1.0000 -0.779544 -21.2125 + 7 1.0000 -0.728787 -19.8313 + 8 1.0000 -0.684888 -18.6367 + 9 1.0000 -0.620864 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2.5365 + 15 0.0000 0.098330 2.6757 + 16 0.0000 0.125126 3.4049 + 17 0.0000 0.146907 3.9975 + 18 0.0000 0.156961 4.2711 + 19 0.0000 0.172631 4.6975 + 20 0.0000 0.187036 5.0895 + 21 0.0000 0.195253 5.3131 + 22 0.0000 0.204246 5.5578 + 23 0.0000 0.234334 6.3766 + 24 0.0000 0.261530 7.1166 + 25 0.0000 0.290267 7.8986 + 26 0.0000 0.307105 8.3568 + 27 0.0000 0.329140 8.9564 + 28 0.0000 0.359946 9.7946 + 29 0.0000 0.373634 10.1671 + 30 0.0000 0.423546 11.5253 + 31 0.0000 0.512940 13.9578 + 32 0.0000 0.527779 14.3616 + 33 0.0000 0.547636 14.9019 + 34 0.0000 0.569494 15.4967 + 35 0.0000 0.613558 16.6958 + 36 0.0000 0.632435 17.2094 + 37 0.0000 0.646731 17.5984 + 38 0.0000 0.692572 18.8458 + 39 0.0000 0.717009 19.5108 + 40 0.0000 0.724846 19.7241 + 41 0.0000 0.745939 20.2980 + 42 0.0000 0.770713 20.9722 + 43 0.0000 0.790388 21.5075 + 44 0.0000 0.805706 21.9244 + 45 0.0000 0.817361 22.2415 + 46 0.0000 0.855741 23.2859 + 47 0.0000 0.866438 23.5770 + 48 0.0000 0.926602 25.2141 + 49 0.0000 0.941255 25.6128 + 50 0.0000 0.954337 25.9688 + 51 0.0000 1.004752 27.3407 + 52 0.0000 1.039012 28.2729 + 53 0.0000 1.052796 28.6480 + 54 0.0000 1.057514 28.7764 + 55 0.0000 1.090351 29.6699 + 56 0.0000 1.159297 31.5461 + 57 0.0000 1.195841 32.5405 + 58 0.0000 1.250240 34.0208 + 59 0.0000 1.297984 35.3199 + 60 0.0000 1.372368 37.3440 + 61 0.0000 1.413603 38.4661 + 62 0.0000 1.491206 40.5778 + 63 0.0000 1.513200 41.1763 + 64 0.0000 1.517201 41.2851 + 65 0.0000 1.537973 41.8504 + 66 0.0000 1.572402 42.7872 + 67 0.0000 1.605995 43.7013 + 68 0.0000 1.666892 45.3584 + 69 0.0000 1.726974 46.9934 + 70 0.0000 1.769856 48.1602 + 71 0.0000 1.805748 49.1369 + 72 0.0000 1.867173 50.8084 + 73 0.0000 1.940153 52.7942 + 74 0.0000 1.960472 53.3472 + 75 0.0000 2.017929 54.9106 + 76 0.0000 2.066733 56.2387 + 77 0.0000 2.099098 57.1194 + 78 0.0000 2.162035 58.8320 + 79 0.0000 2.179144 59.2975 + 80 0.0000 2.283438 62.1355 + 81 0.0000 2.301753 62.6339 + 82 0.0000 2.311056 62.8870 + 83 0.0000 2.376450 64.6665 + 84 0.0000 2.443493 66.4908 + 85 0.0000 2.467294 67.1385 + 86 0.0000 2.490839 67.7792 + 87 0.0000 2.501179 68.0606 + 88 0.0000 2.517549 68.5060 + 89 0.0000 2.532492 68.9126 + 90 0.0000 2.572930 70.0130 + 91 0.0000 2.601187 70.7819 + 92 0.0000 2.646663 72.0194 + 93 0.0000 2.702707 73.5444 + 94 0.0000 2.734787 74.4173 + 95 0.0000 2.753194 74.9182 + 96 0.0000 2.859171 77.8020 + 97 0.0000 2.892624 78.7123 + 98 0.0000 2.935994 79.8925 + 99 0.0000 3.090483 84.0963 + 100 0.0000 3.147941 85.6598 + 101 0.0000 3.181616 86.5762 + 102 0.0000 3.256014 88.6006 + 103 0.0000 3.460724 94.1711 + 104 0.0000 3.768859 102.5559 + 105 0.0000 3.885313 105.7248 + 106 0.0000 4.028413 109.6187 + 107 0.0000 4.159923 113.1973 + 108 0.0000 4.179189 113.7215 + 109 0.0000 4.256519 115.8258 + 110 0.0000 4.358386 118.5977 + 111 0.0000 4.397733 119.6684 + 112 0.0000 4.553549 123.9084 + 113 0.0000 4.623057 125.7998 + 114 0.0000 4.747951 129.1983 + 115 0.0000 4.798022 130.5608 + 116 0.0000 4.819320 131.1404 + 117 0.0000 4.892560 133.1333 + 118 0.0000 4.963288 135.0579 + 119 0.0000 4.999318 136.0384 + 120 0.0000 5.066866 137.8764 + 121 0.0000 5.098979 138.7503 + 122 0.0000 5.168676 140.6468 + 123 0.0000 5.238994 142.5603 + 124 0.0000 5.253609 142.9580 + 125 0.0000 5.318834 144.7328 + 126 0.0000 5.332153 145.0953 + 127 0.0000 5.400529 146.9559 + 128 0.0000 5.558196 151.2462 + 129 0.0000 5.681825 154.6103 + 130 0.0000 5.793398 157.6464 + 131 0.0000 5.998136 163.2176 + 132 0.0000 6.108531 166.2216 + 133 0.0000 6.411154 174.4564 + 134 0.0000 6.501664 176.9193 + 135 0.0000 6.507383 177.0749 + 136 0.0000 6.685113 181.9112 + 137 0.0000 6.708018 182.5344 + 138 0.0000 6.740646 183.4223 + 139 0.0000 6.842842 186.2032 + 140 0.0000 6.908373 187.9864 + 141 0.0000 7.061425 192.1511 + 142 0.0000 7.123612 193.8433 + 143 0.0000 7.175828 195.2642 + 144 0.0000 7.196059 195.8147 + 145 0.0000 7.231827 196.7880 + 146 0.0000 7.260211 197.5604 + 147 0.0000 7.341358 199.7685 + 148 0.0000 7.388276 201.0452 + 149 0.0000 7.432869 202.2587 + 150 0.0000 7.477438 203.4714 + 151 0.0000 7.598494 206.7655 + 152 0.0000 7.627711 207.5606 + 153 0.0000 7.678501 208.9426 + 154 0.0000 7.817842 212.7343 + 155 0.0000 7.927694 215.7235 + 156 0.0000 8.038499 218.7387 + 157 0.0000 8.389810 228.2983 + 158 0.0000 14.096743 383.5919 + 159 0.0000 14.944598 406.6632 + 160 0.0000 16.035361 436.3443 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.355533 0.000000 + 1 N : 0.347603 0.000000 + 2 O : -0.268264 0.000000 + 3 H : 0.276194 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.868812 s : 3.868812 + pz : 1.284146 p : 4.458650 + px : 1.353236 + py : 1.821268 + dz2 : 0.009571 d : 0.023487 + dxz : 0.004247 + dyz : 0.007215 + dx2y2 : 0.002190 + dxy : 0.000263 + f0 : 0.002076 f : 0.004585 + f+1 : 0.000364 + f-1 : 0.001208 + f+2 : 0.000231 + f-2 : 0.000107 + f+3 : 0.000355 + f-3 : 0.000244 + 1 N s : 3.829450 s : 3.829450 + pz : 0.886955 p : 2.652332 + px : 0.996610 + py : 0.768767 + dz2 : 0.032240 d : 0.140795 + dxz : 0.045514 + dyz : 0.017014 + dx2y2 : 0.012686 + dxy : 0.033342 + f0 : 0.008922 f : 0.029821 + f+1 : 0.004139 + f-1 : 0.006024 + f+2 : 0.003707 + f-2 : 0.001511 + f+3 : 0.002294 + f-3 : 0.003224 + 2 O s : 3.878606 s : 3.878606 + pz : 1.859615 p : 4.318156 + px : 1.172499 + py : 1.286042 + dz2 : 0.005124 d : 0.063712 + dxz : 0.015581 + dyz : 0.000831 + dx2y2 : 0.013405 + dxy : 0.028771 + f0 : 0.001151 f : 0.007789 + f+1 : 0.001050 + f-1 : 0.000378 + f+2 : 0.001091 + f-2 : 0.000165 + f+3 : 0.001541 + f-3 : 0.002412 + 3 H s : 0.622976 s : 0.622976 + pz : 0.019258 p : 0.078786 + px : 0.018170 + py : 0.041357 + dz2 : 0.000294 d : 0.022044 + dxz : 0.009764 + dyz : 0.000332 + dx2y2 : 0.002540 + dxy : 0.009114 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.594366 0.000000 + 1 N : -0.258784 0.000000 + 2 O : 0.236559 0.000000 + 3 H : -0.572141 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.120922 s : 3.120922 + pz : 1.218926 p : 3.915946 + px : 1.254932 + py : 1.442088 + dz2 : 0.120961 d : 0.283744 + dxz : 0.066491 + dyz : 0.045022 + dx2y2 : 0.037260 + dxy : 0.014009 + f0 : 0.030480 f : 0.085022 + f+1 : 0.021154 + f-1 : 0.013595 + f+2 : 0.008744 + f-2 : 0.006328 + f+3 : 0.003014 + f-3 : 0.001707 + 1 N s : 3.011721 s : 3.011721 + pz : 0.935951 p : 2.834502 + px : 1.169053 + py : 0.729498 + dz2 : 0.218076 d : 0.959018 + dxz : 0.322142 + dyz : 0.101047 + dx2y2 : 0.166443 + dxy : 0.151310 + f0 : 0.119519 f : 0.453542 + f+1 : 0.070746 + f-1 : 0.059758 + f+2 : 0.075767 + f-2 : 0.022172 + f+3 : 0.052246 + f-3 : 0.053334 + 2 O s : 3.317071 s : 3.317071 + pz : 1.508965 p : 4.002730 + px : 1.381513 + py : 1.112252 + dz2 : 0.046466 d : 0.325915 + dxz : 0.110827 + dyz : 0.005975 + dx2y2 : 0.097123 + dxy : 0.065525 + f0 : 0.015763 f : 0.117724 + f+1 : 0.021824 + f-1 : 0.002760 + f+2 : 0.026001 + f-2 : 0.003982 + f+3 : 0.023083 + f-3 : 0.024312 + 3 H s : 0.622188 s : 0.622188 + pz : 0.136165 p : 0.555786 + px : 0.256775 + py : 0.162847 + dz2 : 0.037128 d : 0.394167 + dxz : 0.129412 + dyz : 0.010435 + dx2y2 : 0.097448 + dxy : 0.119744 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3555 8.0000 -0.3555 1.9223 1.9223 -0.0000 + 1 N 6.6524 7.0000 0.3476 2.5445 2.5445 -0.0000 + 2 O 8.2683 8.0000 -0.2683 1.7427 1.7427 -0.0000 + 3 H 0.7238 1.0000 0.2762 0.9440 0.9440 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.9029 B( 0-O , 3-H ) : 0.9617 B( 1-N , 2-O ) : 1.6721 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.678 sec +Sum of individual times .... 2.305 sec ( 86.1%) + +Fock matrix formation .... 1.826 sec ( 68.2%) +Diagonalization .... 0.185 sec ( 6.9%) +Density matrix formation .... 0.014 sec ( 0.5%) +Population analysis .... 0.111 sec ( 4.2%) +Initial guess .... 0.010 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.006 sec ( 0.2%) +DIIS solution .... 0.158 sec ( 5.9%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.215 sec +Reference energy ... -204.719470598 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.382 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.392 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.023 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.034 s ( 0.000 ms/b) + 151164 b 0 skpd 0.045 s ( 0.000 ms/b) +: 159120 b 0 skpd 0.018 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.033 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.354 sec +AO-integral generation ... 0.251 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.049 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.149 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.250 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090643652 +EMP2(bb)= -0.090643652 +EMP2(ab)= -0.517421022 + +Initial guess performed in 0.133 sec +E(0) ... -204.719470598 +E(MP2) ... -0.698708327 +Initial E(tot) ... -205.418178925 + ... 0.189199053 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.418178925 -0.698708327 -0.000000000 0.025203568 2.92 0.000001836 + *** Turning on DIIS *** + 1 -205.388574506 -0.669103907 0.029604419 0.010726585 2.97 0.058245814 + 2 -205.408251371 -0.688780772 -0.019676865 0.005471738 2.87 0.061111409 + 3 -205.412005091 -0.692534492 -0.003753720 0.002272582 3.02 0.075627742 + 4 -205.413595137 -0.694124539 -0.001590047 0.001737756 3.31 0.082550086 + 5 -205.414169375 -0.694698777 -0.000574237 0.000948724 2.99 0.088452253 + 6 -205.414286708 -0.694816109 -0.000117333 0.000567506 3.04 0.091439631 + 7 -205.414335191 -0.694864593 -0.000048484 0.000225005 3.01 0.092825673 + 8 -205.414348554 -0.694877956 -0.000013363 0.000116147 2.96 0.093341619 + 9 -205.414344128 -0.694873529 0.000004427 0.000030963 2.91 0.093492794 + 10 -205.414349122 -0.694878524 -0.000004994 0.000015182 2.89 0.093537733 + 11 -205.414346390 -0.694875792 0.000002732 0.000012187 2.89 0.093530144 + 12 -205.414347486 -0.694876887 -0.000001096 0.000009505 3.29 0.093540302 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.719470598 +E(CORR) ... -0.694876887 +E(TOT) ... -205.414347486 +Singles norm **1/2 ... 0.093540302 ( 0.046770151, 0.046770151) +T1 diagnostic ... 0.022047661 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.061350 + 10a-> 13a 10b-> 13b 0.046018 + 8b-> 13b -1b-> -1b 0.040999 + 8a-> 13a -1a-> -1a 0.040999 + 10b-> 13b -1b-> -1b 0.035698 + 10a-> 13a -1a-> -1a 0.035698 + 8a-> 13a 10b-> 13b 0.032329 + 10a-> 13a 8b-> 13b 0.032329 + 11a-> 13a 11b-> 13b 0.027898 + 5a-> 13a 5b-> 13b 0.026639 + 9a-> 13a 8b-> 13b 0.025712 + 8a-> 13a 9b-> 13b 0.025712 + 11a-> 26a -1a-> -1a 0.024302 + 11b-> 26b -1b-> -1b 0.024302 + 11a-> 26a 11b-> 26b 0.023263 + 8a-> 22a 8b-> 13b 0.021261 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034953319 + alpha-alpha-alpha ... -0.000899872 ( 2.6%) + alpha-alpha-beta ... -0.016576787 ( 47.4%) + alpha-beta -beta ... -0.016576787 ( 47.4%) + beta -beta -beta ... -0.000899872 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034953319 + +Final correlation energy ... -0.729830207 +E(CCSD) ... -205.414347486 +E(CCSD(T)) ... -205.449300805 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.211422791 sqrt= 1.100646533 +W(HF) = 0.825475637 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.269090 -0.000000 + 1 N : 0.158065 0.000000 + 2 O : -0.151863 -0.000000 + 3 H : 0.262887 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.847761 s : 3.847761 + pz : 1.274900 p : 4.357253 + px : 1.340344 + py : 1.742009 + dz2 : 0.014458 d : 0.055677 + dxz : 0.010300 + dyz : 0.014556 + dx2y2 : 0.008978 + dxy : 0.007384 + f0 : 0.002251 f : 0.008399 + f+1 : 0.000882 + f-1 : 0.001737 + f+2 : 0.000902 + f-2 : 0.000752 + f+3 : 0.001002 + f-3 : 0.000873 + 1 N s : 3.880278 s : 3.880278 + pz : 0.917159 p : 2.761309 + px : 0.980872 + py : 0.863278 + dz2 : 0.037802 d : 0.171144 + dxz : 0.056405 + dyz : 0.025873 + dx2y2 : 0.016446 + dxy : 0.034617 + f0 : 0.008639 f : 0.029204 + f+1 : 0.003839 + f-1 : 0.005967 + f+2 : 0.004007 + f-2 : 0.002064 + f+3 : 0.002032 + f-3 : 0.002656 + 2 O s : 3.866830 s : 3.866830 + pz : 1.774459 p : 4.189560 + px : 1.162562 + py : 1.252540 + dz2 : 0.010140 d : 0.085154 + dxz : 0.023731 + dyz : 0.007193 + dx2y2 : 0.015182 + dxy : 0.028908 + f0 : 0.001648 f : 0.010319 + f+1 : 0.001516 + f-1 : 0.000853 + f+2 : 0.001594 + f-2 : 0.000787 + f+3 : 0.001628 + f-3 : 0.002293 + 3 H s : 0.634926 s : 0.634926 + pz : 0.023067 p : 0.083293 + px : 0.012572 + py : 0.047654 + dz2 : 0.000613 d : 0.018893 + dxz : 0.008720 + dyz : 0.000392 + dx2y2 : 0.001477 + dxy : 0.007691 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.610559 0.000000 + 1 N : -0.309151 0.000000 + 2 O : 0.270976 -0.000000 + 3 H : -0.572384 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.127849 s : 3.127849 + pz : 1.221981 p : 3.854617 + px : 1.248214 + py : 1.384423 + dz2 : 0.127148 d : 0.314986 + dxz : 0.071922 + dyz : 0.051378 + dx2y2 : 0.044791 + dxy : 0.019745 + f0 : 0.031417 f : 0.091989 + f+1 : 0.022600 + f-1 : 0.015270 + f+2 : 0.009401 + f-2 : 0.007000 + f+3 : 0.003893 + f-3 : 0.002409 + 1 N s : 3.016825 s : 3.016825 + pz : 0.944255 p : 2.882308 + px : 1.151062 + py : 0.786991 + dz2 : 0.225201 d : 0.968124 + dxz : 0.319329 + dyz : 0.102934 + dx2y2 : 0.171150 + dxy : 0.149510 + f0 : 0.117291 f : 0.441894 + f+1 : 0.070773 + f-1 : 0.057036 + f+2 : 0.070052 + f-2 : 0.021519 + f+3 : 0.052471 + f-3 : 0.052751 + 2 O s : 3.318943 s : 3.318943 + pz : 1.454071 p : 3.926777 + px : 1.374167 + py : 1.098539 + dz2 : 0.052266 d : 0.356919 + dxz : 0.112836 + dyz : 0.012388 + dx2y2 : 0.102898 + dxy : 0.076532 + f0 : 0.016162 f : 0.126386 + f+1 : 0.022507 + f-1 : 0.003466 + f+2 : 0.025824 + f-2 : 0.005086 + f+3 : 0.025287 + f-3 : 0.028053 + 3 H s : 0.624026 s : 0.624026 + pz : 0.137640 p : 0.564743 + px : 0.259528 + py : 0.167575 + dz2 : 0.038503 d : 0.383615 + dxz : 0.125037 + dyz : 0.010115 + dx2y2 : 0.096243 + dxy : 0.113716 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2691 8.0000 -0.2691 2.2911 1.8270 0.4641 + 1 N 6.8419 7.0000 0.1581 2.8336 2.3533 0.4803 + 2 O 8.1519 8.0000 -0.1519 2.1440 1.6460 0.4980 + 3 H 0.7371 1.0000 0.2629 0.9662 0.8950 0.0712 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8360 B( 0-O , 2-O ) : 0.1005 B( 0-O , 3-H ) : 0.8905 +B( 1-N , 2-O ) : 1.5291 + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 54.486 sec + +Fock Matrix Formation ... 0.215 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.2%) +DIIS Solver ... 1.709 sec ( 3.1%) +State Vector Update ... 0.081 sec ( 0.1%) +Sigma-vector construction ... 37.288 sec ( 68.4%) + <0|H|D> ... 0.005 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.025 sec ( 0.1% of sigma) + (0-ext) ... 0.065 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.024 sec ( 0.1% of sigma) + (2-ext) ... 0.876 sec ( 2.3% of sigma) + (4-ext) ... 21.307 sec ( 57.1% of sigma) + ... 1.348 sec ( 3.6% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.099 sec ( 0.3% of sigma) + Fock-dressing ... 2.042 sec ( 5.5% of sigma) + (ik|jl)-dressing ... 0.073 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 9.015 sec ( 24.2% of sigma) + Pair energies ... 0.006 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.906 sec ( 12.7% of ALL) + I/O of integral and amplitudes ... 0.797 sec ( 11.5% of (T)) + External N**7 contributions ... 3.978 sec ( 57.6% of (T)) + Internal N**7 contributions ... 0.317 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.712 sec ( 24.8% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.449300804824 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.000423046 -0.006322279 0.002872120 + 2 N : -0.000539286 -0.007524591 -0.000506218 + 3 O : 0.002186140 0.006438704 -0.001720421 + 4 H : -0.001223808 0.007408166 -0.000645481 + +Norm of the cartesian gradient ... 0.014545000 +RMS gradient ... 0.004198780 +MAX gradient ... 0.007524591 + +------- +TIMINGS +------- + +Total numerical gradient time ... 345.295 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 488.62 cm**-1 + 7: 605.21 cm**-1 + 8: 801.63 cm**-1 + 9: 1280.18 cm**-1 + 10: 1704.22 cm**-1 + 11: 3736.89 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 -0.057152 0.266364 -0.068409 0.060881 0.019777 -0.061005 + 1 -0.047674 -0.041547 -0.089060 0.004756 0.015697 0.011824 + 2 0.079121 -0.309342 -0.168898 0.061768 0.105822 -0.006703 + 3 0.047405 -0.174727 0.000919 0.000603 -0.641483 -0.001658 + 4 -0.071970 -0.086452 0.096018 0.011709 -0.137867 -0.000848 + 5 -0.042619 0.056597 0.482039 -0.045484 -0.063803 -0.000398 + 6 0.005716 -0.135972 0.062967 -0.071125 0.538982 0.001083 + 7 0.049597 0.070570 -0.012071 -0.007005 0.108814 0.000671 + 8 -0.035419 0.249294 -0.204627 0.039258 -0.018766 0.000039 + 9 0.157659 0.358396 0.073608 0.154223 0.045291 0.974117 + 10 0.969573 0.740676 0.270893 -0.127018 -0.060472 -0.186538 + 11 -0.101405 0.166618 -0.769738 -0.971433 -0.495160 0.111303 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 488.62 0.033083 167.19 0.021129 ( 0.077130 0.096489 -0.076614) + 7: 605.21 0.018305 92.50 0.009438 (-0.055408 0.037654 0.070359) + 8: 801.63 0.021252 107.40 0.008273 (-0.055909 0.020677 0.068700) + 9: 1280.18 0.029135 147.24 0.007102 ( 0.040405 -0.013880 -0.072642) + 10: 1704.22 0.025457 128.65 0.004662 (-0.054432 -0.001902 0.041171) + 11: 3736.89 0.014178 71.65 0.001184 ( 0.032163 -0.007174 -0.009902) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 488.62 E(vib) ... 0.15 +freq. 605.21 E(vib) ... 0.10 +freq. 801.63 E(vib) ... 0.05 +freq. 1280.18 E(vib) ... 0.01 +freq. 1704.22 E(vib) ... 0.00 +freq. 3736.89 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.44930081 Eh +Zero point energy ... 0.01963039 Eh 12.32 kcal/mol +Thermal vibrational correction ... 0.00048196 Eh 0.30 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42635591 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00331450 Eh 2.08 kcal/mol +Non-thermal (ZPE) correction 0.01963039 Eh 12.32 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02294489 Eh 14.40 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42635591 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.42541171 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 3.003306 0.412929 0.365171 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00065106 Eh 0.41 kcal/mol +Rotational entropy ... 0.00988478 Eh 6.20 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02833815 Eh 17.78 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00988478 Eh 6.20 kcal/mol| +| sn= 2 | S(rot)= 0.00923032 Eh 5.79 kcal/mol| +| sn= 3 | S(rot)= 0.00884749 Eh 5.55 kcal/mol| +| sn= 4 | S(rot)= 0.00857587 Eh 5.38 kcal/mol| +| sn= 5 | S(rot)= 0.00836518 Eh 5.25 kcal/mol| +| sn= 6 | S(rot)= 0.00819303 Eh 5.14 kcal/mol| +| sn= 7 | S(rot)= 0.00804749 Eh 5.05 kcal/mol| +| sn= 8 | S(rot)= 0.00792141 Eh 4.97 kcal/mol| +| sn= 9 | S(rot)= 0.00781020 Eh 4.90 kcal/mol| +| sn=10 | S(rot)= 0.00771072 Eh 4.84 kcal/mol| +| sn=11 | S(rot)= 0.00762073 Eh 4.78 kcal/mol| +| sn=12 | S(rot)= 0.00753858 Eh 4.73 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.42541171 Eh +Total entropy correction ... -0.02833815 Eh -17.78 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.45374986 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00444905 Eh -2.79 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.449300806 Eh +Current gradient norm .... 0.014545000 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.024958365 0.123289262 0.179024250 0.488043795 0.523550906 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999855205 +Lowest eigenvalues of augmented Hessian: + -0.000064537 0.122047010 0.178671755 0.488033329 0.523530751 +Length of the computed step .... 0.017019204 +The final length of the internal step .... 0.017019204 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0069480611 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0046353675 RMS(Int)= 0.0069475062 + Iter 1: RMS(Cart)= 0.0000010203 RMS(Int)= 0.0000020000 + Iter 2: RMS(Cart)= 0.0000000043 RMS(Int)= 0.0000000048 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0021371414 0.0001000000 NO + MAX gradient 0.0034918806 0.0003000000 NO + RMS step 0.0069480611 0.0020000000 NO + MAX step 0.0159517253 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0084 Max(Angles) 0.08 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4511 0.002750 -0.0084 1.4427 + 2. B(O 2,N 1) 1.1735 0.003492 -0.0010 1.1724 + 3. B(H 3,O 0) 0.9719 0.002703 -0.0029 0.9690 + 4. A(N 1,O 0,H 3) 102.00 0.000490 0.02 102.02 + 5. A(O 0,N 1,O 2) 110.46 0.000317 0.08 110.55 + 6. D(O 2,N 1,O 0,H 3) 155.45 -0.012631 0.00 155.45 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.267290 0.001985 0.735140 + N 0.165536 -0.205085 -0.625440 + O 1.312708 0.013269 -0.730054 + H -1.210953 0.189830 0.620354 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.505105 0.003752 1.389213 + 1 N 7.0000 0 14.007 0.312818 -0.387554 -1.181910 + 2 O 8.0000 0 15.999 2.480659 0.025075 -1.379603 + 3 H 1.0000 0 1.008 -2.288370 0.358728 1.172300 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.442703961434 0.00000000 0.00000000 + O 2 1 0 1.172444520012 110.54612310 0.00000000 + H 1 2 3 0.969000656245 102.02126066 155.45454572 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.726315379434 0.00000000 0.00000000 + O 2 1 0 2.215599050039 110.54612310 0.00000000 + H 1 2 3 1.831145863893 102.02126066 155.45454572 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.1 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.329452430476 Eh + +SHARK setup successfully completed in 0.5 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.971e-04 +Time for diagonalization ... 0.052 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.374 sec +Total time needed ... 0.776 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7205450624 0.000000000000 0.00036467 0.00000736 0.0016353 0.7000 + 1 -204.7205537990 -0.000008736600 0.00027155 0.00000604 0.0012481 0.7000 + ***Turning on DIIS*** + 2 -204.7205609513 -0.000007152275 0.00060078 0.00001554 0.0009422 0.0000 + 3 -204.7199692052 0.000591746043 0.00022665 0.00000554 0.0002083 0.0000 + 4 -204.7206068654 -0.000637660222 0.00006783 0.00000168 0.0000867 0.0000 + 5 -204.7207916552 -0.000184789784 0.00002465 0.00000058 0.0000396 0.0000 + 6 -204.7204863542 0.000305301075 0.00000895 0.00000026 0.0000184 0.0000 + 7 -204.7205836337 -0.000097279495 0.00000314 0.00000012 0.0000056 0.0000 + 8 -204.7205811095 0.000002524169 0.00000297 0.00000011 0.0000034 0.0000 + 9 -204.7205754368 0.000005672660 0.00000212 0.00000008 0.0000022 0.0000 + 10 -204.7205885542 -0.000013117382 0.00000156 0.00000006 0.0000015 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + +Total Energy : -204.72058267 Eh -5570.73026 eV + Last Energy change ... 5.8875e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.5585e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 11 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.579 sec +Reference energy ... -204.720583912 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 11.052 sec +AO-integral generation ... 0.425 sec +Half transformation ... 0.240 sec +K-integral sorting ... 8.574 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.064 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.074 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.100 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.119 s ( 0.001 ms/b) + 159120 b 0 skpd 0.051 s ( 0.000 ms/b) +: : 218790 b 0 skpd 0.096 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.088 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.068 s ( 0.001 ms/b) + 87516 b 0 skpd 0.111 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.065 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.955 sec +AO-integral generation ... 0.739 sec +Half transformation ... 0.102 sec +J-integral sorting ... 0.084 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.261 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.463 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090515713 +EMP2(bb)= -0.090515713 +EMP2(ab)= -0.516584999 + +Initial guess performed in 0.240 sec +E(0) ... -204.720583912 +E(MP2) ... -0.697616424 +Initial E(tot) ... -205.418200336 + ... 0.188163279 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.418200336 -0.697616424 -0.000000000 0.025199524 6.56 0.000000990 + *** Turning on DIIS *** + 1 -205.389093033 -0.668509120 0.029107304 0.010704292 6.76 0.057771326 + 2 -205.408589773 -0.688005860 -0.019496740 0.005475275 7.01 0.060708673 + 3 -205.412309456 -0.691725543 -0.003719683 0.002255014 6.30 0.075065332 + 4 -205.413877646 -0.693293733 -0.001568190 0.001682858 6.88 0.081900381 + 5 -205.414437824 -0.693853912 -0.000560178 0.000918186 7.35 0.087668005 + 6 -205.414551781 -0.693967868 -0.000113956 0.000546230 6.76 0.090561993 + 7 -205.414598054 -0.694014141 -0.000046273 0.000217756 6.63 0.091878363 + 8 -205.414610529 -0.694026616 -0.000012475 0.000112058 6.54 0.092365523 + 9 -205.414606215 -0.694022303 0.000004313 0.000029961 5.64 0.092507299 + 10 -205.414610931 -0.694027018 -0.000004715 0.000014811 6.02 0.092549251 + 11 -205.414608343 -0.694024431 0.000002587 0.000011899 7.86 0.092542117 + 12 -205.414609380 -0.694025468 -0.000001037 0.000009267 8.01 0.092551399 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.720583912 +E(CORR) ... -0.694025468 +E(TOT) ... -205.414609380 +Singles norm **1/2 ... 0.092551399 ( 0.046275700, 0.046275700) +T1 diagnostic ... 0.021814574 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.060005 + 10a-> 13a 10b-> 13b 0.046757 + 8a-> 13a -1a-> -1a 0.040978 + 8b-> 13b -1b-> -1b 0.040978 + 10a-> 13a -1a-> -1a 0.034488 + 10b-> 13b -1b-> -1b 0.034488 + 10a-> 13a 8b-> 13b 0.032156 + 8a-> 13a 10b-> 13b 0.032156 + 11a-> 13a 11b-> 13b 0.028025 + 5a-> 13a 5b-> 13b 0.026157 + 11b-> 26b -1b-> -1b 0.025868 + 11a-> 26a -1a-> -1a 0.025868 + 11a-> 26a 11b-> 26b 0.025568 + 8a-> 13a 9b-> 13b 0.025107 + 9a-> 13a 8b-> 13b 0.025107 + 8a-> 13a 8b-> 22b 0.021061 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034723345 + alpha-alpha-alpha ... -0.000896661 ( 2.6%) + alpha-alpha-beta ... -0.016465011 ( 47.4%) + alpha-beta -beta ... -0.016465011 ( 47.4%) + beta -beta -beta ... -0.000896661 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034723345 + +Final correlation energy ... -0.728748813 +E(CCSD) ... -205.414609380 +E(CCSD(T)) ... -205.449332725 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210063749 sqrt= 1.100028976 +W(HF) = 0.826402742 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 120.326 sec + +Fock Matrix Formation ... 0.579 sec ( 0.5%) +Initial Guess ... 0.240 sec ( 0.2%) +DIIS Solver ... 5.114 sec ( 4.3%) +State Vector Update ... 0.215 sec ( 0.2%) +Sigma-vector construction ... 82.952 sec ( 68.9%) + <0|H|D> ... 0.008 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.046 sec ( 0.1% of sigma) + (0-ext) ... 0.145 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.058 sec ( 0.1% of sigma) + (2-ext) ... 2.067 sec ( 2.5% of sigma) + (4-ext) ... 48.366 sec ( 58.3% of sigma) + ... 4.240 sec ( 5.1% of sigma) + ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.021 sec ( 0.0% of sigma) + (1-ext) ... 0.232 sec ( 0.3% of sigma) + Fock-dressing ... 5.422 sec ( 6.5% of sigma) + (ik|jl)-dressing ... 0.203 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 17.983 sec ( 21.7% of sigma) + Pair energies ... 0.021 sec ( 0.0% of sigma) +Total Time for computing (T) ... 16.104 sec ( 13.4% of ALL) + I/O of integral and amplitudes ... 1.666 sec ( 10.3% of (T)) + External N**7 contributions ... 9.530 sec ( 59.2% of (T)) + Internal N**7 contributions ... 0.857 sec ( 5.3% of (T)) + N**6 triples energy contributions ... 3.096 sec ( 19.2% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.449332725287 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.001993026 -0.006295937 0.000247947 + 2 N : 0.001834635 -0.006625694 0.001637938 + 3 O : -0.001311031 0.005922157 -0.001281079 + 4 H : 0.001469422 0.006999473 -0.000604805 + +Norm of the cartesian gradient ... 0.013548820 +RMS gradient ... 0.003911207 +MAX gradient ... 0.006999473 + +------- +TIMINGS +------- + +Total numerical gradient time ... 885.756 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.449332725 Eh +Current gradient norm .... 0.013548820 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999887 +Lowest eigenvalues of augmented Hessian: + -0.000000037 0.123937123 0.179387794 0.485562507 0.523695775 +Length of the computed step .... 0.000474669 +The final length of the internal step .... 0.000474669 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0001937827 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001196792 RMS(Int)= 0.0001937839 + Iter 1: RMS(Cart)= 0.0000000029 RMS(Int)= 0.0000000050 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000319196 0.0000050000 NO + RMS gradient 0.0000436683 0.0001000000 YES + MAX gradient 0.0000784674 0.0003000000 YES + RMS step 0.0001937827 0.0020000000 YES + MAX step 0.0004730104 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0003 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4427 -0.000078 0.0003 1.4430 + 2. B(O 2,N 1) 1.1724 -0.000065 0.0000 1.1724 + 3. B(H 3,O 0) 0.9690 -0.000003 0.0000 0.9690 + 4. A(N 1,O 0,H 3) 102.02 -0.000011 -0.00 102.02 + 5. A(O 0,N 1,O 2) 110.55 -0.000030 0.00 110.55 + 6. D(O 2,N 1,O 0,H 3) 155.45 -0.012858 -0.00 155.45 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.267360 0.001999 0.735259 + N 0.165601 -0.205097 -0.625540 + O 1.312777 0.013261 -0.730116 + H -1.211017 0.189837 0.620397 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.505237 0.003779 1.389438 + 1 N 7.0000 0 14.007 0.312940 -0.387577 -1.182099 + 2 O 8.0000 0 15.999 2.480790 0.025059 -1.379720 + 3 H 1.0000 0 1.008 -2.288491 0.358740 1.172381 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.442954267741 0.00000000 0.00000000 + O 2 1 0 1.172446411871 110.54673841 0.00000000 + H 1 2 3 0.969002275781 102.01909093 155.45454572 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.726788389804 0.00000000 0.00000000 + O 2 1 0 2.215602625136 110.54673841 0.00000000 + H 1 2 3 1.831148924372 102.01909093 155.45454572 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.1 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.3 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.4 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.323919900055 Eh + +SHARK setup successfully completed in 1.4 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.3239199001 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.972e-04 +Time for diagonalization ... 0.039 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.118 sec +Total time needed ... 0.420 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7205599567 0.000000000000 0.00000830 0.00000018 0.0000437 0.7000 + 1 -204.7205599640 -0.000000007297 0.00000630 0.00000015 0.0000344 0.7000 + ***Turning on DIIS*** + 2 -204.7205599701 -0.000000006100 0.00001560 0.00000040 0.0000267 0.0000 + 3 -204.7205690646 -0.000009094519 0.00000617 0.00000016 0.0000071 0.0000 + 4 -204.7205576656 0.000011399018 0.00000242 0.00000005 0.0000019 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72055559 Eh -5570.72953 eV + +Components: +Nuclear Repulsion : 69.32391990 Eh 1886.39976 eV +Electronic Energy : -274.04447549 Eh -7457.12929 eV +One Electron Energy: -418.35542389 Eh -11384.02984 eV +Two Electron Energy: 144.31094840 Eh 3926.90055 eV + +Virial components: +Potential Energy : -408.96592213 Eh -11128.52850 eV +Kinetic Energy : 204.24536654 Eh 5557.79898 eV +Virial Ratio : 2.00232656 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.0754e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.1083e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.4900e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.5486e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.670668 -562.4775 + 1 1.0000 -20.636220 -561.5401 + 2 1.0000 -15.799628 -429.9297 + 3 1.0000 -1.606419 -43.7129 + 4 1.0000 -1.396611 -38.0037 + 5 1.0000 -0.948912 -25.8212 + 6 1.0000 -0.781624 -21.2691 + 7 1.0000 -0.729502 -19.8508 + 8 1.0000 -0.686212 -18.6728 + 9 1.0000 -0.620928 -16.8963 + 10 1.0000 -0.529159 -14.3991 + 11 1.0000 -0.460883 -12.5413 + 12 0.0000 0.028605 0.7784 + 13 0.0000 0.078631 2.1396 + 14 0.0000 0.093397 2.5414 + 15 0.0000 0.098376 2.6769 + 16 0.0000 0.125012 3.4018 + 17 0.0000 0.146835 3.9956 + 18 0.0000 0.157052 4.2736 + 19 0.0000 0.172545 4.6952 + 20 0.0000 0.186847 5.0844 + 21 0.0000 0.195336 5.3154 + 22 0.0000 0.204488 5.5644 + 23 0.0000 0.234724 6.3872 + 24 0.0000 0.261786 7.1236 + 25 0.0000 0.291729 7.9384 + 26 0.0000 0.309531 8.4228 + 27 0.0000 0.329469 8.9653 + 28 0.0000 0.360195 9.8014 + 29 0.0000 0.374465 10.1897 + 30 0.0000 0.424065 11.5394 + 31 0.0000 0.513377 13.9697 + 32 0.0000 0.528156 14.3719 + 33 0.0000 0.548388 14.9224 + 34 0.0000 0.569732 15.5032 + 35 0.0000 0.613779 16.7018 + 36 0.0000 0.633484 17.2380 + 37 0.0000 0.646878 17.6025 + 38 0.0000 0.692504 18.8440 + 39 0.0000 0.717493 19.5240 + 40 0.0000 0.724763 19.7218 + 41 0.0000 0.745577 20.2882 + 42 0.0000 0.771449 20.9922 + 43 0.0000 0.789426 21.4814 + 44 0.0000 0.806003 21.9325 + 45 0.0000 0.817888 22.2559 + 46 0.0000 0.856679 23.3114 + 47 0.0000 0.867256 23.5992 + 48 0.0000 0.926614 25.2145 + 49 0.0000 0.941330 25.6149 + 50 0.0000 0.954244 25.9663 + 51 0.0000 1.004745 27.3405 + 52 0.0000 1.039915 28.2975 + 53 0.0000 1.054013 28.6812 + 54 0.0000 1.058559 28.8049 + 55 0.0000 1.091579 29.7034 + 56 0.0000 1.159823 31.5604 + 57 0.0000 1.197286 32.5798 + 58 0.0000 1.251283 34.0491 + 59 0.0000 1.298766 35.3412 + 60 0.0000 1.372420 37.3455 + 61 0.0000 1.413822 38.4721 + 62 0.0000 1.491711 40.5915 + 63 0.0000 1.513445 41.1829 + 64 0.0000 1.517460 41.2922 + 65 0.0000 1.539565 41.8937 + 66 0.0000 1.573230 42.8098 + 67 0.0000 1.606985 43.7283 + 68 0.0000 1.667823 45.3838 + 69 0.0000 1.728876 47.0451 + 70 0.0000 1.771036 48.1923 + 71 0.0000 1.807432 49.1827 + 72 0.0000 1.869496 50.8716 + 73 0.0000 1.941258 52.8243 + 74 0.0000 1.961987 53.3884 + 75 0.0000 2.018864 54.9361 + 76 0.0000 2.070148 56.3316 + 77 0.0000 2.100788 57.1653 + 78 0.0000 2.163413 58.8695 + 79 0.0000 2.179491 59.3070 + 80 0.0000 2.284127 62.1542 + 81 0.0000 2.303831 62.6904 + 82 0.0000 2.313432 62.9517 + 83 0.0000 2.375506 64.6408 + 84 0.0000 2.445460 66.5444 + 85 0.0000 2.468104 67.1605 + 86 0.0000 2.491523 67.7978 + 87 0.0000 2.502121 68.0862 + 88 0.0000 2.520290 68.5806 + 89 0.0000 2.533604 68.9429 + 90 0.0000 2.573741 70.0350 + 91 0.0000 2.601948 70.8026 + 92 0.0000 2.646596 72.0175 + 93 0.0000 2.705794 73.6284 + 94 0.0000 2.736520 74.4645 + 95 0.0000 2.755876 74.9912 + 96 0.0000 2.862487 77.8922 + 97 0.0000 2.897104 78.8342 + 98 0.0000 2.944360 80.1201 + 99 0.0000 3.095288 84.2271 + 100 0.0000 3.151936 85.7685 + 101 0.0000 3.181057 86.5610 + 102 0.0000 3.260072 88.7111 + 103 0.0000 3.464445 94.2723 + 104 0.0000 3.773502 102.6822 + 105 0.0000 3.890759 105.8729 + 106 0.0000 4.029304 109.6429 + 107 0.0000 4.163287 113.2888 + 108 0.0000 4.182631 113.8152 + 109 0.0000 4.260553 115.9355 + 110 0.0000 4.362082 118.6983 + 111 0.0000 4.400010 119.7304 + 112 0.0000 4.558166 124.0340 + 113 0.0000 4.626516 125.8939 + 114 0.0000 4.751320 129.2900 + 115 0.0000 4.805436 130.7626 + 116 0.0000 4.821142 131.1899 + 117 0.0000 4.892767 133.1390 + 118 0.0000 4.965858 135.1279 + 119 0.0000 5.001827 136.1066 + 120 0.0000 5.070865 137.9853 + 121 0.0000 5.100641 138.7955 + 122 0.0000 5.173735 140.7845 + 123 0.0000 5.241218 142.6208 + 124 0.0000 5.256494 143.0365 + 125 0.0000 5.326214 144.9337 + 126 0.0000 5.336905 145.2246 + 127 0.0000 5.410300 147.2217 + 128 0.0000 5.562455 151.3621 + 129 0.0000 5.684980 154.6962 + 130 0.0000 5.796678 157.7356 + 131 0.0000 6.001317 163.3041 + 132 0.0000 6.113124 166.3466 + 133 0.0000 6.416458 174.6007 + 134 0.0000 6.502970 176.9548 + 135 0.0000 6.509350 177.1284 + 136 0.0000 6.686651 181.9530 + 137 0.0000 6.708514 182.5479 + 138 0.0000 6.741256 183.4389 + 139 0.0000 6.848076 186.3456 + 140 0.0000 6.913391 188.1229 + 141 0.0000 7.068390 192.3407 + 142 0.0000 7.126296 193.9164 + 143 0.0000 7.181028 195.4057 + 144 0.0000 7.201974 195.9757 + 145 0.0000 7.233572 196.8355 + 146 0.0000 7.263162 197.6407 + 147 0.0000 7.346063 199.8965 + 148 0.0000 7.391108 201.1223 + 149 0.0000 7.438423 202.4098 + 150 0.0000 7.479571 203.5295 + 151 0.0000 7.604913 206.9402 + 152 0.0000 7.634689 207.7505 + 153 0.0000 7.686624 209.1637 + 154 0.0000 7.826298 212.9644 + 155 0.0000 7.942995 216.1399 + 156 0.0000 8.050788 219.0731 + 157 0.0000 8.397683 228.5126 + 158 0.0000 14.135713 384.6523 + 159 0.0000 15.020535 408.7295 + 160 0.0000 16.086189 437.7274 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.670668 -562.4775 + 1 1.0000 -20.636220 -561.5401 + 2 1.0000 -15.799628 -429.9297 + 3 1.0000 -1.606419 -43.7129 + 4 1.0000 -1.396611 -38.0037 + 5 1.0000 -0.948912 -25.8212 + 6 1.0000 -0.781624 -21.2691 + 7 1.0000 -0.729502 -19.8508 + 8 1.0000 -0.686212 -18.6728 + 9 1.0000 -0.620928 -16.8963 + 10 1.0000 -0.529159 -14.3991 + 11 1.0000 -0.460883 -12.5413 + 12 0.0000 0.028605 0.7784 + 13 0.0000 0.078631 2.1396 + 14 0.0000 0.093397 2.5414 + 15 0.0000 0.098376 2.6769 + 16 0.0000 0.125012 3.4018 + 17 0.0000 0.146835 3.9956 + 18 0.0000 0.157052 4.2736 + 19 0.0000 0.172545 4.6952 + 20 0.0000 0.186847 5.0844 + 21 0.0000 0.195336 5.3154 + 22 0.0000 0.204488 5.5644 + 23 0.0000 0.234724 6.3872 + 24 0.0000 0.261786 7.1236 + 25 0.0000 0.291729 7.9384 + 26 0.0000 0.309531 8.4228 + 27 0.0000 0.329469 8.9653 + 28 0.0000 0.360195 9.8014 + 29 0.0000 0.374465 10.1897 + 30 0.0000 0.424065 11.5394 + 31 0.0000 0.513377 13.9697 + 32 0.0000 0.528156 14.3719 + 33 0.0000 0.548388 14.9224 + 34 0.0000 0.569732 15.5032 + 35 0.0000 0.613779 16.7018 + 36 0.0000 0.633484 17.2380 + 37 0.0000 0.646878 17.6025 + 38 0.0000 0.692504 18.8440 + 39 0.0000 0.717493 19.5240 + 40 0.0000 0.724763 19.7218 + 41 0.0000 0.745577 20.2882 + 42 0.0000 0.771449 20.9922 + 43 0.0000 0.789426 21.4814 + 44 0.0000 0.806003 21.9325 + 45 0.0000 0.817888 22.2559 + 46 0.0000 0.856679 23.3114 + 47 0.0000 0.867256 23.5992 + 48 0.0000 0.926614 25.2145 + 49 0.0000 0.941330 25.6149 + 50 0.0000 0.954244 25.9663 + 51 0.0000 1.004745 27.3405 + 52 0.0000 1.039915 28.2975 + 53 0.0000 1.054013 28.6812 + 54 0.0000 1.058559 28.8049 + 55 0.0000 1.091579 29.7034 + 56 0.0000 1.159823 31.5604 + 57 0.0000 1.197286 32.5798 + 58 0.0000 1.251283 34.0491 + 59 0.0000 1.298766 35.3412 + 60 0.0000 1.372420 37.3455 + 61 0.0000 1.413822 38.4721 + 62 0.0000 1.491711 40.5915 + 63 0.0000 1.513445 41.1829 + 64 0.0000 1.517460 41.2922 + 65 0.0000 1.539565 41.8937 + 66 0.0000 1.573230 42.8098 + 67 0.0000 1.606985 43.7283 + 68 0.0000 1.667823 45.3838 + 69 0.0000 1.728876 47.0451 + 70 0.0000 1.771036 48.1923 + 71 0.0000 1.807432 49.1827 + 72 0.0000 1.869496 50.8716 + 73 0.0000 1.941258 52.8243 + 74 0.0000 1.961987 53.3884 + 75 0.0000 2.018864 54.9361 + 76 0.0000 2.070148 56.3316 + 77 0.0000 2.100788 57.1653 + 78 0.0000 2.163413 58.8695 + 79 0.0000 2.179491 59.3070 + 80 0.0000 2.284127 62.1542 + 81 0.0000 2.303831 62.6904 + 82 0.0000 2.313432 62.9517 + 83 0.0000 2.375506 64.6408 + 84 0.0000 2.445460 66.5444 + 85 0.0000 2.468104 67.1605 + 86 0.0000 2.491523 67.7978 + 87 0.0000 2.502121 68.0862 + 88 0.0000 2.520290 68.5806 + 89 0.0000 2.533604 68.9429 + 90 0.0000 2.573741 70.0350 + 91 0.0000 2.601948 70.8026 + 92 0.0000 2.646596 72.0175 + 93 0.0000 2.705794 73.6284 + 94 0.0000 2.736520 74.4645 + 95 0.0000 2.755876 74.9912 + 96 0.0000 2.862487 77.8922 + 97 0.0000 2.897104 78.8342 + 98 0.0000 2.944360 80.1201 + 99 0.0000 3.095288 84.2271 + 100 0.0000 3.151936 85.7685 + 101 0.0000 3.181057 86.5610 + 102 0.0000 3.260072 88.7111 + 103 0.0000 3.464445 94.2723 + 104 0.0000 3.773502 102.6822 + 105 0.0000 3.890759 105.8729 + 106 0.0000 4.029304 109.6429 + 107 0.0000 4.163287 113.2888 + 108 0.0000 4.182631 113.8152 + 109 0.0000 4.260553 115.9355 + 110 0.0000 4.362082 118.6983 + 111 0.0000 4.400010 119.7304 + 112 0.0000 4.558166 124.0340 + 113 0.0000 4.626516 125.8939 + 114 0.0000 4.751320 129.2900 + 115 0.0000 4.805436 130.7626 + 116 0.0000 4.821142 131.1899 + 117 0.0000 4.892767 133.1390 + 118 0.0000 4.965858 135.1279 + 119 0.0000 5.001827 136.1066 + 120 0.0000 5.070865 137.9853 + 121 0.0000 5.100641 138.7955 + 122 0.0000 5.173735 140.7845 + 123 0.0000 5.241218 142.6208 + 124 0.0000 5.256494 143.0365 + 125 0.0000 5.326214 144.9337 + 126 0.0000 5.336905 145.2246 + 127 0.0000 5.410300 147.2217 + 128 0.0000 5.562455 151.3621 + 129 0.0000 5.684980 154.6962 + 130 0.0000 5.796678 157.7356 + 131 0.0000 6.001317 163.3041 + 132 0.0000 6.113124 166.3466 + 133 0.0000 6.416458 174.6007 + 134 0.0000 6.502970 176.9548 + 135 0.0000 6.509350 177.1284 + 136 0.0000 6.686651 181.9530 + 137 0.0000 6.708514 182.5479 + 138 0.0000 6.741256 183.4389 + 139 0.0000 6.848076 186.3456 + 140 0.0000 6.913391 188.1229 + 141 0.0000 7.068390 192.3407 + 142 0.0000 7.126296 193.9164 + 143 0.0000 7.181028 195.4057 + 144 0.0000 7.201974 195.9757 + 145 0.0000 7.233572 196.8355 + 146 0.0000 7.263162 197.6407 + 147 0.0000 7.346063 199.8965 + 148 0.0000 7.391108 201.1223 + 149 0.0000 7.438423 202.4098 + 150 0.0000 7.479571 203.5295 + 151 0.0000 7.604913 206.9402 + 152 0.0000 7.634689 207.7505 + 153 0.0000 7.686624 209.1637 + 154 0.0000 7.826298 212.9644 + 155 0.0000 7.942995 216.1399 + 156 0.0000 8.050788 219.0731 + 157 0.0000 8.397683 228.5126 + 158 0.0000 14.135713 384.6523 + 159 0.0000 15.020535 408.7295 + 160 0.0000 16.086189 437.7274 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.348652 0.000000 + 1 N : 0.345227 0.000000 + 2 O : -0.270738 0.000000 + 3 H : 0.274162 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.867259 s : 3.867259 + pz : 1.283005 p : 4.453339 + px : 1.351802 + py : 1.818532 + dz2 : 0.009519 d : 0.023436 + dxz : 0.004211 + dyz : 0.007385 + dx2y2 : 0.002076 + dxy : 0.000245 + f0 : 0.002110 f : 0.004618 + f+1 : 0.000359 + f-1 : 0.001229 + f+2 : 0.000229 + f-2 : 0.000106 + f+3 : 0.000345 + f-3 : 0.000239 + 1 N s : 3.829775 s : 3.829775 + pz : 0.887224 p : 2.653566 + px : 0.997405 + py : 0.768937 + dz2 : 0.032453 d : 0.141490 + dxz : 0.045470 + dyz : 0.017386 + dx2y2 : 0.012657 + dxy : 0.033525 + f0 : 0.008954 f : 0.029942 + f+1 : 0.004129 + f-1 : 0.006105 + f+2 : 0.003735 + f-2 : 0.001496 + f+3 : 0.002296 + f-3 : 0.003226 + 2 O s : 3.878181 s : 3.878181 + pz : 1.861519 p : 4.321125 + px : 1.172438 + py : 1.287168 + dz2 : 0.005146 d : 0.063652 + dxz : 0.015510 + dyz : 0.000828 + dx2y2 : 0.013361 + dxy : 0.028809 + f0 : 0.001141 f : 0.007779 + f+1 : 0.001061 + f-1 : 0.000376 + f+2 : 0.001086 + f-2 : 0.000163 + f+3 : 0.001535 + f-3 : 0.002416 + 3 H s : 0.624032 s : 0.624032 + pz : 0.019564 p : 0.079417 + px : 0.018197 + py : 0.041656 + dz2 : 0.000294 d : 0.022390 + dxz : 0.009923 + dyz : 0.000335 + dx2y2 : 0.002618 + dxy : 0.009220 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.599830 0.000000 + 1 N : -0.263564 0.000000 + 2 O : 0.237650 0.000000 + 3 H : -0.573915 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.116402 s : 3.116402 + pz : 1.219559 p : 3.910001 + px : 1.253060 + py : 1.437381 + dz2 : 0.122143 d : 0.287161 + dxz : 0.067388 + dyz : 0.045778 + dx2y2 : 0.037594 + dxy : 0.014257 + f0 : 0.030953 f : 0.086607 + f+1 : 0.021559 + f-1 : 0.013881 + f+2 : 0.008975 + f-2 : 0.006486 + f+3 : 0.003028 + f-3 : 0.001724 + 1 N s : 3.007051 s : 3.007051 + pz : 0.938478 p : 2.834890 + px : 1.167780 + py : 0.728632 + dz2 : 0.219845 d : 0.965098 + dxz : 0.323763 + dyz : 0.102530 + dx2y2 : 0.166784 + dxy : 0.152175 + f0 : 0.120258 f : 0.456525 + f+1 : 0.071408 + f-1 : 0.060544 + f+2 : 0.076288 + f-2 : 0.022276 + f+3 : 0.052305 + f-3 : 0.053447 + 2 O s : 3.315672 s : 3.315672 + pz : 1.509183 p : 4.002531 + px : 1.381198 + py : 1.112151 + dz2 : 0.046517 d : 0.326002 + dxz : 0.111016 + dyz : 0.006055 + dx2y2 : 0.096912 + dxy : 0.065502 + f0 : 0.015812 f : 0.118144 + f+1 : 0.021974 + f-1 : 0.002761 + f+2 : 0.026190 + f-2 : 0.004036 + f+3 : 0.023060 + f-3 : 0.024312 + 3 H s : 0.622164 s : 0.622164 + pz : 0.136730 p : 0.556961 + px : 0.257024 + py : 0.163207 + dz2 : 0.037314 d : 0.394790 + dxz : 0.129801 + dyz : 0.010526 + dx2y2 : 0.097330 + dxy : 0.119819 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3487 8.0000 -0.3487 1.9239 1.9239 -0.0000 + 1 N 6.6548 7.0000 0.3452 2.5393 2.5393 0.0000 + 2 O 8.2707 8.0000 -0.2707 1.7371 1.7371 -0.0000 + 3 H 0.7258 1.0000 0.2742 0.9448 0.9448 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.9037 B( 0-O , 3-H ) : 0.9636 B( 1-N , 2-O ) : 1.6674 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 6 sec + +Total time .... 6.696 sec +Sum of individual times .... 5.272 sec ( 78.7%) + +Fock matrix formation .... 2.420 sec ( 36.1%) +Diagonalization .... 1.310 sec ( 19.6%) +Density matrix formation .... 0.011 sec ( 0.2%) +Population analysis .... 0.257 sec ( 3.8%) +Initial guess .... 0.022 sec ( 0.3%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.012 sec ( 0.2%) +DIIS solution .... 1.251 sec ( 18.7%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.849 sec +Reference energy ... -204.720559989 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 13.686 sec +AO-integral generation ... 0.381 sec +Half transformation ... 0.188 sec +K-integral sorting ... 10.224 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.069 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.081 s ( 0.000 ms/b) + 277134 b 0 skpd 0.091 s ( 0.000 ms/b) +: : 151164 b 0 skpd 0.129 s ( 0.001 ms/b) + 159120 b 0 skpd 0.046 s ( 0.000 ms/b) +: : 218790 b 0 skpd 0.094 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.082 s ( 0.001 ms/b) + 87516 b 0 skpd 0.066 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.106 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.064 s ( 0.002 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.960 sec +AO-integral generation ... 0.726 sec +Half transformation ... 0.108 sec +J-integral sorting ... 0.092 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.268 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.441 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090518418 +EMP2(bb)= -0.090518418 +EMP2(ab)= -0.516603452 + +Initial guess performed in 0.199 sec +E(0) ... -204.720559989 +E(MP2) ... -0.697640289 +Initial E(tot) ... -205.418200278 + ... 0.188186487 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.418200278 -0.697640289 -0.000000000 0.025197703 6.25 0.000001009 + *** Turning on DIIS *** + 1 -205.389081590 -0.668521601 0.029118688 0.010703820 5.91 0.057783110 + 2 -205.408582504 -0.688022515 -0.019500914 0.005474562 6.02 0.060718584 + 3 -205.412302947 -0.691742957 -0.003720442 0.002255298 6.66 0.075079404 + 4 -205.413871659 -0.693311670 -0.001568713 0.001684559 6.44 0.081916833 + 5 -205.414432209 -0.693872220 -0.000560550 0.000919088 7.09 0.087688308 + 6 -205.414546263 -0.693986274 -0.000114054 0.000546823 7.81 0.090585062 + 7 -205.414592598 -0.694032609 -0.000046335 0.000217933 7.23 0.091903414 + 8 -205.414605098 -0.694045108 -0.000012500 0.000112157 7.06 0.092391353 + 9 -205.414600781 -0.694040791 0.000004317 0.000029983 6.58 0.092533371 + 10 -205.414605503 -0.694045514 -0.000004723 0.000014833 6.25 0.092575404 + 11 -205.414602912 -0.694042922 0.000002591 0.000011915 6.24 0.092568256 + 12 -205.414603951 -0.694043961 -0.000001039 0.000009279 6.65 0.092577565 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.720559989 +E(CORR) ... -0.694043961 +E(TOT) ... -205.414603951 +Singles norm **1/2 ... 0.092577565 ( 0.046288783, 0.046288783) +T1 diagnostic ... 0.021820741 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.060042 + 10a-> 13a 10b-> 13b 0.046728 + 8b-> 13b -1b-> -1b 0.040973 + 8a-> 13a -1a-> -1a 0.040973 + 10a-> 13a -1a-> -1a 0.034526 + 10b-> 13b -1b-> -1b 0.034526 + 10a-> 13a 8b-> 13b 0.032157 + 8a-> 13a 10b-> 13b 0.032157 + 11a-> 13a 11b-> 13b 0.028022 + 5a-> 13a 5b-> 13b 0.026169 + 11b-> 26b -1b-> -1b 0.025833 + 11a-> 26a -1a-> -1a 0.025833 + 11a-> 26a 11b-> 26b 0.025521 + 9a-> 13a 8b-> 13b 0.025125 + 8a-> 13a 9b-> 13b 0.025125 + 8a-> 22a 8b-> 13b 0.021069 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034728791 + alpha-alpha-alpha ... -0.000896737 ( 2.6%) + alpha-alpha-beta ... -0.016467659 ( 47.4%) + alpha-beta -beta ... -0.016467659 ( 47.4%) + beta -beta -beta ... -0.000896737 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034728791 + +Final correlation energy ... -0.728772752 +E(CCSD) ... -205.414603951 +E(CCSD(T)) ... -205.449332742 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210095652 sqrt= 1.100043477 +W(HF) = 0.826380955 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.262803 -0.000000 + 1 N : 0.156230 0.000000 + 2 O : -0.154902 0.000000 + 3 H : 0.261475 -0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.846375 s : 3.846375 + pz : 1.273666 p : 4.352354 + px : 1.338981 + py : 1.739708 + dz2 : 0.014399 d : 0.055649 + dxz : 0.010286 + dyz : 0.014707 + dx2y2 : 0.008883 + dxy : 0.007374 + f0 : 0.002279 f : 0.008425 + f+1 : 0.000882 + f-1 : 0.001752 + f+2 : 0.000900 + f-2 : 0.000751 + f+3 : 0.000993 + f-3 : 0.000868 + 1 N s : 3.880910 s : 3.880910 + pz : 0.916335 p : 2.761684 + px : 0.981705 + py : 0.863644 + dz2 : 0.038006 d : 0.171855 + dxz : 0.056442 + dyz : 0.026184 + dx2y2 : 0.016431 + dxy : 0.034792 + f0 : 0.008671 f : 0.029321 + f+1 : 0.003828 + f-1 : 0.006035 + f+2 : 0.004040 + f-2 : 0.002053 + f+3 : 0.002035 + f-3 : 0.002658 + 2 O s : 3.866405 s : 3.866405 + pz : 1.777421 p : 4.193002 + px : 1.162285 + py : 1.253296 + dz2 : 0.010173 d : 0.085170 + dxz : 0.023667 + dyz : 0.007197 + dx2y2 : 0.015159 + dxy : 0.028973 + f0 : 0.001640 f : 0.010325 + f+1 : 0.001528 + f-1 : 0.000853 + f+2 : 0.001592 + f-2 : 0.000787 + f+3 : 0.001626 + f-3 : 0.002299 + 3 H s : 0.635572 s : 0.635572 + pz : 0.023338 p : 0.083726 + px : 0.012563 + py : 0.047825 + dz2 : 0.000626 d : 0.019226 + dxz : 0.008868 + dyz : 0.000397 + dx2y2 : 0.001548 + dxy : 0.007788 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.615796 -0.000000 + 1 N : -0.313265 -0.000000 + 2 O : 0.271657 0.000000 + 3 H : -0.574188 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.123393 s : 3.123393 + pz : 1.222288 p : 3.848955 + px : 1.246298 + py : 1.380369 + dz2 : 0.128267 d : 0.318302 + dxz : 0.072782 + dyz : 0.052163 + dx2y2 : 0.045114 + dxy : 0.019976 + f0 : 0.031878 f : 0.093553 + f+1 : 0.022972 + f-1 : 0.015589 + f+2 : 0.009626 + f-2 : 0.007159 + f+3 : 0.003906 + f-3 : 0.002424 + 1 N s : 3.012209 s : 3.012209 + pz : 0.945953 p : 2.882065 + px : 1.149943 + py : 0.786169 + dz2 : 0.227010 d : 0.974202 + dxz : 0.321181 + dyz : 0.104281 + dx2y2 : 0.171487 + dxy : 0.150242 + f0 : 0.118033 f : 0.444790 + f+1 : 0.071380 + f-1 : 0.057768 + f+2 : 0.070613 + f-2 : 0.021633 + f+3 : 0.052519 + f-3 : 0.052843 + 2 O s : 3.317544 s : 3.317544 + pz : 1.455107 p : 3.926979 + px : 1.373694 + py : 1.098178 + dz2 : 0.052319 d : 0.357054 + dxz : 0.113071 + dyz : 0.012470 + dx2y2 : 0.102683 + dxy : 0.076511 + f0 : 0.016197 f : 0.126767 + f+1 : 0.022654 + f-1 : 0.003467 + f+2 : 0.025994 + f-2 : 0.005138 + f+3 : 0.025258 + f-3 : 0.028058 + 3 H s : 0.624042 s : 0.624042 + pz : 0.138273 p : 0.565795 + px : 0.259751 + py : 0.167770 + dz2 : 0.038687 d : 0.384351 + dxz : 0.125478 + dyz : 0.010218 + dx2y2 : 0.096145 + dxy : 0.113824 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2628 8.0000 -0.2628 2.2898 1.8287 0.4611 + 1 N 6.8438 7.0000 0.1562 2.8274 2.3497 0.4777 + 2 O 8.1549 8.0000 -0.1549 2.1374 1.6406 0.4968 + 3 H 0.7385 1.0000 0.2615 0.9664 0.8957 0.0707 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8377 B( 0-O , 3-H ) : 0.8921 B( 1-N , 2-O ) : 1.5250 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 123.306 sec + +Fock Matrix Formation ... 0.849 sec ( 0.7%) +Initial Guess ... 0.199 sec ( 0.2%) +DIIS Solver ... 5.297 sec ( 4.3%) +State Vector Update ... 0.189 sec ( 0.2%) +Sigma-vector construction ... 80.707 sec ( 65.5%) + <0|H|D> ... 0.008 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.049 sec ( 0.1% of sigma) + (0-ext) ... 0.161 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.058 sec ( 0.1% of sigma) + (2-ext) ... 2.066 sec ( 2.6% of sigma) + (4-ext) ... 46.224 sec ( 57.3% of sigma) + ... 4.142 sec ( 5.1% of sigma) + ... 0.008 sec ( 0.0% of sigma) + (1-ext) ... 0.022 sec ( 0.0% of sigma) + (1-ext) ... 0.263 sec ( 0.3% of sigma) + Fock-dressing ... 5.497 sec ( 6.8% of sigma) + (ik|jl)-dressing ... 0.235 sec ( 0.3% of sigma) + (ij|ab),(ia|jb)-dressing ... 17.823 sec ( 22.1% of sigma) + Pair energies ... 0.033 sec ( 0.0% of sigma) +Total Time for computing (T) ... 18.029 sec ( 14.6% of ALL) + I/O of integral and amplitudes ... 2.066 sec ( 11.5% of (T)) + External N**7 contributions ... 8.977 sec ( 49.8% of (T)) + Internal N**7 contributions ... 0.950 sec ( 5.3% of (T)) + N**6 triples energy contributions ... 3.233 sec ( 17.9% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.449332741579 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.042.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.042.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.716470, -0.097969 -0.323749) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.65163 -0.13480 -0.80019 +Nuclear contribution : -1.48878 0.22765 0.74541 + ----------------------------------------- +Total Dipole Moment : -0.83715 0.09285 -0.05477 + ----------------------------------------- +Magnitude (a.u.) : 0.84406 +Magnitude (Debye) : 2.14544 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.026535 0.415668 0.367644 +Rotational constants in MHz : 90733.227853 12461.419064 11021.692313 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.573154 -0.570827 -0.241027 +x,y,z [Debye]: 1.456843 -1.450926 -0.612642 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.716470, -0.097969 -0.323749) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.82092 -0.11456 -0.75709 +Nuclear contribution : -1.48878 0.22765 0.74541 + ----------------------------------------- +Total Dipole Moment : -0.66786 0.11310 -0.01168 + ----------------------------------------- +Magnitude (a.u.) : 0.67747 +Magnitude (Debye) : 1.72199 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.026535 0.415668 0.367644 +Rotational constants in MHz : 90733.227853 12461.419064 11021.692313 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.479771 -0.422833 -0.223597 +x,y,z [Debye]: 1.219482 -1.074755 -0.568340 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 43 * + * * + * Dihedral ( 2, 1, 0, 3) : 163.63636364 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0397159716 RMS(Int)= 0.0002426450 + Iter 1: RMS(Cart)= 0.0000674853 RMS(Int)= 0.0000012482 + Iter 2: RMS(Cart)= 0.0000003471 RMS(Int)= 0.0000000064 + Iter 3: RMS(Cart)= 0.0000000018 RMS(Int)= 0.0000000000 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4430 0.000000 + 2. B(O 2,N 1) 1.1746 0.000000 + 3. B(H 3,O 0) 0.9718 0.000000 + 4. A(N 1,O 0,H 3) 101.9874 0.000000 + 5. A(O 0,N 1,O 2) 110.4953 0.000000 + 6. D(O 2,N 1,O 0,H 3) 163.6364 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.262700 0.035755 0.731606 + N 0.161779 -0.168780 -0.632281 + O 1.322900 -0.019627 -0.728391 + H -1.221978 0.152652 0.629067 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.496431 0.067568 1.382535 + 1 N 7.0000 0 14.007 0.305718 -0.318948 -1.194838 + 2 O 8.0000 0 15.999 2.499919 -0.037090 -1.376460 + 3 H 1.0000 0 1.008 -2.309204 0.288470 1.188763 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.442954267741 0.00000000 0.00000000 + O 2 1 0 1.172446411871 110.54673841 0.00000000 + H 1 2 3 0.969002275781 102.01909093 155.45454572 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.726788389804 0.00000000 0.00000000 + O 2 1 0 2.215602625136 110.54673841 0.00000000 + H 1 2 3 1.831148924372 102.01909093 155.45454572 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.1 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.2 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.244396143192 Eh + +SHARK setup successfully completed in 0.6 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.2443961432 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.987e-04 +Time for diagonalization ... 0.034 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.003 sec +Total time needed ... 0.063 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.1 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7167933521 0.000000000000 0.00182734 0.00005416 0.0198713 0.7000 + 1 -204.7176975259 -0.000904173854 0.00173759 0.00004870 0.0164287 0.7000 + ***Turning on DIIS*** + 2 -204.7184681332 -0.000770607289 0.00473717 0.00013127 0.0133307 0.0000 + 3 -204.7217525303 -0.003284397062 0.00184401 0.00005241 0.0052336 0.0000 + 4 -204.7203810250 0.001371505260 0.00087644 0.00002347 0.0020201 0.0000 + 5 -204.7218306659 -0.001449640868 0.00052199 0.00001813 0.0010062 0.0000 + 6 -204.7210490992 0.000781566687 0.00062822 0.00002154 0.0005644 0.0000 + 7 -204.7208618851 0.000187214050 0.00032320 0.00001118 0.0002803 0.0000 + 8 -204.7214935863 -0.000631701176 0.00018016 0.00000678 0.0002025 0.0000 + 9 -204.7210913206 0.000402265711 0.00014847 0.00000481 0.0001249 0.0000 + 10 -204.7212755804 -0.000184259775 0.00006412 0.00000196 0.0000554 0.0000 + 11 -204.7213183146 -0.000042734179 0.00002322 0.00000068 0.0000244 0.0000 + 12 -204.7212476451 0.000070669433 0.00000639 0.00000019 0.0000069 0.0000 + 13 -204.7212673886 -0.000019743458 0.00000183 0.00000006 0.0000024 0.0000 + 14 -204.7212616553 0.000005733245 0.00000082 0.00000002 0.0000013 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 15 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72126296 Eh -5570.74878 eV + +Components: +Nuclear Repulsion : 69.24439614 Eh 1884.23581 eV +Electronic Energy : -273.96565910 Eh -7454.98459 eV +One Electron Energy: -418.20384284 Eh -11379.90511 eV +Two Electron Energy: 144.23818374 Eh 3924.92052 eV + +Virial components: +Potential Energy : -408.94652753 Eh -11128.00075 eV +Kinetic Energy : 204.22526457 Eh 5557.25197 eV +Virial Ratio : 2.00242868 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.3010e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.5737e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.4838e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.3344e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.669579 -562.4479 + 1 1.0000 -20.638183 -561.5935 + 2 1.0000 -15.800310 -429.9483 + 3 1.0000 -1.604184 -43.6521 + 4 1.0000 -1.396550 -38.0021 + 5 1.0000 -0.948766 -25.8172 + 6 1.0000 -0.781290 -21.2600 + 7 1.0000 -0.729032 -19.8380 + 8 1.0000 -0.682792 -18.5797 + 9 1.0000 -0.623209 -16.9584 + 10 1.0000 -0.528604 -14.3840 + 11 1.0000 -0.461239 -12.5510 + 12 0.0000 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3.9573 + 18 0.0000 0.156880 4.2689 + 19 0.0000 0.172440 4.6923 + 20 0.0000 0.187208 5.0942 + 21 0.0000 0.196066 5.3352 + 22 0.0000 0.204766 5.5720 + 23 0.0000 0.233680 6.3587 + 24 0.0000 0.259652 7.0655 + 25 0.0000 0.293356 7.9826 + 26 0.0000 0.306140 8.3305 + 27 0.0000 0.329375 8.9627 + 28 0.0000 0.362578 9.8663 + 29 0.0000 0.377945 10.2844 + 30 0.0000 0.423717 11.5299 + 31 0.0000 0.515942 14.0395 + 32 0.0000 0.529568 14.4103 + 33 0.0000 0.547720 14.9042 + 34 0.0000 0.570432 15.5223 + 35 0.0000 0.613802 16.7024 + 36 0.0000 0.631986 17.1972 + 37 0.0000 0.647312 17.6143 + 38 0.0000 0.686379 18.6773 + 39 0.0000 0.717308 19.5189 + 40 0.0000 0.719669 19.5832 + 41 0.0000 0.747028 20.3277 + 42 0.0000 0.771639 20.9974 + 43 0.0000 0.787373 21.4255 + 44 0.0000 0.806792 21.9539 + 45 0.0000 0.815971 22.2037 + 46 0.0000 0.858144 23.3513 + 47 0.0000 0.872261 23.7354 + 48 0.0000 0.926715 25.2172 + 49 0.0000 0.939055 25.5530 + 50 0.0000 0.950471 25.8636 + 51 0.0000 1.000247 27.2181 + 52 0.0000 1.044415 28.4200 + 53 0.0000 1.058434 28.8015 + 54 0.0000 1.067840 29.0574 + 55 0.0000 1.097658 29.8688 + 56 0.0000 1.160349 31.5747 + 57 0.0000 1.193391 32.4738 + 58 0.0000 1.250471 34.0270 + 59 0.0000 1.285158 34.9709 + 60 0.0000 1.367640 37.2154 + 61 0.0000 1.423273 38.7292 + 62 0.0000 1.493513 40.6405 + 63 0.0000 1.517478 41.2927 + 64 0.0000 1.522584 41.4316 + 65 0.0000 1.540044 41.9067 + 66 0.0000 1.562557 42.5193 + 67 0.0000 1.603642 43.6373 + 68 0.0000 1.663908 45.2772 + 69 0.0000 1.729193 47.0537 + 70 0.0000 1.760832 47.9147 + 71 0.0000 1.812940 49.3326 + 72 0.0000 1.861055 50.6419 + 73 0.0000 1.951765 53.1102 + 74 0.0000 1.962795 53.4104 + 75 0.0000 2.008552 54.6555 + 76 0.0000 2.075134 56.4673 + 77 0.0000 2.102345 57.2077 + 78 0.0000 2.161940 58.8294 + 79 0.0000 2.172911 59.1279 + 80 0.0000 2.282793 62.1180 + 81 0.0000 2.302767 62.6615 + 82 0.0000 2.319611 63.1198 + 83 0.0000 2.378103 64.7115 + 84 0.0000 2.445452 66.5441 + 85 0.0000 2.468549 67.1726 + 86 0.0000 2.494869 67.8888 + 87 0.0000 2.501797 68.0773 + 88 0.0000 2.518077 68.5203 + 89 0.0000 2.540184 69.1219 + 90 0.0000 2.570447 69.9454 + 91 0.0000 2.600881 70.7736 + 92 0.0000 2.635993 71.7290 + 93 0.0000 2.676142 72.8215 + 94 0.0000 2.751460 74.8710 + 95 0.0000 2.762388 75.1684 + 96 0.0000 2.860775 77.8456 + 97 0.0000 2.905117 79.0522 + 98 0.0000 2.937863 79.9433 + 99 0.0000 3.101089 84.3849 + 100 0.0000 3.149424 85.7002 + 101 0.0000 3.183773 86.6349 + 102 0.0000 3.251173 88.4689 + 103 0.0000 3.457463 94.0824 + 104 0.0000 3.792291 103.1935 + 105 0.0000 3.875205 105.4497 + 106 0.0000 4.027805 109.6021 + 107 0.0000 4.166393 113.3733 + 108 0.0000 4.175182 113.6125 + 109 0.0000 4.237072 115.2966 + 110 0.0000 4.359935 118.6399 + 111 0.0000 4.387529 119.3907 + 112 0.0000 4.568406 124.3127 + 113 0.0000 4.620801 125.7384 + 114 0.0000 4.747882 129.1964 + 115 0.0000 4.806239 130.7844 + 116 0.0000 4.843533 131.7992 + 117 0.0000 4.894147 133.1765 + 118 0.0000 4.970200 135.2460 + 119 0.0000 5.001435 136.0960 + 120 0.0000 5.068624 137.9243 + 121 0.0000 5.094837 138.6375 + 122 0.0000 5.166402 140.5849 + 123 0.0000 5.246856 142.7742 + 124 0.0000 5.253901 142.9659 + 125 0.0000 5.323691 144.8650 + 126 0.0000 5.334160 145.1499 + 127 0.0000 5.395498 146.8190 + 128 0.0000 5.566041 151.4597 + 129 0.0000 5.675434 154.4364 + 130 0.0000 5.794446 157.6749 + 131 0.0000 5.996359 163.1692 + 132 0.0000 6.107460 166.1924 + 133 0.0000 6.420102 174.6999 + 134 0.0000 6.505423 177.0215 + 135 0.0000 6.506807 177.0592 + 136 0.0000 6.679288 181.7527 + 137 0.0000 6.710898 182.6128 + 138 0.0000 6.742071 183.4611 + 139 0.0000 6.844902 186.2593 + 140 0.0000 6.911468 188.0706 + 141 0.0000 7.063345 192.2034 + 142 0.0000 7.122416 193.8108 + 143 0.0000 7.175727 195.2615 + 144 0.0000 7.213100 196.2784 + 145 0.0000 7.240979 197.0370 + 146 0.0000 7.258710 197.5195 + 147 0.0000 7.336910 199.6475 + 148 0.0000 7.383878 200.9255 + 149 0.0000 7.431943 202.2334 + 150 0.0000 7.476879 203.4562 + 151 0.0000 7.603472 206.9010 + 152 0.0000 7.638443 207.8526 + 153 0.0000 7.689507 209.2421 + 154 0.0000 7.794721 212.1051 + 155 0.0000 7.947846 216.2719 + 156 0.0000 8.053633 219.1505 + 157 0.0000 8.404167 228.6890 + 158 0.0000 14.134334 384.6148 + 159 0.0000 15.008521 408.4026 + 160 0.0000 16.009387 435.6376 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.351552 0.000000 + 1 N : 0.346085 0.000000 + 2 O : -0.273186 0.000000 + 3 H : 0.278654 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.868106 s : 3.868106 + pz : 1.285630 p : 4.455064 + px : 1.342678 + py : 1.826756 + dz2 : 0.009583 d : 0.023759 + dxz : 0.003806 + dyz : 0.007655 + dx2y2 : 0.002326 + dxy : 0.000389 + f0 : 0.002136 f : 0.004623 + f+1 : 0.000341 + f-1 : 0.001254 + f+2 : 0.000269 + f-2 : 0.000074 + f+3 : 0.000417 + f-3 : 0.000131 + 1 N s : 3.829650 s : 3.829650 + pz : 0.890308 p : 2.651637 + px : 1.005866 + py : 0.755462 + dz2 : 0.032987 d : 0.142898 + dxz : 0.046050 + dyz : 0.016918 + dx2y2 : 0.011426 + dxy : 0.035516 + f0 : 0.008890 f : 0.029731 + f+1 : 0.004120 + f-1 : 0.006092 + f+2 : 0.003889 + f-2 : 0.001149 + f+3 : 0.001929 + f-3 : 0.003661 + 2 O s : 3.878027 s : 3.878027 + pz : 1.869734 p : 4.323825 + px : 1.168354 + py : 1.285737 + dz2 : 0.005223 d : 0.063515 + dxz : 0.015722 + dyz : 0.000532 + dx2y2 : 0.011654 + dxy : 0.030383 + f0 : 0.001145 f : 0.007820 + f+1 : 0.001074 + f-1 : 0.000370 + f+2 : 0.001196 + f-2 : 0.000075 + f+3 : 0.001297 + f-3 : 0.002663 + 3 H s : 0.621335 s : 0.621335 + pz : 0.019389 p : 0.077773 + px : 0.016981 + py : 0.041403 + dz2 : 0.000247 d : 0.022238 + dxz : 0.010311 + dyz : -0.000023 + dx2y2 : 0.001577 + dxy : 0.010126 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.597768 0.000000 + 1 N : -0.262959 0.000000 + 2 O : 0.234906 0.000000 + 3 H : -0.569715 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.118129 s : 3.118129 + pz : 1.220452 p : 3.909505 + px : 1.248844 + py : 1.440209 + dz2 : 0.124121 d : 0.287965 + dxz : 0.067218 + dyz : 0.044519 + dx2y2 : 0.040034 + dxy : 0.012074 + f0 : 0.031534 f : 0.086632 + f+1 : 0.021919 + f-1 : 0.013318 + f+2 : 0.008660 + f-2 : 0.006433 + f+3 : 0.003731 + f-3 : 0.001037 + 1 N s : 3.007718 s : 3.007718 + pz : 0.942645 p : 2.833782 + px : 1.179670 + py : 0.711468 + dz2 : 0.219375 d : 0.965019 + dxz : 0.327298 + dyz : 0.099741 + dx2y2 : 0.171266 + dxy : 0.147339 + f0 : 0.121187 f : 0.456440 + f+1 : 0.072083 + f-1 : 0.060408 + f+2 : 0.080785 + f-2 : 0.017159 + f+3 : 0.051439 + f-3 : 0.053379 + 2 O s : 3.316810 s : 3.316810 + pz : 1.515470 p : 4.005475 + px : 1.385118 + py : 1.104887 + dz2 : 0.045794 d : 0.325117 + dxz : 0.112994 + dyz : 0.004717 + dx2y2 : 0.101902 + dxy : 0.059711 + f0 : 0.016061 f : 0.117692 + f+1 : 0.021876 + f-1 : 0.002278 + f+2 : 0.027753 + f-2 : 0.002657 + f+3 : 0.023711 + f-3 : 0.023357 + 3 H s : 0.621404 s : 0.621404 + pz : 0.135076 p : 0.553842 + px : 0.259408 + py : 0.159358 + dz2 : 0.038107 d : 0.394470 + dxz : 0.132188 + dyz : 0.006596 + dx2y2 : 0.095177 + dxy : 0.122402 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3516 8.0000 -0.3516 1.9348 1.9348 0.0000 + 1 N 6.6539 7.0000 0.3461 2.5402 2.5402 0.0000 + 2 O 8.2732 8.0000 -0.2732 1.7342 1.7342 0.0000 + 3 H 0.7213 1.0000 0.2787 0.9397 0.9397 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.9157 B( 0-O , 3-H ) : 0.9617 B( 1-N , 2-O ) : 1.6617 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 9 sec + +Total time .... 9.604 sec +Sum of individual times .... 7.589 sec ( 79.0%) + +Fock matrix formation .... 5.431 sec ( 56.5%) +Diagonalization .... 1.079 sec ( 11.2%) +Density matrix formation .... 0.025 sec ( 0.3%) +Population analysis .... 0.235 sec ( 2.4%) +Initial guess .... 0.052 sec ( 0.5%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.011 sec ( 0.1%) +DIIS solution .... 0.768 sec ( 8.0%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.632 sec +Reference energy ... -204.721264003 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 13.519 sec +AO-integral generation ... 0.366 sec +Half transformation ... 0.179 sec +K-integral sorting ... 10.362 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.065 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.085 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.084 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.130 s ( 0.001 ms/b) +: 159120 b 0 skpd 0.046 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.096 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.082 s ( 0.001 ms/b) + 87516 b 0 skpd 0.063 s ( 0.001 ms/b) +: 87516 b 0 skpd 0.108 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.071 s ( 0.003 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 1.115 sec +AO-integral generation ... 0.733 sec +Half transformation ... 0.101 sec +J-integral sorting ... 0.238 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.339 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.461 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090684576 +EMP2(bb)= -0.090684576 +EMP2(ab)= -0.517247792 + +Initial guess performed in 0.195 sec +E(0) ... -204.721264003 +E(MP2) ... -0.698616944 +Initial E(tot) ... -205.419880947 + ... 0.188936686 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.419880947 -0.698616944 -0.000000000 0.026357229 6.22 0.000002276 + *** Turning on DIIS *** + 1 -205.390230913 -0.668966910 0.029650035 0.011503127 6.67 0.058354219 + 2 -205.409883281 -0.688619278 -0.019652369 0.005785354 6.97 0.061213158 + 3 -205.413616236 -0.692352233 -0.003732955 0.002407690 7.52 0.075752463 + 4 -205.415203451 -0.693939448 -0.001587215 0.001687594 7.92 0.082692446 + 5 -205.415775154 -0.694511151 -0.000571703 0.000905533 6.08 0.088571523 + 6 -205.415890800 -0.694626797 -0.000115646 0.000537067 6.50 0.091493158 + 7 -205.415937486 -0.694673483 -0.000046687 0.000208329 7.01 0.092807287 + 8 -205.415950126 -0.694686123 -0.000012640 0.000107646 6.99 0.093285981 + 9 -205.415945826 -0.694681823 0.000004300 0.000028090 8.41 0.093424330 + 10 -205.415950492 -0.694686489 -0.000004666 0.000009965 7.64 0.093463568 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.721264003 +E(CORR) ... -0.694686489 +E(TOT) ... -205.415950492 +Singles norm **1/2 ... 0.093463568 ( 0.046731784, 0.046731784) +T1 diagnostic ... 0.022029574 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.064210 + 10a-> 13a 10b-> 13b 0.050552 + 8a-> 13a -1a-> -1a 0.043480 + 8b-> 13b -1b-> -1b 0.043480 + 10a-> 13a 8b-> 13b 0.034915 + 8a-> 13a 10b-> 13b 0.034915 + 10a-> 13a -1a-> -1a 0.034674 + 10b-> 13b -1b-> -1b 0.034674 + 11a-> 13a 11b-> 13b 0.027942 + 11b-> 26b -1b-> -1b 0.026559 + 11a-> 26a -1a-> -1a 0.026559 + 5a-> 13a 5b-> 13b 0.026135 + 11a-> 26a 11b-> 26b 0.026063 + 8a-> 13a 8b-> 22b 0.022894 + 8a-> 22a 8b-> 13b 0.022894 + 10a-> 13a 11b-> 26b 0.021708 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034938262 + alpha-alpha-alpha ... -0.000902247 ( 2.6%) + alpha-alpha-beta ... -0.016566884 ( 47.4%) + alpha-beta -beta ... -0.016566884 ( 47.4%) + beta -beta -beta ... -0.000902247 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034938262 + +Final correlation energy ... -0.729624751 +E(CCSD) ... -205.415950492 +E(CCSD(T)) ... -205.450888754 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210897338 sqrt= 1.100407805 +W(HF) = 0.825833841 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.263145 0.000000 + 1 N : 0.155789 -0.000000 + 2 O : -0.157988 0.000000 + 3 H : 0.265344 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.847648 s : 3.847648 + pz : 1.276587 p : 4.351019 + px : 1.330007 + py : 1.744425 + dz2 : 0.014497 d : 0.056038 + dxz : 0.009978 + dyz : 0.014959 + dx2y2 : 0.009059 + dxy : 0.007545 + f0 : 0.002297 f : 0.008440 + f+1 : 0.000872 + f-1 : 0.001778 + f+2 : 0.000944 + f-2 : 0.000717 + f+3 : 0.001065 + f-3 : 0.000767 + 1 N s : 3.879835 s : 3.879835 + pz : 0.917727 p : 2.762068 + px : 0.987050 + py : 0.857291 + dz2 : 0.038399 d : 0.173159 + dxz : 0.057233 + dyz : 0.025776 + dx2y2 : 0.015550 + dxy : 0.036201 + f0 : 0.008629 f : 0.029149 + f+1 : 0.003817 + f-1 : 0.006016 + f+2 : 0.004183 + f-2 : 0.001769 + f+3 : 0.001850 + f-3 : 0.002885 + 2 O s : 3.867057 s : 3.867057 + pz : 1.785343 p : 4.195434 + px : 1.159223 + py : 1.250868 + dz2 : 0.010200 d : 0.085120 + dxz : 0.024055 + dyz : 0.006881 + dx2y2 : 0.013728 + dxy : 0.030257 + f0 : 0.001646 f : 0.010377 + f+1 : 0.001539 + f-1 : 0.000849 + f+2 : 0.001693 + f-2 : 0.000716 + f+3 : 0.001460 + f-3 : 0.002472 + 3 H s : 0.633604 s : 0.633604 + pz : 0.023258 p : 0.081992 + px : 0.011019 + py : 0.047715 + dz2 : 0.000588 d : 0.019060 + dxz : 0.009210 + dyz : 0.000091 + dx2y2 : 0.000581 + dxy : 0.008591 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.614636 -0.000000 + 1 N : -0.313677 0.000000 + 2 O : 0.268744 -0.000000 + 3 H : -0.569704 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.125344 s : 3.125344 + pz : 1.223674 p : 3.847180 + px : 1.242485 + py : 1.381020 + dz2 : 0.130199 d : 0.319237 + dxz : 0.072500 + dyz : 0.051156 + dx2y2 : 0.047732 + dxy : 0.017649 + f0 : 0.032358 f : 0.093604 + f+1 : 0.023298 + f-1 : 0.015198 + f+2 : 0.009335 + f-2 : 0.007067 + f+3 : 0.004681 + f-3 : 0.001667 + 1 N s : 3.012870 s : 3.012870 + pz : 0.948878 p : 2.882366 + px : 1.159503 + py : 0.773986 + dz2 : 0.226584 d : 0.973950 + dxz : 0.324228 + dyz : 0.101521 + dx2y2 : 0.176961 + dxy : 0.144656 + f0 : 0.118979 f : 0.444490 + f+1 : 0.072179 + f-1 : 0.057494 + f+2 : 0.074684 + f-2 : 0.016843 + f+3 : 0.051803 + f-3 : 0.052508 + 2 O s : 3.318632 s : 3.318632 + pz : 1.461236 p : 3.929746 + px : 1.377861 + py : 1.090649 + dz2 : 0.051621 d : 0.356492 + dxz : 0.115010 + dyz : 0.011082 + dx2y2 : 0.107095 + dxy : 0.071684 + f0 : 0.016392 f : 0.126386 + f+1 : 0.022596 + f-1 : 0.003019 + f+2 : 0.027527 + f-2 : 0.003695 + f+3 : 0.025244 + f-3 : 0.027914 + 3 H s : 0.623493 s : 0.623493 + pz : 0.136613 p : 0.562279 + px : 0.261902 + py : 0.163765 + dz2 : 0.039419 d : 0.383932 + dxz : 0.127693 + dyz : 0.006541 + dx2y2 : 0.094481 + dxy : 0.115797 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2631 8.0000 -0.2631 2.3036 1.8402 0.4634 + 1 N 6.8442 7.0000 0.1558 2.8310 2.3528 0.4782 + 2 O 8.1580 8.0000 -0.1580 2.1370 1.6394 0.4976 + 3 H 0.7347 1.0000 0.2653 0.9618 0.8911 0.0707 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8500 B( 0-O , 2-O ) : 0.1007 B( 0-O , 3-H ) : 0.8896 +B( 1-N , 2-O ) : 1.5200 + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 114.503 sec + +Fock Matrix Formation ... 0.632 sec ( 0.6%) +Initial Guess ... 0.195 sec ( 0.2%) +DIIS Solver ... 4.965 sec ( 4.3%) +State Vector Update ... 0.229 sec ( 0.2%) +Sigma-vector construction ... 72.732 sec ( 63.5%) + <0|H|D> ... 0.007 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.039 sec ( 0.1% of sigma) + (0-ext) ... 0.137 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.049 sec ( 0.1% of sigma) + (2-ext) ... 1.808 sec ( 2.5% of sigma) + (4-ext) ... 41.840 sec ( 57.5% of sigma) + ... 4.315 sec ( 5.9% of sigma) + ... 0.005 sec ( 0.0% of sigma) + (1-ext) ... 0.018 sec ( 0.0% of sigma) + (1-ext) ... 0.186 sec ( 0.3% of sigma) + Fock-dressing ... 4.621 sec ( 6.4% of sigma) + (ik|jl)-dressing ... 0.168 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 15.628 sec ( 21.5% of sigma) + Pair energies ... 0.038 sec ( 0.1% of sigma) +Total Time for computing (T) ... 17.511 sec ( 15.3% of ALL) + I/O of integral and amplitudes ... 2.077 sec ( 11.9% of (T)) + External N**7 contributions ... 9.226 sec ( 52.7% of (T)) + Internal N**7 contributions ... 0.950 sec ( 5.4% of (T)) + N**6 triples energy contributions ... 3.502 sec ( 20.0% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.450888754359 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.001217481 -0.004799793 0.002503766 + 2 N : -0.002010638 -0.005784664 -0.001006689 + 3 O : 0.003136322 0.004963235 -0.000873278 + 4 H : -0.002343165 0.005621222 -0.000623800 + +Norm of the cartesian gradient ... 0.011917133 +RMS gradient ... 0.003440180 +MAX gradient ... 0.005784664 + +------- +TIMINGS +------- + +Total numerical gradient time ... 886.106 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: -1049.35 cm**-1 ***imaginary mode*** + 7: 519.33 cm**-1 + 8: 882.60 cm**-1 + 9: 1295.63 cm**-1 + 10: 1718.64 cm**-1 + 11: 3702.74 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 -0.011667 0.430658 -0.070319 0.062696 0.026146 -0.062623 + 1 -0.056838 -0.030111 -0.051270 -0.000610 0.019564 0.003945 + 2 -0.004142 -0.523493 -0.162296 0.061127 0.120447 -0.006171 + 3 0.007218 -0.302900 -0.010091 0.007085 -0.635781 -0.000812 + 4 -0.066834 -0.024279 0.110478 -0.003205 -0.102543 -0.004635 + 5 0.023945 0.138180 0.482280 -0.045876 -0.096062 0.000878 + 6 0.002666 -0.187295 0.080118 -0.079381 0.526749 0.000855 + 7 0.052798 0.049300 -0.034344 0.003466 0.074884 0.003628 + 8 -0.014862 0.380243 -0.209599 0.040592 -0.003706 -0.000718 + 9 0.042564 0.346398 -0.015311 0.166373 0.059138 0.991684 + 10 0.992839 0.032813 -0.176316 -0.000796 -0.074170 -0.055791 + 11 -0.031109 0.353537 -0.798957 -0.976998 -0.518055 0.097152 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 7: 519.33 0.029790 150.55 0.017901 (-0.086178 0.008109 0.102021) + 8: 882.60 0.021307 107.68 0.007534 (-0.056980 0.003404 0.065385) + 9: 1295.63 0.036463 184.27 0.008783 ( 0.048140 -0.004711 -0.080267) + 10: 1718.64 0.021857 110.45 0.003969 (-0.051281 -0.000223 0.036591) + 11: 3702.74 0.014397 72.76 0.001213 ( 0.033156 -0.002706 -0.010334) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 7 +The total number of vibrations considered is 5 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 519.33 E(vib) ... 0.13 +freq. 882.60 E(vib) ... 0.04 +freq. 1295.63 E(vib) ... 0.01 +freq. 1718.64 E(vib) ... 0.00 +freq. 3702.74 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.45088875 Eh +Zero point energy ... 0.01849630 Eh 11.61 kcal/mol +Thermal vibrational correction ... 0.00028123 Eh 0.18 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42927868 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00311377 Eh 1.95 kcal/mol +Non-thermal (ZPE) correction 0.01849630 Eh 11.61 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02161007 Eh 13.56 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42927868 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.42833447 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 3.037401 0.415244 0.366295 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00037752 Eh 0.24 kcal/mol +Rotational entropy ... 0.00987536 Eh 6.20 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02805519 Eh 17.60 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00987536 Eh 6.20 kcal/mol| +| sn= 2 | S(rot)= 0.00922090 Eh 5.79 kcal/mol| +| sn= 3 | S(rot)= 0.00883807 Eh 5.55 kcal/mol| +| sn= 4 | S(rot)= 0.00856645 Eh 5.38 kcal/mol| +| sn= 5 | S(rot)= 0.00835576 Eh 5.24 kcal/mol| +| sn= 6 | S(rot)= 0.00818361 Eh 5.14 kcal/mol| +| sn= 7 | S(rot)= 0.00803807 Eh 5.04 kcal/mol| +| sn= 8 | S(rot)= 0.00791199 Eh 4.96 kcal/mol| +| sn= 9 | S(rot)= 0.00780078 Eh 4.90 kcal/mol| +| sn=10 | S(rot)= 0.00770130 Eh 4.83 kcal/mol| +| sn=11 | S(rot)= 0.00761131 Eh 4.78 kcal/mol| +| sn=12 | S(rot)= 0.00752916 Eh 4.72 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.42833447 Eh +Total entropy correction ... -0.02805519 Eh -17.60 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.45638967 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00550091 Eh -3.45 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.450888752 Eh +Current gradient norm .... 0.011917135 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.004927511 0.103290452 0.225754948 0.469282555 0.546171215 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999891614 +Lowest eigenvalues of augmented Hessian: + -0.000059340 0.102249610 0.225732468 0.468292621 0.545742935 +Length of the computed step .... 0.014724374 +The final length of the internal step .... 0.014724374 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0060112006 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0041739655 RMS(Int)= 0.0060109711 + Iter 1: RMS(Cart)= 0.0000008603 RMS(Int)= 0.0000009334 + Iter 2: RMS(Cart)= 0.0000000024 RMS(Int)= 0.0000000026 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0021974321 0.0001000000 NO + MAX gradient 0.0037506268 0.0003000000 NO + RMS step 0.0060112006 0.0020000000 NO + MAX step 0.0128513368 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0068 Max(Angles) 0.05 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4430 0.002299 -0.0068 1.4362 + 2. B(O 2,N 1) 1.1746 0.003751 -0.0014 1.1732 + 3. B(H 3,O 0) 0.9718 0.003006 -0.0035 0.9683 + 4. A(N 1,O 0,H 3) 101.99 0.000629 0.03 102.02 + 5. A(O 0,N 1,O 2) 110.50 -0.000432 0.05 110.54 + 6. D(O 2,N 1,O 0,H 3) 163.64 -0.009507 0.00 163.64 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.261993 0.035522 0.728457 + N 0.160105 -0.168165 -0.629104 + O 1.319774 -0.019483 -0.726406 + H -1.217885 0.152126 0.627053 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.495094 0.067127 1.376584 + 1 N 7.0000 0 14.007 0.302554 -0.317786 -1.188834 + 2 O 8.0000 0 15.999 2.494012 -0.036818 -1.372709 + 3 H 1.0000 0 1.008 -2.301470 0.287476 1.184959 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.436184140031 0.00000000 0.00000000 + O 2 1 0 1.173203912291 110.54450292 0.00000000 + H 1 2 3 0.968302825716 102.01829211 163.63636355 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.713994702541 0.00000000 0.00000000 + O 2 1 0 2.217034093475 110.54450292 0.00000000 + H 1 2 3 1.829827155305 102.01829211 163.63636355 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.445753992969 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.971e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7222847637 0.000000000000 0.00032186 0.00000688 0.0013760 0.7000 + 1 -204.7222910745 -0.000006310800 0.00024298 0.00000560 0.0010384 0.7000 + ***Turning on DIIS*** + 2 -204.7222961687 -0.000005094189 0.00054482 0.00001423 0.0007747 0.0000 + 3 -204.7217250539 0.000571114844 0.00019769 0.00000457 0.0001647 0.0000 + 4 -204.7222426972 -0.000517643318 0.00005321 0.00000142 0.0000912 0.0000 + 5 -204.7225461090 -0.000303411817 0.00002351 0.00000049 0.0000416 0.0000 + 6 -204.7222378071 0.000308301947 0.00000826 0.00000021 0.0000171 0.0000 + 7 -204.7223066180 -0.000068810910 0.00000274 0.00000007 0.0000045 0.0000 + 8 -204.7223144833 -0.000007865332 0.00000108 0.00000004 0.0000017 0.0000 + 9 -204.7223073349 0.000007148356 0.00000070 0.00000003 0.0000010 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 10 CYCLES * + ***************************************************** + +Total Energy : -204.72231450 Eh -5570.77739 eV + Last Energy change ... -7.1675e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.7984e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.203 sec +Reference energy ... -204.722312203 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.360 sec +AO-integral generation ... 0.143 sec +Half transformation ... 0.079 sec +K-integral sorting ... 5.366 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.025 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.025 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.029 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.046 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.036 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.352 sec +AO-integral generation ... 0.248 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.048 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.153 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.250 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090561080 +EMP2(bb)= -0.090561080 +EMP2(ab)= -0.516458521 + +Initial guess performed in 0.131 sec +E(0) ... -204.722312203 +E(MP2) ... -0.697580681 +Initial E(tot) ... -205.419892884 + ... 0.187964085 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.419892884 -0.697580681 -0.000000000 0.026301818 2.80 0.000001653 + *** Turning on DIIS *** + 1 -205.390709197 -0.668396994 0.029183687 0.011440760 2.79 0.057913366 + 2 -205.410192343 -0.687880140 -0.019483146 0.005771695 2.89 0.060834172 + 3 -205.413892825 -0.691580621 -0.003700481 0.002384989 2.93 0.075224144 + 4 -205.415459216 -0.693147012 -0.001566391 0.001642175 2.85 0.082081771 + 5 -205.416017902 -0.693705698 -0.000558686 0.000880043 2.88 0.087839822 + 6 -205.416130534 -0.693818331 -0.000112633 0.000519221 2.90 0.090681013 + 7 -205.416175347 -0.693863144 -0.000044812 0.000202108 3.02 0.091937975 + 8 -205.416187244 -0.693875041 -0.000011897 0.000104176 2.90 0.092392958 + 9 -205.416183046 -0.693870843 0.000004198 0.000027266 2.87 0.092523850 + 10 -205.416187479 -0.693875276 -0.000004433 0.000009769 2.89 0.092560695 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.722312203 +E(CORR) ... -0.693875276 +E(TOT) ... -205.416187479 +Singles norm **1/2 ... 0.092560695 ( 0.046280347, 0.046280347) +T1 diagnostic ... 0.021816765 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.063029 + 10a-> 13a 10b-> 13b 0.050965 + 8b-> 13b -1b-> -1b 0.043321 + 8a-> 13a -1a-> -1a 0.043321 + 8a-> 13a 10b-> 13b 0.034631 + 10a-> 13a 8b-> 13b 0.034631 + 10a-> 13a -1a-> -1a 0.033704 + 10b-> 13b -1b-> -1b 0.033704 + 11a-> 13a 11b-> 13b 0.027997 + 11b-> 26b -1b-> -1b 0.027435 + 11a-> 26a -1a-> -1a 0.027435 + 11a-> 26a 11b-> 26b 0.027263 + 5a-> 13a 5b-> 13b 0.025698 + 8a-> 13a 8b-> 22b 0.022755 + 8a-> 22a 8b-> 13b 0.022755 + 11a-> 26a 10b-> 13b 0.022340 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034724759 + alpha-alpha-alpha ... -0.000899112 ( 2.6%) + alpha-alpha-beta ... -0.016463267 ( 47.4%) + alpha-beta -beta ... -0.016463267 ( 47.4%) + beta -beta -beta ... -0.000899112 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034724759 + +Final correlation energy ... -0.728600034 +E(CCSD) ... -205.416187479 +E(CCSD(T)) ... -205.450912238 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209633131 sqrt= 1.099833229 +W(HF) = 0.826696934 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 46.999 sec + +Fock Matrix Formation ... 0.203 sec ( 0.4%) +Initial Guess ... 0.131 sec ( 0.3%) +DIIS Solver ... 1.464 sec ( 3.1%) +State Vector Update ... 0.073 sec ( 0.2%) +Sigma-vector construction ... 30.177 sec ( 64.2%) + <0|H|D> ... 0.003 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (0-ext) ... 0.054 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (2-ext) ... 0.734 sec ( 2.4% of sigma) + (4-ext) ... 16.839 sec ( 55.8% of sigma) + ... 1.109 sec ( 3.7% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.085 sec ( 0.3% of sigma) + Fock-dressing ... 1.646 sec ( 5.5% of sigma) + (ik|jl)-dressing ... 0.059 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 7.551 sec ( 25.0% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.957 sec ( 14.8% of ALL) + I/O of integral and amplitudes ... 0.816 sec ( 11.7% of (T)) + External N**7 contributions ... 3.906 sec ( 56.1% of (T)) + Internal N**7 contributions ... 0.312 sec ( 4.5% of (T)) + N**6 triples energy contributions ... 1.695 sec ( 24.4% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.450912237629 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.001023884 -0.004135845 0.000433378 + 2 N : 0.000689609 -0.005080008 0.000747475 + 3 O : -0.000958950 0.004263676 -0.000663490 + 4 H : 0.001293225 0.004952177 -0.000517363 + +Norm of the cartesian gradient ... 0.009549085 +RMS gradient ... 0.002756583 +MAX gradient ... 0.005080008 + +------- +TIMINGS +------- + +Total numerical gradient time ... 329.505 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.450912238 Eh +Current gradient norm .... 0.009549085 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999998581 +Lowest eigenvalues of augmented Hessian: + -0.000001627 0.101848995 0.228725233 0.470671639 0.564968425 +Length of the computed step .... 0.001684441 +The final length of the internal step .... 0.001684441 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0006876700 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0007004639 RMS(Int)= 0.0006876664 + Iter 1: RMS(Cart)= 0.0000001492 RMS(Int)= 0.0000002707 + Iter 2: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000001 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000234852 0.0000050000 NO + RMS gradient 0.0004108423 0.0001000000 NO + MAX gradient 0.0007337871 0.0003000000 NO + RMS step 0.0006876700 0.0020000000 YES + MAX step 0.0011779716 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0005 Max(Angles) 0.07 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4362 -0.000157 0.0003 1.4365 + 2. B(O 2,N 1) 1.1732 -0.000266 0.0000 1.1732 + 3. B(H 3,O 0) 0.9683 -0.000562 0.0005 0.9688 + 4. A(N 1,O 0,H 3) 102.02 -0.000252 0.03 102.05 + 5. A(O 0,N 1,O 2) 110.54 -0.000734 0.07 110.61 + 6. D(O 2,N 1,O 0,H 3) 163.64 -0.009119 -0.00 163.64 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.262218 0.035486 0.728686 + N 0.160584 -0.168071 -0.628957 + O 1.320244 -0.019603 -0.727069 + H -1.218609 0.152187 0.627340 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.495520 0.067060 1.377016 + 1 N 7.0000 0 14.007 0.303460 -0.317608 -1.188556 + 2 O 8.0000 0 15.999 2.494899 -0.037043 -1.373962 + 3 H 1.0000 0 1.008 -2.302837 0.287592 1.185501 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.436450342784 0.00000000 0.00000000 + O 2 1 0 1.173234169505 110.61199573 0.00000000 + H 1 2 3 0.968800360922 102.05016257 163.63636355 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.714497752838 0.00000000 0.00000000 + O 2 1 0 2.217091271323 110.61199573 0.00000000 + H 1 2 3 1.830767360587 102.05016257 163.63636355 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.429089345605 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.972e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7222594595 0.000000000000 0.00003555 0.00000086 0.0001884 0.7000 + 1 -204.7222595869 -0.000000127366 0.00002972 0.00000072 0.0001527 0.7000 + ***Turning on DIIS*** + 2 -204.7222596907 -0.000000103763 0.00007526 0.00000191 0.0001213 0.0000 + 3 -204.7223088245 -0.000049133868 0.00002761 0.00000068 0.0000445 0.0000 + 4 -204.7222717765 0.000037048039 0.00000509 0.00000020 0.0000120 0.0000 + 5 -204.7222373596 0.000034416877 0.00000347 0.00000010 0.0000086 0.0000 + 6 -204.7222637971 -0.000026437460 0.00000153 0.00000004 0.0000025 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + +Total Energy : -204.72225971 Eh -5570.77590 eV + Last Energy change ... 4.0880e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.5635e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.210 sec +Reference energy ... -204.722260026 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.350 sec +AO-integral generation ... 0.142 sec +Half transformation ... 0.079 sec +K-integral sorting ... 5.362 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.026 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.025 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.029 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.046 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.353 sec +AO-integral generation ... 0.249 sec +Half transformation ... 0.042 sec +J-integral sorting ... 0.048 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.150 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.255 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090568152 +EMP2(bb)= -0.090568152 +EMP2(ab)= -0.516498133 + +Initial guess performed in 0.133 sec +E(0) ... -204.722260026 +E(MP2) ... -0.697634437 +Initial E(tot) ... -205.419894463 + ... 0.188016302 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.419894463 -0.697634437 -0.000000000 0.026315521 3.05 0.000001298 + *** Turning on DIIS *** + 1 -205.390682818 -0.668422793 0.029211645 0.011447627 2.85 0.057945433 + 2 -205.410176047 -0.687916021 -0.019493228 0.005774331 2.90 0.060861922 + 3 -205.413878340 -0.691618314 -0.003702293 0.002386389 2.87 0.075262050 + 4 -205.415446211 -0.693186185 -0.001567871 0.001644358 2.91 0.082125855 + 5 -205.416005753 -0.693745727 -0.000559542 0.000881196 2.92 0.087891361 + 6 -205.416118553 -0.693858527 -0.000112800 0.000519834 2.93 0.090736956 + 7 -205.416163471 -0.693903445 -0.000044918 0.000202291 3.25 0.091996226 + 8 -205.416175392 -0.693915366 -0.000011922 0.000104269 3.05 0.092451935 + 9 -205.416171191 -0.693911165 0.000004201 0.000027292 2.96 0.092582997 + 10 -205.416175635 -0.693915609 -0.000004444 0.000009685 2.99 0.092619922 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.722260026 +E(CORR) ... -0.693915609 +E(TOT) ... -205.416175635 +Singles norm **1/2 ... 0.092619922 ( 0.046309961, 0.046309961) +T1 diagnostic ... 0.021830725 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.063084 + 10a-> 13a 10b-> 13b 0.050943 + 8b-> 13b -1b-> -1b 0.043341 + 8a-> 13a -1a-> -1a 0.043341 + 10a-> 13a 8b-> 13b 0.034625 + 8a-> 13a 10b-> 13b 0.034625 + 10a-> 13a -1a-> -1a 0.033753 + 10b-> 13b -1b-> -1b 0.033753 + 11a-> 13a 11b-> 13b 0.028018 + 11b-> 26b -1b-> -1b 0.027455 + 11a-> 26a -1a-> -1a 0.027455 + 11a-> 26a 11b-> 26b 0.027274 + 5a-> 13a 5b-> 13b 0.025710 + 8a-> 13a 8b-> 22b 0.022760 + 8a-> 22a 8b-> 13b 0.022760 + 10a-> 13a 11b-> 26b 0.022342 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034736997 + alpha-alpha-alpha ... -0.000899355 ( 2.6%) + alpha-alpha-beta ... -0.016469143 ( 47.4%) + alpha-beta -beta ... -0.016469143 ( 47.4%) + beta -beta -beta ... -0.000899355 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034736997 + +Final correlation energy ... -0.728652606 +E(CCSD) ... -205.416175635 +E(CCSD(T)) ... -205.450912632 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209702591 sqrt= 1.099864806 +W(HF) = 0.826649465 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 47.974 sec + +Fock Matrix Formation ... 0.210 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.3%) +DIIS Solver ... 1.448 sec ( 3.0%) +State Vector Update ... 0.075 sec ( 0.2%) +Sigma-vector construction ... 31.165 sec ( 65.0%) + <0|H|D> ... 0.003 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.018 sec ( 0.1% of sigma) + (0-ext) ... 0.055 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (2-ext) ... 0.737 sec ( 2.4% of sigma) + (4-ext) ... 17.658 sec ( 56.7% of sigma) + ... 1.142 sec ( 3.7% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.088 sec ( 0.3% of sigma) + Fock-dressing ... 1.650 sec ( 5.3% of sigma) + (ik|jl)-dressing ... 0.059 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 7.641 sec ( 24.5% of sigma) + Pair energies ... 0.005 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.942 sec ( 14.5% of ALL) + I/O of integral and amplitudes ... 0.836 sec ( 12.0% of (T)) + External N**7 contributions ... 3.903 sec ( 56.2% of (T)) + Internal N**7 contributions ... 0.316 sec ( 4.5% of (T)) + N**6 triples energy contributions ... 1.698 sec ( 24.5% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.450912631701 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.000889453 -0.004534008 0.000131514 + 2 N : 0.000867079 -0.004711307 0.001311026 + 3 O : -0.000764168 0.004225764 -0.000989066 + 4 H : 0.000786542 0.005019551 -0.000453474 + +Norm of the cartesian gradient ... 0.009564107 +RMS gradient ... 0.002760920 +MAX gradient ... 0.005019551 + +------- +TIMINGS +------- + +Total numerical gradient time ... 330.753 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.450912632 Eh +Current gradient norm .... 0.009564107 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999996620 +Lowest eigenvalues of augmented Hessian: + -0.000000706 0.089397118 0.205245780 0.456275477 0.740575959 +Length of the computed step .... 0.002599931 +The final length of the internal step .... 0.002599931 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0010614175 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0007093729 RMS(Int)= 0.0010614675 + Iter 1: RMS(Cart)= 0.0000000924 RMS(Int)= 0.0000001496 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000003941 0.0000050000 YES + RMS gradient 0.0001368474 0.0001000000 NO + MAX gradient 0.0002902939 0.0003000000 YES + RMS step 0.0010614175 0.0020000000 YES + MAX step 0.0025211153 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0013 Max(Angles) 0.02 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4365 -0.000290 0.0013 1.4378 + 2. B(O 2,N 1) 1.1732 -0.000085 -0.0001 1.1731 + 3. B(H 3,O 0) 0.9688 -0.000062 0.0003 0.9691 + 4. A(N 1,O 0,H 3) 102.05 -0.000034 -0.01 102.04 + 5. A(O 0,N 1,O 2) 110.61 0.000126 0.02 110.63 + 6. D(O 2,N 1,O 0,H 3) 163.64 -0.009107 -0.00 163.64 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 4 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.262525 0.035544 0.729367 + N 0.161056 -0.168106 -0.629431 + O 1.320613 -0.019676 -0.727511 + H -1.219144 0.152238 0.627575 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.496100 0.067168 1.378303 + 1 N 7.0000 0 14.007 0.304352 -0.317673 -1.189451 + 2 O 8.0000 0 15.999 2.495598 -0.037182 -1.374797 + 3 H 1.0000 0 1.008 -2.303847 0.287688 1.185945 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.437784459597 0.00000000 0.00000000 + O 2 1 0 1.173125805046 110.62752865 0.00000000 + H 1 2 3 0.969070844778 102.04076090 163.63636355 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.717018868247 0.00000000 0.00000000 + O 2 1 0 2.216886492173 110.62752865 0.00000000 + H 1 2 3 1.831278500998 102.04076090 163.63636355 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.400000629589 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.973e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.006 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7221368169 0.000000000000 0.00004298 0.00000105 0.0002458 0.7000 + 1 -204.7221370443 -0.000000227413 0.00003421 0.00000089 0.0001894 0.7000 + ***Turning on DIIS*** + 2 -204.7221372333 -0.000000189034 0.00008297 0.00000235 0.0001446 0.0000 + 3 -204.7221894612 -0.000052227851 0.00003210 0.00000095 0.0000341 0.0000 + 4 -204.7221258139 0.000063647217 0.00001207 0.00000030 0.0000117 0.0000 + 5 -204.7221115719 0.000014242054 0.00000393 0.00000009 0.0000056 0.0000 + 6 -204.7221481367 -0.000036564821 0.00000267 0.00000005 0.0000041 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + +Total Energy : -204.72213951 Eh -5570.77263 eV + Last Energy change ... 8.6273e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.3721e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.211 sec +Reference energy ... -204.722137858 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.433 sec +AO-integral generation ... 0.142 sec +Half transformation ... 0.079 sec +K-integral sorting ... 5.437 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.026 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.025 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.045 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.023 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.039 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.362 sec +AO-integral generation ... 0.254 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.054 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.146 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.254 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090582080 +EMP2(bb)= -0.090582080 +EMP2(ab)= -0.516591341 + +Initial guess performed in 0.133 sec +E(0) ... -204.722137858 +E(MP2) ... -0.697755502 +Initial E(tot) ... -205.419893360 + ... 0.188133642 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.419893360 -0.697755502 -0.000000000 0.026298115 2.84 0.000000694 + *** Turning on DIIS *** + 1 -205.390624118 -0.668486260 0.029269242 0.011442840 2.88 0.058007069 + 2 -205.410138434 -0.688000575 -0.019514315 0.005768528 2.90 0.060913740 + 3 -205.413844648 -0.691706789 -0.003706214 0.002387588 2.88 0.075335922 + 4 -205.415415194 -0.693277335 -0.001570546 0.001654672 2.93 0.082212393 + 5 -205.415976703 -0.693838845 -0.000561510 0.000886394 2.97 0.087999227 + 6 -205.416090054 -0.693952196 -0.000113351 0.000523056 2.93 0.090860555 + 7 -205.416135319 -0.693997460 -0.000045264 0.000203106 3.02 0.092130648 + 8 -205.416147368 -0.694009509 -0.000012049 0.000104707 3.07 0.092590339 + 9 -205.416143148 -0.694005289 0.000004220 0.000027367 2.94 0.092722562 + 10 -205.416147627 -0.694009769 -0.000004479 0.000009671 2.89 0.092759836 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.722137858 +E(CORR) ... -0.694009769 +E(TOT) ... -205.416147627 +Singles norm **1/2 ... 0.092759836 ( 0.046379918, 0.046379918) +T1 diagnostic ... 0.021863703 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.063299 + 10a-> 13a 10b-> 13b 0.050748 + 8a-> 13a -1a-> -1a 0.043301 + 8b-> 13b -1b-> -1b 0.043301 + 8a-> 13a 10b-> 13b 0.034617 + 10a-> 13a 8b-> 13b 0.034617 + 10b-> 13b -1b-> -1b 0.033989 + 10a-> 13a -1a-> -1a 0.033989 + 11a-> 13a 11b-> 13b 0.028000 + 11a-> 26a -1a-> -1a 0.027330 + 11b-> 26b -1b-> -1b 0.027330 + 11a-> 26a 11b-> 26b 0.027166 + 5a-> 13a 5b-> 13b 0.025774 + 8a-> 22a 8b-> 13b 0.022820 + 8a-> 13a 8b-> 22b 0.022820 + 11a-> 26a 10b-> 13b 0.022263 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034764624 + alpha-alpha-alpha ... -0.000899768 ( 2.6%) + alpha-alpha-beta ... -0.016482544 ( 47.4%) + alpha-beta -beta ... -0.016482544 ( 47.4%) + beta -beta -beta ... -0.000899768 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034764624 + +Final correlation energy ... -0.728774393 +E(CCSD) ... -205.416147627 +E(CCSD(T)) ... -205.450912251 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209867374 sqrt= 1.099939714 +W(HF) = 0.826536876 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 47.508 sec + +Fock Matrix Formation ... 0.211 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.3%) +DIIS Solver ... 1.356 sec ( 2.9%) +State Vector Update ... 0.067 sec ( 0.1%) +Sigma-vector construction ... 30.842 sec ( 64.9%) + <0|H|D> ... 0.003 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.019 sec ( 0.1% of sigma) + (0-ext) ... 0.054 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (2-ext) ... 0.739 sec ( 2.4% of sigma) + (4-ext) ... 17.622 sec ( 57.1% of sigma) + ... 1.056 sec ( 3.4% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.084 sec ( 0.3% of sigma) + Fock-dressing ... 1.622 sec ( 5.3% of sigma) + (ik|jl)-dressing ... 0.058 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 7.459 sec ( 24.2% of sigma) + Pair energies ... 0.004 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.855 sec ( 14.4% of ALL) + I/O of integral and amplitudes ... 0.839 sec ( 12.2% of (T)) + External N**7 contributions ... 3.920 sec ( 57.2% of (T)) + Internal N**7 contributions ... 0.315 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.699 sec ( 24.8% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.450912251295 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.001185421 -0.004510948 0.000482734 + 2 N : 0.001262402 -0.004743115 0.001071287 + 3 O : -0.000595738 0.004212975 -0.001118767 + 4 H : 0.000518758 0.005041088 -0.000435254 + +Norm of the cartesian gradient ... 0.009615206 +RMS gradient ... 0.002775671 +MAX gradient ... 0.005041088 + +------- +TIMINGS +------- + +Total numerical gradient time ... 319.025 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 283.82 cm**-1 + 7: 698.45 cm**-1 + 8: 856.78 cm**-1 + 9: 1292.00 cm**-1 + 10: 1746.72 cm**-1 + 11: 3775.14 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 -0.114567 0.128991 -0.111439 0.066001 0.035498 -0.062131 + 1 -0.044147 -0.068241 -0.043183 0.005181 0.009395 0.007476 + 2 0.141695 -0.195679 -0.092625 0.060808 0.110716 -0.005900 + 3 0.093106 -0.080333 0.018244 0.007340 -0.628827 -0.000863 + 4 -0.064111 -0.058052 0.107715 0.003280 -0.114299 -0.000177 + 5 -0.043429 0.113751 0.436298 -0.050092 -0.094623 0.000052 + 6 0.030874 -0.073369 0.099257 -0.082337 0.508995 0.000762 + 7 0.040024 0.061234 -0.038596 -0.001782 0.084197 0.000166 + 8 -0.094117 0.098709 -0.238022 0.044324 0.005643 -0.000325 + 9 0.034576 0.233453 -0.060166 0.157287 0.095883 0.986053 + 10 0.956330 0.917904 -0.198796 -0.099532 0.102774 -0.118854 + 11 -0.151684 -0.041549 -0.814684 -0.972601 -0.531977 0.098082 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 283.82 0.033504 169.32 0.036839 ( 0.108536 0.102300 -0.120803) + 7: 698.45 0.024163 122.11 0.010796 (-0.049747 0.064985 0.064017) + 8: 856.78 0.015573 78.70 0.005672 (-0.050509 0.001602 0.055841) + 9: 1292.00 0.032330 163.38 0.007809 ( 0.043708 -0.010722 -0.076049) + 10: 1746.72 0.021187 107.07 0.003785 (-0.050163 0.003130 0.035483) + 11: 3775.14 0.014562 73.59 0.001204 ( 0.032793 -0.005369 -0.009977) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 283.82 E(vib) ... 0.28 +freq. 698.45 E(vib) ... 0.07 +freq. 856.78 E(vib) ... 0.04 +freq. 1292.00 E(vib) ... 0.01 +freq. 1746.72 E(vib) ... 0.00 +freq. 3775.14 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.45091225 Eh +Zero point energy ... 0.01971276 Eh 12.37 kcal/mol +Thermal vibrational correction ... 0.00063091 Eh 0.40 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42773603 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00346346 Eh 2.17 kcal/mol +Non-thermal (ZPE) correction 0.01971276 Eh 12.37 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02317622 Eh 14.54 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42773603 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.42679182 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 3.060878 0.416859 0.367887 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00096056 Eh 0.60 kcal/mol +Rotational entropy ... 0.00986785 Eh 6.19 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02863073 Eh 17.97 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00986785 Eh 6.19 kcal/mol| +| sn= 2 | S(rot)= 0.00921339 Eh 5.78 kcal/mol| +| sn= 3 | S(rot)= 0.00883056 Eh 5.54 kcal/mol| +| sn= 4 | S(rot)= 0.00855893 Eh 5.37 kcal/mol| +| sn= 5 | S(rot)= 0.00834825 Eh 5.24 kcal/mol| +| sn= 6 | S(rot)= 0.00817610 Eh 5.13 kcal/mol| +| sn= 7 | S(rot)= 0.00803055 Eh 5.04 kcal/mol| +| sn= 8 | S(rot)= 0.00790448 Eh 4.96 kcal/mol| +| sn= 9 | S(rot)= 0.00779327 Eh 4.89 kcal/mol| +| sn=10 | S(rot)= 0.00769379 Eh 4.83 kcal/mol| +| sn=11 | S(rot)= 0.00760380 Eh 4.77 kcal/mol| +| sn=12 | S(rot)= 0.00752164 Eh 4.72 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.42679182 Eh +Total entropy correction ... -0.02863073 Eh -17.97 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.45542255 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00451030 Eh -2.83 kcal/mol + + +Actual Hessian File stored as input.002.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.450912252 Eh +Current gradient norm .... 0.009615207 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating recalculated hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.015816891 0.110399045 0.195850850 0.514102474 0.609331083 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999997316 +Lowest eigenvalues of augmented Hessian: + -0.000001344 0.107980693 0.195160277 0.514003284 0.605366387 +Length of the computed step .... 0.002316993 +The final length of the internal step .... 0.002316993 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0009459084 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0007785731 RMS(Int)= 0.0009458372 + Iter 1: RMS(Cart)= 0.0000001446 RMS(Int)= 0.0000002902 + Iter 2: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000001 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change 0.0000003795 0.0000050000 YES + RMS gradient 0.0003124534 0.0001000000 NO + MAX gradient 0.0006430389 0.0003000000 NO + RMS step 0.0009459084 0.0020000000 YES + MAX step 0.0020528122 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0011 Max(Angles) 0.05 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4378 0.000316 -0.0011 1.4367 + 2. B(O 2,N 1) 1.1731 0.000038 0.0002 1.1733 + 3. B(H 3,O 0) 0.9691 0.000141 -0.0001 0.9689 + 4. A(N 1,O 0,H 3) 102.04 0.000226 -0.02 102.02 + 5. A(O 0,N 1,O 2) 110.63 0.000643 -0.05 110.57 + 6. D(O 2,N 1,O 0,H 3) 163.64 -0.009105 0.00 163.64 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 5 * + ************************************************************* + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.425182489003 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.972e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7222175001 0.000000000000 0.00002890 0.00000094 0.0001896 0.7000 + 1 -204.7222177051 -0.000000204934 0.00002545 0.00000081 0.0001465 0.7000 + ***Turning on DIIS*** + 2 -204.7222178760 -0.000000170924 0.00007501 0.00000221 0.0001121 0.0000 + 3 -204.7221913678 0.000026508177 0.00003469 0.00000094 0.0000321 0.0000 + 4 -204.7222187189 -0.000027351042 0.00000956 0.00000030 0.0000141 0.0000 + 5 -204.7222334275 -0.000014708632 0.00000480 0.00000010 0.0000096 0.0000 + 6 -204.7222155945 0.000017832936 0.00000286 0.00000006 0.0000027 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + +Total Energy : -204.72221820 Eh -5570.77477 eV + Last Energy change ... -2.6039e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.5301e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.201 sec +Reference energy ... -204.722218454 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.374 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.079 sec +K-integral sorting ... 5.380 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.026 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.025 s ( 0.000 ms/b) + 277134 b 0 skpd 0.034 s ( 0.000 ms/b) +: : 151164 b 0 skpd 0.052 s ( 0.000 ms/b) + 159120 b 0 skpd 0.019 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.036 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.037 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.028 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.045 s ( 0.001 ms/b) +: 27846 b 0 skpd 0.026 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.399 sec +AO-integral generation ... 0.289 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.053 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.155 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.254 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090573132 +EMP2(bb)= -0.090573132 +EMP2(ab)= -0.516530954 + +Initial guess performed in 0.131 sec +E(0) ... -204.722218454 +E(MP2) ... -0.697677218 +Initial E(tot) ... -205.419895672 + ... 0.188053767 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.419895672 -0.697677218 -0.000000000 0.026313503 2.82 0.000001167 + *** Turning on DIIS *** + 1 -205.390667658 -0.668449204 0.029228014 0.011448488 2.78 0.057955798 + 2 -205.410166643 -0.687948188 -0.019498985 0.005774183 2.83 0.060870690 + 3 -205.413870160 -0.691651706 -0.003703517 0.002387115 2.82 0.075274602 + 4 -205.415438574 -0.693220119 -0.001568414 0.001645895 2.86 0.082140018 + 5 -205.415998446 -0.693779992 -0.000559873 0.000882102 2.89 0.087908637 + 6 -205.416111333 -0.693892879 -0.000112887 0.000520575 2.90 0.090756604 + 7 -205.416156308 -0.693937853 -0.000044975 0.000202567 2.96 0.092018023 + 8 -205.416168260 -0.693949805 -0.000011952 0.000104428 2.92 0.092474733 + 9 -205.416164054 -0.693945600 0.000004206 0.000027327 2.86 0.092606151 + 10 -205.416168506 -0.693950052 -0.000004452 0.000009756 2.82 0.092643172 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.722218454 +E(CORR) ... -0.693950052 +E(TOT) ... -205.416168506 +Singles norm **1/2 ... 0.092643172 ( 0.046321586, 0.046321586) +T1 diagnostic ... 0.021836205 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.063124 + 10a-> 13a 10b-> 13b 0.050934 + 8a-> 13a -1a-> -1a 0.043343 + 8b-> 13b -1b-> -1b 0.043343 + 10a-> 13a 8b-> 13b 0.034645 + 8a-> 13a 10b-> 13b 0.034645 + 10b-> 13b -1b-> -1b 0.033784 + 10a-> 13a -1a-> -1a 0.033784 + 11a-> 13a 11b-> 13b 0.028004 + 11a-> 26a -1a-> -1a 0.027417 + 11b-> 26b -1b-> -1b 0.027417 + 11a-> 26a 11b-> 26b 0.027244 + 5a-> 13a 5b-> 13b 0.025731 + 8a-> 13a 8b-> 22b 0.022765 + 8a-> 22a 8b-> 13b 0.022765 + 10a-> 13a 11b-> 26b 0.022325 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034744391 + alpha-alpha-alpha ... -0.000899442 ( 2.6%) + alpha-alpha-beta ... -0.016472754 ( 47.4%) + alpha-beta -beta ... -0.016472754 ( 47.4%) + beta -beta -beta ... -0.000899442 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034744391 + +Final correlation energy ... -0.728694443 +E(CCSD) ... -205.416168506 +E(CCSD(T)) ... -205.450912898 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209747941 sqrt= 1.099885422 +W(HF) = 0.826618477 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 46.672 sec + +Fock Matrix Formation ... 0.201 sec ( 0.4%) +Initial Guess ... 0.131 sec ( 0.3%) +DIIS Solver ... 1.382 sec ( 3.0%) +State Vector Update ... 0.066 sec ( 0.1%) +Sigma-vector construction ... 30.022 sec ( 64.3%) + <0|H|D> ... 0.003 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (0-ext) ... 0.055 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (2-ext) ... 0.736 sec ( 2.5% of sigma) + (4-ext) ... 16.779 sec ( 55.9% of sigma) + ... 1.029 sec ( 3.4% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.084 sec ( 0.3% of sigma) + Fock-dressing ... 1.624 sec ( 5.4% of sigma) + (ik|jl)-dressing ... 0.059 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 7.518 sec ( 25.0% of sigma) + Pair energies ... 0.004 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.837 sec ( 14.6% of ALL) + I/O of integral and amplitudes ... 0.822 sec ( 12.0% of (T)) + External N**7 contributions ... 3.914 sec ( 57.2% of (T)) + Internal N**7 contributions ... 0.313 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.706 sec ( 25.0% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.450912897721 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.000641536 -0.004512640 0.000289319 + 2 N : 0.000603284 -0.004778875 0.001080727 + 3 O : -0.000643093 0.004268022 -0.000848061 + 4 H : 0.000681345 0.005023493 -0.000521985 + +Norm of the cartesian gradient ... 0.009515762 +RMS gradient ... 0.002746964 +MAX gradient ... 0.005023493 + +------- +TIMINGS +------- + +Total numerical gradient time ... 329.141 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.450912898 Eh +Current gradient norm .... 0.009515762 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999397 +Lowest eigenvalues of augmented Hessian: + -0.000000314 0.125816427 0.231291435 0.497592959 0.696386059 +Length of the computed step .... 0.001098283 +The final length of the internal step .... 0.001098283 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0004483723 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0002925262 RMS(Int)= 0.0004483845 + Iter 1: RMS(Cart)= 0.0000000339 RMS(Int)= 0.0000000506 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000006455 0.0000050000 YES + RMS gradient 0.0001463565 0.0001000000 NO + MAX gradient 0.0002445248 0.0003000000 YES + RMS step 0.0004483723 0.0020000000 YES + MAX step 0.0010617147 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0006 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4367 -0.000245 0.0006 1.4373 + 2. B(O 2,N 1) 1.1733 0.000028 -0.0001 1.1732 + 3. B(H 3,O 0) 0.9689 0.000050 -0.0000 0.9689 + 4. A(N 1,O 0,H 3) 102.02 -0.000139 0.01 102.03 + 5. A(O 0,N 1,O 2) 110.57 -0.000215 0.01 110.58 + 6. D(O 2,N 1,O 0,H 3) 163.64 -0.009105 0.00 163.64 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 5 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.262260 0.035542 0.729008 + N 0.160663 -0.168173 -0.629430 + O 1.320317 -0.019581 -0.727013 + H -1.218719 0.152212 0.627435 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.495599 0.067164 1.377626 + 1 N 7.0000 0 14.007 0.303609 -0.317800 -1.189450 + 2 O 8.0000 0 15.999 2.495037 -0.037003 -1.373856 + 3 H 1.0000 0 1.008 -2.303045 0.287639 1.185680 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.437259993442 0.00000000 0.00000000 + O 2 1 0 1.173200148004 110.58048028 0.00000000 + H 1 2 3 0.968887755055 102.03236279 163.63636355 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.716027770846 0.00000000 0.00000000 + O 2 1 0 2.217026980003 110.58048028 0.00000000 + H 1 2 3 1.830932511563 102.03236279 163.63636355 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.415212570297 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.4152125703 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.973e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7221851780 0.000000000000 0.00001557 0.00000042 0.0001033 0.7000 + 1 -204.7221852224 -0.000000044411 0.00001282 0.00000036 0.0000809 0.7000 + ***Turning on DIIS*** + 2 -204.7221852593 -0.000000036935 0.00003339 0.00000096 0.0000626 0.0000 + 3 -204.7221902385 -0.000004979179 0.00001238 0.00000039 0.0000165 0.0000 + 4 -204.7221826884 0.000007550109 0.00000509 0.00000013 0.0000057 0.0000 + 5 -204.7221811264 0.000001561983 0.00000175 0.00000004 0.0000026 0.0000 + 6 -204.7221867338 -0.000005607419 0.00000128 0.00000002 0.0000019 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72218551 Eh -5570.77388 eV + +Components: +Nuclear Repulsion : 69.41521257 Eh 1888.88396 eV +Electronic Energy : -274.13739808 Eh -7459.65784 eV +One Electron Energy: -418.53519244 Eh -11388.92159 eV +Two Electron Energy: 144.39779437 Eh 3929.26374 eV + +Virial components: +Potential Energy : -408.96891349 Eh -11128.60990 eV +Kinetic Energy : 204.24672798 Eh 5557.83602 eV +Virial Ratio : 2.00232786 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.2287e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.1848e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 9.4758e-09 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.1033e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.668399 -562.4157 + 1 1.0000 -20.638549 -561.6035 + 2 1.0000 -15.799313 -429.9212 + 3 1.0000 -1.605620 -43.6911 + 4 1.0000 -1.399048 -38.0700 + 5 1.0000 -0.948667 -25.8145 + 6 1.0000 -0.783072 -21.3085 + 7 1.0000 -0.729732 -19.8570 + 8 1.0000 -0.684009 -18.6128 + 9 1.0000 -0.623454 -16.9651 + 10 1.0000 -0.528891 -14.3918 + 11 1.0000 -0.461046 -12.5457 + 12 0.0000 0.028384 0.7724 + 13 0.0000 0.079768 2.1706 + 14 0.0000 0.093612 2.5473 + 15 0.0000 0.097965 2.6658 + 16 0.0000 0.127008 3.4561 + 17 0.0000 0.145443 3.9577 + 18 0.0000 0.156929 4.2703 + 19 0.0000 0.172380 4.6907 + 20 0.0000 0.187056 5.0900 + 21 0.0000 0.196102 5.3362 + 22 0.0000 0.204963 5.5773 + 23 0.0000 0.233950 6.3661 + 24 0.0000 0.259913 7.0726 + 25 0.0000 0.294054 8.0016 + 26 0.0000 0.308174 8.3858 + 27 0.0000 0.329617 8.9693 + 28 0.0000 0.362868 9.8741 + 29 0.0000 0.378583 10.3018 + 30 0.0000 0.424390 11.5482 + 31 0.0000 0.516328 14.0500 + 32 0.0000 0.529858 14.4182 + 33 0.0000 0.548307 14.9202 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53.1287 + 74 0.0000 1.964518 53.4572 + 75 0.0000 2.008982 54.6672 + 76 0.0000 2.077603 56.5344 + 77 0.0000 2.103154 57.2297 + 78 0.0000 2.162368 58.8410 + 79 0.0000 2.174617 59.1743 + 80 0.0000 2.283674 62.1419 + 81 0.0000 2.304088 62.6974 + 82 0.0000 2.321316 63.1662 + 83 0.0000 2.377656 64.6993 + 84 0.0000 2.447050 66.5876 + 85 0.0000 2.469118 67.1881 + 86 0.0000 2.495378 67.9027 + 87 0.0000 2.502513 68.0969 + 88 0.0000 2.519774 68.5665 + 89 0.0000 2.541272 69.1515 + 90 0.0000 2.571747 69.9808 + 91 0.0000 2.601750 70.7972 + 92 0.0000 2.635979 71.7286 + 93 0.0000 2.678584 72.8880 + 94 0.0000 2.753520 74.9271 + 95 0.0000 2.764182 75.2172 + 96 0.0000 2.863347 77.9156 + 97 0.0000 2.907828 79.1260 + 98 0.0000 2.944436 80.1222 + 99 0.0000 3.104273 84.4716 + 100 0.0000 3.152438 85.7822 + 101 0.0000 3.183370 86.6239 + 102 0.0000 3.254648 88.5635 + 103 0.0000 3.460591 94.1675 + 104 0.0000 3.796760 103.3151 + 105 0.0000 3.879305 105.5612 + 106 0.0000 4.028990 109.6344 + 107 0.0000 4.170017 113.4719 + 108 0.0000 4.178547 113.7040 + 109 0.0000 4.240498 115.3898 + 110 0.0000 4.363765 118.7441 + 111 0.0000 4.389601 119.4471 + 112 0.0000 4.572349 124.4199 + 113 0.0000 4.624280 125.8331 + 114 0.0000 4.751490 129.2946 + 115 0.0000 4.811605 130.9304 + 116 0.0000 4.845152 131.8433 + 117 0.0000 4.894447 133.1847 + 118 0.0000 4.972590 135.3111 + 119 0.0000 5.003348 136.1480 + 120 0.0000 5.071877 138.0128 + 121 0.0000 5.097308 138.7048 + 122 0.0000 5.171204 140.7156 + 123 0.0000 5.249640 142.8500 + 124 0.0000 5.255223 143.0019 + 125 0.0000 5.330680 145.0552 + 126 0.0000 5.339130 145.2851 + 127 0.0000 5.403798 147.0448 + 128 0.0000 5.568471 151.5258 + 129 0.0000 5.678639 154.5236 + 130 0.0000 5.797064 157.7461 + 131 0.0000 5.997759 163.2073 + 132 0.0000 6.111349 166.2983 + 133 0.0000 6.424559 174.8211 + 134 0.0000 6.506322 177.0460 + 135 0.0000 6.508172 177.0964 + 136 0.0000 6.680476 181.7850 + 137 0.0000 6.712063 182.6445 + 138 0.0000 6.742624 183.4761 + 139 0.0000 6.848918 186.3685 + 140 0.0000 6.915328 188.1757 + 141 0.0000 7.069220 192.3633 + 142 0.0000 7.124275 193.8614 + 143 0.0000 7.181296 195.4130 + 144 0.0000 7.218077 196.4139 + 145 0.0000 7.243241 197.0986 + 146 0.0000 7.261383 197.5923 + 147 0.0000 7.341941 199.7844 + 148 0.0000 7.386924 201.0084 + 149 0.0000 7.436049 202.3452 + 150 0.0000 7.478465 203.4994 + 151 0.0000 7.610842 207.1015 + 152 0.0000 7.642814 207.9715 + 153 0.0000 7.695886 209.4157 + 154 0.0000 7.803600 212.3467 + 155 0.0000 7.959773 216.5964 + 156 0.0000 8.062228 219.3844 + 157 0.0000 8.411529 228.8894 + 158 0.0000 14.172044 385.6409 + 159 0.0000 15.076132 410.2424 + 160 0.0000 16.064383 437.1341 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.346088 0.000000 + 1 N : 0.344470 0.000000 + 2 O : -0.274726 0.000000 + 3 H : 0.276344 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.866817 s : 3.866817 + pz : 1.285139 p : 4.450976 + px : 1.341177 + py : 1.824660 + dz2 : 0.009511 d : 0.023657 + dxz : 0.003787 + dyz : 0.007775 + dx2y2 : 0.002196 + dxy : 0.000388 + f0 : 0.002161 f : 0.004638 + f+1 : 0.000334 + f-1 : 0.001268 + f+2 : 0.000268 + f-2 : 0.000073 + f+3 : 0.000407 + f-3 : 0.000127 + 1 N s : 3.829961 s : 3.829961 + pz : 0.890324 p : 2.652322 + px : 1.006494 + py : 0.755504 + dz2 : 0.033125 d : 0.143440 + dxz : 0.046062 + dyz : 0.017186 + dx2y2 : 0.011405 + dxy : 0.035662 + f0 : 0.008911 f : 0.029807 + f+1 : 0.004104 + f-1 : 0.006149 + f+2 : 0.003907 + f-2 : 0.001142 + f+3 : 0.001936 + f-3 : 0.003658 + 2 O s : 3.877494 s : 3.877494 + pz : 1.870781 p : 4.325840 + px : 1.168418 + py : 1.286640 + dz2 : 0.005241 d : 0.063574 + dxz : 0.015718 + dyz : 0.000534 + dx2y2 : 0.011632 + dxy : 0.030449 + f0 : 0.001139 f : 0.007818 + f+1 : 0.001081 + f-1 : 0.000369 + f+2 : 0.001194 + f-2 : 0.000075 + f+3 : 0.001292 + f-3 : 0.002667 + 3 H s : 0.622643 s : 0.622643 + pz : 0.019715 p : 0.078449 + px : 0.016973 + py : 0.041761 + dz2 : 0.000254 d : 0.022565 + dxz : 0.010456 + dyz : -0.000025 + dx2y2 : 0.001641 + dxy : 0.010239 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.602674 0.000000 + 1 N : -0.266328 0.000000 + 2 O : 0.236133 0.000000 + 3 H : -0.572480 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.114457 s : 3.114457 + pz : 1.220863 p : 3.904864 + px : 1.247568 + py : 1.436433 + dz2 : 0.124900 d : 0.290277 + dxz : 0.067858 + dyz : 0.044998 + dx2y2 : 0.040267 + dxy : 0.012254 + f0 : 0.031856 f : 0.087728 + f+1 : 0.022197 + f-1 : 0.013500 + f+2 : 0.008827 + f-2 : 0.006556 + f+3 : 0.003744 + f-3 : 0.001049 + 1 N s : 3.004121 s : 3.004121 + pz : 0.944127 p : 2.833971 + px : 1.178922 + py : 0.710922 + dz2 : 0.220558 d : 0.969665 + dxz : 0.328727 + dyz : 0.100720 + dx2y2 : 0.171554 + dxy : 0.148106 + f0 : 0.121689 f : 0.458570 + f+1 : 0.072533 + f-1 : 0.060913 + f+2 : 0.081182 + f-2 : 0.017265 + f+3 : 0.051498 + f-3 : 0.053491 + 2 O s : 3.315396 s : 3.315396 + pz : 1.515003 p : 4.004958 + px : 1.385244 + py : 1.104711 + dz2 : 0.045850 d : 0.325407 + dxz : 0.113233 + dyz : 0.004781 + dx2y2 : 0.101759 + dxy : 0.059784 + f0 : 0.016114 f : 0.118106 + f+1 : 0.021998 + f-1 : 0.002279 + f+2 : 0.027913 + f-2 : 0.002700 + f+3 : 0.023710 + f-3 : 0.023392 + 3 H s : 0.621766 s : 0.621766 + pz : 0.135759 p : 0.555556 + px : 0.259828 + py : 0.159970 + dz2 : 0.038265 d : 0.395157 + dxz : 0.132572 + dyz : 0.006641 + dx2y2 : 0.095097 + dxy : 0.122583 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3461 8.0000 -0.3461 1.9365 1.9365 0.0000 + 1 N 6.6555 7.0000 0.3445 2.5361 2.5361 0.0000 + 2 O 8.2747 8.0000 -0.2747 1.7302 1.7302 -0.0000 + 3 H 0.7237 1.0000 0.2763 0.9409 0.9409 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.9160 B( 0-O , 3-H ) : 0.9638 B( 1-N , 2-O ) : 1.6583 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.455 sec +Sum of individual times .... 1.093 sec ( 75.1%) + +Fock matrix formation .... 0.801 sec ( 55.1%) +Diagonalization .... 0.088 sec ( 6.1%) +Density matrix formation .... 0.007 sec ( 0.5%) +Population analysis .... 0.120 sec ( 8.3%) +Initial guess .... 0.009 sec ( 0.6%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.3%) +DIIS solution .... 0.067 sec ( 4.6%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.203 sec +Reference energy ... -204.722185380 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.377 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.079 sec +K-integral sorting ... 5.381 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.026 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.025 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.029 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.045 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.023 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.353 sec +AO-integral generation ... 0.248 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.049 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.154 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.251 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090576391 +EMP2(bb)= -0.090576391 +EMP2(ab)= -0.516555863 + +Initial guess performed in 0.131 sec +E(0) ... -204.722185380 +E(MP2) ... -0.697708645 +Initial E(tot) ... -205.419894025 + ... 0.188086798 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.419894025 -0.697708645 -0.000000000 0.026300344 2.76 0.000000979 + *** Turning on DIIS *** + 1 -205.390649788 -0.668464408 0.029244237 0.011443044 2.75 0.057976773 + 2 -205.410154969 -0.687969590 -0.019505182 0.005770124 2.84 0.060888262 + 3 -205.413859622 -0.691674242 -0.003704652 0.002386968 2.86 0.075300061 + 4 -205.415428876 -0.693243497 -0.001569254 0.001650394 2.86 0.082170204 + 5 -205.415989465 -0.693804085 -0.000560589 0.000884301 2.88 0.087947376 + 6 -205.416102578 -0.693917198 -0.000113113 0.000521872 2.87 0.090801924 + 7 -205.416147692 -0.693962312 -0.000045114 0.000202850 2.93 0.092067798 + 8 -205.416159695 -0.693974315 -0.000012003 0.000104574 2.94 0.092526089 + 9 -205.416155482 -0.693970102 0.000004213 0.000027345 3.14 0.092657954 + 10 -205.416159947 -0.693974567 -0.000004465 0.000009771 2.80 0.092695108 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.722185380 +E(CORR) ... -0.693974567 +E(TOT) ... -205.416159947 +Singles norm **1/2 ... 0.092695108 ( 0.046347554, 0.046347554) +T1 diagnostic ... 0.021848446 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.063213 + 10a-> 13a 10b-> 13b 0.050833 + 8a-> 13a -1a-> -1a 0.043313 + 8b-> 13b -1b-> -1b 0.043313 + 10a-> 13a 8b-> 13b 0.034634 + 8a-> 13a 10b-> 13b 0.034634 + 10a-> 13a -1a-> -1a 0.033890 + 10b-> 13b -1b-> -1b 0.033890 + 11a-> 13a 11b-> 13b 0.027994 + 11b-> 26b -1b-> -1b 0.027362 + 11a-> 26a -1a-> -1a 0.027362 + 11a-> 26a 11b-> 26b 0.027200 + 5a-> 13a 5b-> 13b 0.025753 + 8a-> 22a 8b-> 13b 0.022796 + 8a-> 13a 8b-> 22b 0.022796 + 10a-> 13a 11b-> 26b 0.022290 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034752889 + alpha-alpha-alpha ... -0.000899562 ( 2.6%) + alpha-alpha-beta ... -0.016476883 ( 47.4%) + alpha-beta -beta ... -0.016476883 ( 47.4%) + beta -beta -beta ... -0.000899562 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034752889 + +Final correlation energy ... -0.728727456 +E(CCSD) ... -205.416159947 +E(CCSD(T)) ... -205.450912836 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209799820 sqrt= 1.099909005 +W(HF) = 0.826583029 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.258319 -0.000000 + 1 N : 0.154622 0.000000 + 2 O : -0.159955 -0.000000 + 3 H : 0.263652 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.846581 s : 3.846581 + pz : 1.275948 p : 4.347325 + px : 1.328637 + py : 1.742740 + dz2 : 0.014431 d : 0.055964 + dxz : 0.009973 + dyz : 0.015065 + dx2y2 : 0.008948 + dxy : 0.007547 + f0 : 0.002318 f : 0.008451 + f+1 : 0.000869 + f-1 : 0.001788 + f+2 : 0.000943 + f-2 : 0.000716 + f+3 : 0.001054 + f-3 : 0.000764 + 1 N s : 3.880359 s : 3.880359 + pz : 0.917097 p : 2.762109 + px : 0.987733 + py : 0.857279 + dz2 : 0.038526 d : 0.173690 + dxz : 0.057285 + dyz : 0.025999 + dx2y2 : 0.015535 + dxy : 0.036345 + f0 : 0.008648 f : 0.029219 + f+1 : 0.003801 + f-1 : 0.006064 + f+2 : 0.004203 + f-2 : 0.001764 + f+3 : 0.001857 + f-3 : 0.002883 + 2 O s : 3.866551 s : 3.866551 + pz : 1.787106 p : 4.197791 + px : 1.159091 + py : 1.251593 + dz2 : 0.010227 d : 0.085229 + dxz : 0.024055 + dyz : 0.006888 + dx2y2 : 0.013717 + dxy : 0.030342 + f0 : 0.001642 f : 0.010385 + f+1 : 0.001548 + f-1 : 0.000849 + f+2 : 0.001693 + f-2 : 0.000716 + f+3 : 0.001458 + f-3 : 0.002479 + 3 H s : 0.634496 s : 0.634496 + pz : 0.023552 p : 0.082491 + px : 0.010974 + py : 0.047965 + dz2 : 0.000603 d : 0.019361 + dxz : 0.009340 + dyz : 0.000090 + dx2y2 : 0.000638 + dxy : 0.008690 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.619329 -0.000000 + 1 N : -0.316507 0.000000 + 2 O : 0.269617 0.000000 + 3 H : -0.572438 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.121711 s : 3.121711 + pz : 1.223800 p : 3.842799 + px : 1.241192 + py : 1.377808 + dz2 : 0.130932 d : 0.321478 + dxz : 0.073118 + dyz : 0.051656 + dx2y2 : 0.047955 + dxy : 0.017817 + f0 : 0.032666 f : 0.094683 + f+1 : 0.023557 + f-1 : 0.015401 + f+2 : 0.009500 + f-2 : 0.007191 + f+3 : 0.004691 + f-3 : 0.001678 + 1 N s : 3.009307 s : 3.009307 + pz : 0.949873 p : 2.882068 + px : 1.158918 + py : 0.773277 + dz2 : 0.227787 d : 0.978571 + dxz : 0.325787 + dyz : 0.102412 + dx2y2 : 0.177240 + dxy : 0.145345 + f0 : 0.119475 f : 0.446561 + f+1 : 0.072596 + f-1 : 0.057966 + f+2 : 0.075110 + f-2 : 0.016950 + f+3 : 0.051855 + f-3 : 0.052608 + 2 O s : 3.317221 s : 3.317221 + pz : 1.461373 p : 3.929582 + px : 1.377848 + py : 1.090362 + dz2 : 0.051677 d : 0.356807 + dxz : 0.115287 + dyz : 0.011147 + dx2y2 : 0.106945 + dxy : 0.071751 + f0 : 0.016437 f : 0.126772 + f+1 : 0.022714 + f-1 : 0.003021 + f+2 : 0.027675 + f-2 : 0.003739 + f+3 : 0.025237 + f-3 : 0.027949 + 3 H s : 0.623860 s : 0.623860 + pz : 0.137337 p : 0.563885 + px : 0.262306 + py : 0.164242 + dz2 : 0.039576 d : 0.384693 + dxz : 0.128112 + dyz : 0.006597 + dx2y2 : 0.094413 + dxy : 0.115996 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2583 8.0000 -0.2583 2.3028 1.8417 0.4611 + 1 N 6.8454 7.0000 0.1546 2.8259 2.3499 0.4760 + 2 O 8.1600 8.0000 -0.1600 2.1320 1.6356 0.4964 + 3 H 0.7363 1.0000 0.2637 0.9624 0.8921 0.0703 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8509 B( 0-O , 3-H ) : 0.8913 B( 1-N , 2-O ) : 1.5171 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 46.701 sec + +Fock Matrix Formation ... 0.203 sec ( 0.4%) +Initial Guess ... 0.131 sec ( 0.3%) +DIIS Solver ... 1.356 sec ( 2.9%) +State Vector Update ... 0.064 sec ( 0.1%) +Sigma-vector construction ... 30.207 sec ( 64.7%) + <0|H|D> ... 0.003 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.018 sec ( 0.1% of sigma) + (0-ext) ... 0.054 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (2-ext) ... 0.729 sec ( 2.4% of sigma) + (4-ext) ... 16.991 sec ( 56.2% of sigma) + ... 1.059 sec ( 3.5% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.087 sec ( 0.3% of sigma) + Fock-dressing ... 1.624 sec ( 5.4% of sigma) + (ik|jl)-dressing ... 0.059 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 7.458 sec ( 24.7% of sigma) + Pair energies ... 0.004 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.662 sec ( 14.3% of ALL) + I/O of integral and amplitudes ... 0.756 sec ( 11.3% of (T)) + External N**7 contributions ... 3.882 sec ( 58.3% of (T)) + Internal N**7 contributions ... 0.306 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.583 sec ( 23.8% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.450912836072 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.043.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.043.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.721507, -0.078254 -0.327678) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.63413 -0.12569 -0.78537 +Nuclear contribution : -1.49844 0.18241 0.75397 + ----------------------------------------- +Total Dipole Moment : -0.86431 0.05673 -0.03140 + ----------------------------------------- +Magnitude (a.u.) : 0.86674 +Magnitude (Debye) : 2.20307 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.058374 0.417240 0.368147 +Rotational constants in MHz : 91687.757172 12508.541102 11036.773148 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.612201 -0.591830 -0.161810 +x,y,z [Debye]: 1.556092 -1.504312 -0.411287 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.721507, -0.078254 -0.327678) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.80433 -0.10847 -0.73759 +Nuclear contribution : -1.49844 0.18241 0.75397 + ----------------------------------------- +Total Dipole Moment : -0.69411 0.07395 0.01638 + ----------------------------------------- +Magnitude (a.u.) : 0.69823 +Magnitude (Debye) : 1.77475 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.058374 0.417240 0.368147 +Rotational constants in MHz : 91687.757172 12508.541102 11036.773148 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.521114 -0.439791 -0.150144 +x,y,z [Debye]: 1.324567 -1.117860 -0.381636 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 44 * + * * + * Dihedral ( 2, 1, 0, 3) : 171.81818182 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0396338257 RMS(Int)= 0.0002464042 + Iter 1: RMS(Cart)= 0.0000683891 RMS(Int)= 0.0000012780 + Iter 2: RMS(Cart)= 0.0000003547 RMS(Int)= 0.0000000066 + Iter 3: RMS(Cart)= 0.0000000018 RMS(Int)= 0.0000000000 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4373 0.000000 + 2. B(O 2,N 1) 1.1754 0.000000 + 3. B(H 3,O 0) 0.9717 0.000000 + 4. A(N 1,O 0,H 3) 102.0039 0.000000 + 5. A(O 0,N 1,O 2) 110.5312 0.000000 + 6. D(O 2,N 1,O 0,H 3) 171.8182 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.259362 0.069692 0.724789 + N 0.157927 -0.131338 -0.635805 + O 1.327317 -0.052718 -0.724225 + H -1.225881 0.114364 0.635240 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.490124 0.131700 1.369654 + 1 N 7.0000 0 14.007 0.298439 -0.248194 -1.201497 + 2 O 8.0000 0 15.999 2.508266 -0.099623 -1.368587 + 3 H 1.0000 0 1.008 -2.316579 0.216117 1.200430 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.437259993442 0.00000000 0.00000000 + O 2 1 0 1.173200148004 110.58048028 0.00000000 + H 1 2 3 0.968887755055 102.03236279 163.63636355 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.716027770846 0.00000000 0.00000000 + O 2 1 0 2.217026980003 110.58048028 0.00000000 + H 1 2 3 1.830932511563 102.03236279 163.63636355 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.339211317017 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.3392113170 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.984e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7180141249 0.000000000000 0.00183928 0.00005346 0.0198391 0.7000 + 1 -204.7189157931 -0.000901668198 0.00174456 0.00004810 0.0163996 0.7000 + ***Turning on DIIS*** + 2 -204.7196837740 -0.000767980833 0.00474748 0.00012973 0.0133044 0.0000 + 3 -204.7230891385 -0.003405364586 0.00189323 0.00005184 0.0052362 0.0000 + 4 -204.7215578832 0.001531255343 0.00087748 0.00002292 0.0020174 0.0000 + 5 -204.7230135736 -0.001455690404 0.00074413 0.00002459 0.0009859 0.0000 + 6 -204.7223857429 0.000627830740 0.00049048 0.00001591 0.0005002 0.0000 + 7 -204.7219469656 0.000438777317 0.00029545 0.00000995 0.0002692 0.0000 + 8 -204.7227934501 -0.000846484543 0.00019152 0.00000694 0.0001926 0.0000 + 9 -204.7223449556 0.000448494503 0.00011008 0.00000338 0.0001025 0.0000 + 10 -204.7223778597 -0.000032904086 0.00005568 0.00000165 0.0000505 0.0000 + 11 -204.7225159663 -0.000138106636 0.00002793 0.00000079 0.0000197 0.0000 + 12 -204.7224454664 0.000070499947 0.00000528 0.00000015 0.0000051 0.0000 + 13 -204.7224626194 -0.000017153020 0.00000152 0.00000004 0.0000021 0.0000 + 14 -204.7224574481 0.000005171292 0.00000070 0.00000002 0.0000010 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 15 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72245734 Eh -5570.78128 eV + +Components: +Nuclear Repulsion : 69.33921132 Eh 1886.81586 eV +Electronic Energy : -274.06166865 Eh -7457.59714 eV +One Electron Energy: -418.39059474 Eh -11384.98688 eV +Two Electron Energy: 144.32892608 Eh 3927.38974 eV + +Virial components: +Potential Energy : -408.95088502 Eh -11128.11932 eV +Kinetic Energy : 204.22842769 Eh 5557.33805 eV +Virial Ratio : 2.00241901 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.1205e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.2369e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.3238e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.4281e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.667656 -562.3955 + 1 1.0000 -20.640066 -561.6447 + 2 1.0000 -15.799851 -429.9358 + 3 1.0000 -1.603543 -43.6346 + 4 1.0000 -1.398773 -38.0625 + 5 1.0000 -0.948615 -25.8131 + 6 1.0000 -0.782534 -21.2938 + 7 1.0000 -0.729242 -19.8437 + 8 1.0000 -0.681421 -18.5424 + 9 1.0000 -0.624802 -17.0017 + 10 1.0000 -0.528439 -14.3796 + 11 1.0000 -0.461429 -12.5561 + 12 0.0000 0.028233 0.7683 + 13 0.0000 0.079570 2.1652 + 14 0.0000 0.093707 2.5499 + 15 0.0000 0.097674 2.6579 + 16 0.0000 0.128490 3.4964 + 17 0.0000 0.144327 3.9273 + 18 0.0000 0.156816 4.2672 + 19 0.0000 0.172267 4.6876 + 20 0.0000 0.187340 5.0978 + 21 0.0000 0.196473 5.3463 + 22 0.0000 0.205233 5.5847 + 23 0.0000 0.233216 6.3461 + 24 0.0000 0.258473 7.0334 + 25 0.0000 0.295650 8.0450 + 26 0.0000 0.305257 8.3065 + 27 0.0000 0.329548 8.9675 + 28 0.0000 0.364252 9.9118 + 29 0.0000 0.380867 10.3639 + 30 0.0000 0.423885 11.5345 + 31 0.0000 0.520560 14.1652 + 32 0.0000 0.528885 14.3917 + 33 0.0000 0.547168 14.8892 + 34 0.0000 0.571990 15.5646 + 35 0.0000 0.613395 16.6913 + 36 0.0000 0.631620 17.1873 + 37 0.0000 0.648000 17.6330 + 38 0.0000 0.681731 18.5508 + 39 0.0000 0.715573 19.4717 + 40 0.0000 0.717676 19.5289 + 41 0.0000 0.747969 20.3533 + 42 0.0000 0.773623 21.0514 + 43 0.0000 0.784057 21.3353 + 44 0.0000 0.808639 22.0042 + 45 0.0000 0.814157 22.1543 + 46 0.0000 0.859800 23.3964 + 47 0.0000 0.876377 23.8474 + 48 0.0000 0.926160 25.2021 + 49 0.0000 0.938771 25.5453 + 50 0.0000 0.947332 25.7782 + 51 0.0000 0.996824 27.1250 + 52 0.0000 1.047484 28.5035 + 53 0.0000 1.061021 28.8719 + 54 0.0000 1.076852 29.3026 + 55 0.0000 1.103232 30.0205 + 56 0.0000 1.160297 31.5733 + 57 0.0000 1.193614 32.4799 + 58 0.0000 1.251976 34.0680 + 59 0.0000 1.272994 34.6399 + 60 0.0000 1.364293 37.1243 + 61 0.0000 1.431075 38.9415 + 62 0.0000 1.491304 40.5804 + 63 0.0000 1.521142 41.3924 + 64 0.0000 1.524681 41.4887 + 65 0.0000 1.545510 42.0555 + 66 0.0000 1.553084 42.2616 + 67 0.0000 1.606210 43.7072 + 68 0.0000 1.659940 45.1693 + 69 0.0000 1.728482 47.0344 + 70 0.0000 1.754783 47.7501 + 71 0.0000 1.818928 49.4956 + 72 0.0000 1.855874 50.5009 + 73 0.0000 1.959959 53.3332 + 74 0.0000 1.968473 53.5649 + 75 0.0000 2.000285 54.4305 + 76 0.0000 2.073577 56.4249 + 77 0.0000 2.116340 57.5885 + 78 0.0000 2.148029 58.4508 + 79 0.0000 2.180477 59.3338 + 80 0.0000 2.274749 61.8991 + 81 0.0000 2.306798 62.7712 + 82 0.0000 2.325701 63.2855 + 83 0.0000 2.380552 64.7781 + 84 0.0000 2.448198 66.6189 + 85 0.0000 2.468534 67.1722 + 86 0.0000 2.498307 67.9824 + 87 0.0000 2.502029 68.0837 + 88 0.0000 2.519437 68.5574 + 89 0.0000 2.542823 69.1937 + 90 0.0000 2.568583 69.8947 + 91 0.0000 2.602565 70.8194 + 92 0.0000 2.620190 71.2990 + 93 0.0000 2.663851 72.4871 + 94 0.0000 2.765193 75.2447 + 95 0.0000 2.772992 75.4570 + 96 0.0000 2.843885 77.3860 + 97 0.0000 2.927152 79.6518 + 98 0.0000 2.941539 80.0434 + 99 0.0000 3.109129 84.6037 + 100 0.0000 3.147889 85.6584 + 101 0.0000 3.184131 86.6446 + 102 0.0000 3.246324 88.3370 + 103 0.0000 3.455593 94.0315 + 104 0.0000 3.815652 103.8292 + 105 0.0000 3.860880 105.0599 + 106 0.0000 4.028637 109.6248 + 107 0.0000 4.171337 113.5078 + 108 0.0000 4.176161 113.6391 + 109 0.0000 4.219625 114.8218 + 110 0.0000 4.362869 118.7197 + 111 0.0000 4.376704 119.0962 + 112 0.0000 4.575749 124.5124 + 113 0.0000 4.626438 125.8918 + 114 0.0000 4.747218 129.1784 + 115 0.0000 4.810338 130.8959 + 116 0.0000 4.861762 132.2953 + 117 0.0000 4.891191 133.0961 + 118 0.0000 4.978269 135.4656 + 119 0.0000 5.001480 136.0972 + 120 0.0000 5.071173 137.9936 + 121 0.0000 5.088902 138.4761 + 122 0.0000 5.166017 140.5745 + 123 0.0000 5.246472 142.7637 + 124 0.0000 5.255400 143.0067 + 125 0.0000 5.329421 145.0209 + 126 0.0000 5.346455 145.4844 + 127 0.0000 5.383648 146.4965 + 128 0.0000 5.572086 151.6242 + 129 0.0000 5.670679 154.3070 + 130 0.0000 5.794564 157.6781 + 131 0.0000 5.992794 163.0722 + 132 0.0000 6.108311 166.2156 + 133 0.0000 6.427849 174.9107 + 134 0.0000 6.506072 177.0392 + 135 0.0000 6.508138 177.0954 + 136 0.0000 6.675096 181.6386 + 137 0.0000 6.713759 182.6907 + 138 0.0000 6.743689 183.5051 + 139 0.0000 6.845270 186.2693 + 140 0.0000 6.912547 188.1000 + 141 0.0000 7.065556 192.2636 + 142 0.0000 7.119748 193.7382 + 143 0.0000 7.177182 195.3011 + 144 0.0000 7.225494 196.6157 + 145 0.0000 7.250322 197.2913 + 146 0.0000 7.257721 197.4926 + 147 0.0000 7.333790 199.5626 + 148 0.0000 7.381025 200.8479 + 149 0.0000 7.430969 202.2069 + 150 0.0000 7.476942 203.4579 + 151 0.0000 7.604525 206.9296 + 152 0.0000 7.643447 207.9888 + 153 0.0000 7.695416 209.4029 + 154 0.0000 7.783482 211.7993 + 155 0.0000 7.962273 216.6645 + 156 0.0000 8.062262 219.3853 + 157 0.0000 8.416312 229.0195 + 158 0.0000 14.165926 385.4744 + 159 0.0000 15.059342 409.7855 + 160 0.0000 15.993666 435.2098 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.667656 -562.3955 + 1 1.0000 -20.640066 -561.6447 + 2 1.0000 -15.799851 -429.9358 + 3 1.0000 -1.603543 -43.6346 + 4 1.0000 -1.398773 -38.0625 + 5 1.0000 -0.948615 -25.8131 + 6 1.0000 -0.782534 -21.2938 + 7 1.0000 -0.729242 -19.8437 + 8 1.0000 -0.681421 -18.5424 + 9 1.0000 -0.624802 -17.0017 + 10 1.0000 -0.528439 -14.3796 + 11 1.0000 -0.461429 -12.5561 + 12 0.0000 0.028233 0.7683 + 13 0.0000 0.079570 2.1652 + 14 0.0000 0.093707 2.5499 + 15 0.0000 0.097674 2.6579 + 16 0.0000 0.128490 3.4964 + 17 0.0000 0.144327 3.9273 + 18 0.0000 0.156816 4.2672 + 19 0.0000 0.172267 4.6876 + 20 0.0000 0.187340 5.0978 + 21 0.0000 0.196473 5.3463 + 22 0.0000 0.205233 5.5847 + 23 0.0000 0.233216 6.3461 + 24 0.0000 0.258473 7.0334 + 25 0.0000 0.295650 8.0450 + 26 0.0000 0.305257 8.3065 + 27 0.0000 0.329548 8.9675 + 28 0.0000 0.364252 9.9118 + 29 0.0000 0.380867 10.3639 + 30 0.0000 0.423885 11.5345 + 31 0.0000 0.520560 14.1652 + 32 0.0000 0.528885 14.3917 + 33 0.0000 0.547168 14.8892 + 34 0.0000 0.571990 15.5646 + 35 0.0000 0.613395 16.6913 + 36 0.0000 0.631620 17.1873 + 37 0.0000 0.648000 17.6330 + 38 0.0000 0.681731 18.5508 + 39 0.0000 0.715573 19.4717 + 40 0.0000 0.717676 19.5289 + 41 0.0000 0.747969 20.3533 + 42 0.0000 0.773623 21.0514 + 43 0.0000 0.784057 21.3353 + 44 0.0000 0.808639 22.0042 + 45 0.0000 0.814157 22.1543 + 46 0.0000 0.859800 23.3964 + 47 0.0000 0.876377 23.8474 + 48 0.0000 0.926160 25.2021 + 49 0.0000 0.938771 25.5453 + 50 0.0000 0.947332 25.7782 + 51 0.0000 0.996824 27.1250 + 52 0.0000 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67.9824 + 87 0.0000 2.502029 68.0837 + 88 0.0000 2.519437 68.5574 + 89 0.0000 2.542823 69.1937 + 90 0.0000 2.568583 69.8947 + 91 0.0000 2.602565 70.8194 + 92 0.0000 2.620190 71.2990 + 93 0.0000 2.663851 72.4871 + 94 0.0000 2.765193 75.2447 + 95 0.0000 2.772992 75.4570 + 96 0.0000 2.843885 77.3860 + 97 0.0000 2.927152 79.6518 + 98 0.0000 2.941539 80.0434 + 99 0.0000 3.109129 84.6037 + 100 0.0000 3.147889 85.6584 + 101 0.0000 3.184131 86.6446 + 102 0.0000 3.246324 88.3370 + 103 0.0000 3.455593 94.0315 + 104 0.0000 3.815652 103.8292 + 105 0.0000 3.860880 105.0599 + 106 0.0000 4.028637 109.6248 + 107 0.0000 4.171337 113.5078 + 108 0.0000 4.176161 113.6391 + 109 0.0000 4.219625 114.8218 + 110 0.0000 4.362869 118.7197 + 111 0.0000 4.376704 119.0962 + 112 0.0000 4.575749 124.5124 + 113 0.0000 4.626438 125.8918 + 114 0.0000 4.747218 129.1784 + 115 0.0000 4.810338 130.8959 + 116 0.0000 4.861762 132.2953 + 117 0.0000 4.891191 133.0961 + 118 0.0000 4.978269 135.4656 + 119 0.0000 5.001480 136.0972 + 120 0.0000 5.071173 137.9936 + 121 0.0000 5.088902 138.4761 + 122 0.0000 5.166017 140.5745 + 123 0.0000 5.246472 142.7637 + 124 0.0000 5.255400 143.0067 + 125 0.0000 5.329421 145.0209 + 126 0.0000 5.346455 145.4844 + 127 0.0000 5.383648 146.4965 + 128 0.0000 5.572086 151.6242 + 129 0.0000 5.670679 154.3070 + 130 0.0000 5.794564 157.6781 + 131 0.0000 5.992794 163.0722 + 132 0.0000 6.108311 166.2156 + 133 0.0000 6.427849 174.9107 + 134 0.0000 6.506072 177.0392 + 135 0.0000 6.508138 177.0954 + 136 0.0000 6.675096 181.6386 + 137 0.0000 6.713759 182.6907 + 138 0.0000 6.743689 183.5051 + 139 0.0000 6.845270 186.2693 + 140 0.0000 6.912547 188.1000 + 141 0.0000 7.065556 192.2636 + 142 0.0000 7.119748 193.7382 + 143 0.0000 7.177182 195.3011 + 144 0.0000 7.225494 196.6157 + 145 0.0000 7.250322 197.2913 + 146 0.0000 7.257721 197.4926 + 147 0.0000 7.333790 199.5626 + 148 0.0000 7.381025 200.8479 + 149 0.0000 7.430969 202.2069 + 150 0.0000 7.476942 203.4579 + 151 0.0000 7.604525 206.9296 + 152 0.0000 7.643447 207.9888 + 153 0.0000 7.695416 209.4029 + 154 0.0000 7.783482 211.7993 + 155 0.0000 7.962273 216.6645 + 156 0.0000 8.062262 219.3853 + 157 0.0000 8.416312 229.0195 + 158 0.0000 14.165926 385.4744 + 159 0.0000 15.059342 409.7855 + 160 0.0000 15.993666 435.2098 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.348633 0.000000 + 1 N : 0.345124 0.000000 + 2 O : -0.276570 0.000000 + 3 H : 0.280080 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.867586 s : 3.867586 + pz : 1.287288 p : 4.452453 + px : 1.336863 + py : 1.828303 + dz2 : 0.009706 d : 0.023941 + dxz : 0.003466 + dyz : 0.007888 + dx2y2 : 0.002330 + dxy : 0.000550 + f0 : 0.002184 f : 0.004653 + f+1 : 0.000341 + f-1 : 0.001276 + f+2 : 0.000292 + f-2 : 0.000046 + f+3 : 0.000453 + f-3 : 0.000061 + 1 N s : 3.829603 s : 3.829603 + pz : 0.894247 p : 2.651195 + px : 1.011743 + py : 0.745204 + dz2 : 0.033478 d : 0.144403 + dxz : 0.046295 + dyz : 0.016828 + dx2y2 : 0.010691 + dxy : 0.037111 + f0 : 0.008879 f : 0.029675 + f+1 : 0.004105 + f-1 : 0.006139 + f+2 : 0.003996 + f-2 : 0.000918 + f+3 : 0.001648 + f-3 : 0.003990 + 2 O s : 3.877594 s : 3.877594 + pz : 1.878651 p : 4.327800 + px : 1.165512 + py : 1.283636 + dz2 : 0.005324 d : 0.063339 + dxz : 0.015779 + dyz : 0.000331 + dx2y2 : 0.010484 + dxy : 0.031421 + f0 : 0.001142 f : 0.007837 + f+1 : 0.001090 + f-1 : 0.000372 + f+2 : 0.001269 + f-2 : 0.000009 + f+3 : 0.001140 + f-3 : 0.002815 + 3 H s : 0.620400 s : 0.620400 + pz : 0.019479 p : 0.077147 + px : 0.016300 + py : 0.041368 + dz2 : 0.000213 d : 0.022374 + dxz : 0.010674 + dyz : -0.000256 + dx2y2 : 0.001019 + dxy : 0.010724 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.600146 0.000000 + 1 N : -0.265954 0.000000 + 2 O : 0.233824 0.000000 + 3 H : -0.568016 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.116096 s : 3.116096 + pz : 1.221515 p : 3.905107 + px : 1.245197 + py : 1.438395 + dz2 : 0.126589 d : 0.290897 + dxz : 0.067770 + dyz : 0.043865 + dx2y2 : 0.041709 + dxy : 0.010963 + f0 : 0.032373 f : 0.087755 + f+1 : 0.022415 + f-1 : 0.012999 + f+2 : 0.008527 + f-2 : 0.006581 + f+3 : 0.004180 + f-3 : 0.000680 + 1 N s : 3.004920 s : 3.004920 + pz : 0.948634 p : 2.833362 + px : 1.186295 + py : 0.698434 + dz2 : 0.219792 d : 0.969214 + dxz : 0.331004 + dyz : 0.098894 + dx2y2 : 0.174968 + dxy : 0.144556 + f0 : 0.122519 f : 0.458458 + f+1 : 0.072997 + f-1 : 0.060823 + f+2 : 0.084146 + f-2 : 0.013921 + f+3 : 0.050851 + f-3 : 0.053201 + 2 O s : 3.316603 s : 3.316603 + pz : 1.521143 p : 4.007341 + px : 1.387149 + py : 1.099049 + dz2 : 0.045099 d : 0.324559 + dxz : 0.114699 + dyz : 0.003998 + dx2y2 : 0.105248 + dxy : 0.055514 + f0 : 0.016397 f : 0.117673 + f+1 : 0.021683 + f-1 : 0.001969 + f+2 : 0.028924 + f-2 : 0.001884 + f+3 : 0.024292 + f-3 : 0.022524 + 3 H s : 0.620871 s : 0.620871 + pz : 0.134166 p : 0.552547 + px : 0.260900 + py : 0.157481 + dz2 : 0.039016 d : 0.394597 + dxz : 0.133615 + dyz : 0.004031 + dx2y2 : 0.093886 + dxy : 0.124050 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3486 8.0000 -0.3486 1.9431 1.9431 -0.0000 + 1 N 6.6549 7.0000 0.3451 2.5374 2.5374 -0.0000 + 2 O 8.2766 8.0000 -0.2766 1.7284 1.7284 0.0000 + 3 H 0.7199 1.0000 0.2801 0.9370 0.9370 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.9241 B( 0-O , 3-H ) : 0.9618 B( 1-N , 2-O ) : 1.6546 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.603 sec +Sum of individual times .... 2.217 sec ( 85.2%) + +Fock matrix formation .... 1.749 sec ( 67.2%) +Diagonalization .... 0.176 sec ( 6.8%) +Density matrix formation .... 0.013 sec ( 0.5%) +Population analysis .... 0.121 sec ( 4.7%) +Initial guess .... 0.009 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.2%) +DIIS solution .... 0.149 sec ( 5.7%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.205 sec +Reference energy ... -204.722458101 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.398 sec +AO-integral generation ... 0.142 sec +Half transformation ... 0.079 sec +K-integral sorting ... 5.405 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.025 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.028 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.034 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.045 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.361 sec +AO-integral generation ... 0.256 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.151 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.251 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090703627 +EMP2(bb)= -0.090703627 +EMP2(ab)= -0.517096355 + +Initial guess performed in 0.132 sec +E(0) ... -204.722458101 +E(MP2) ... -0.698503609 +Initial E(tot) ... -205.420961711 + ... 0.188718881 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.420961711 -0.698503609 -0.000000000 0.027198097 2.77 0.000001830 + *** Turning on DIIS *** + 1 -205.391306930 -0.668848829 0.029654780 0.011964464 2.73 0.058387523 + 2 -205.410934341 -0.688476239 -0.019627411 0.006011166 2.86 0.061242346 + 3 -205.414651884 -0.692193783 -0.003717543 0.002483741 2.83 0.075774789 + 4 -205.416235644 -0.693777543 -0.001583760 0.001643633 2.85 0.082711178 + 5 -205.416803859 -0.694345758 -0.000568215 0.000872878 2.87 0.088549534 + 6 -205.416917710 -0.694459608 -0.000113851 0.000515129 2.84 0.091410684 + 7 -205.416962940 -0.694504839 -0.000045230 0.000197745 2.86 0.092669637 + 8 -205.416975005 -0.694516904 -0.000012065 0.000102322 2.90 0.093122005 + 9 -205.416970816 -0.694512715 0.000004189 0.000026457 2.84 0.093251888 + 10 -205.416975257 -0.694517156 -0.000004441 0.000009231 2.78 0.093287613 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.722458101 +E(CORR) ... -0.694517156 +E(TOT) ... -205.416975257 +Singles norm **1/2 ... 0.093287613 ( 0.046643806, 0.046643806) +T1 diagnostic ... 0.021988101 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.066446 + 10a-> 13a 10b-> 13b 0.053434 + 8b-> 13b -1b-> -1b 0.045252 + 8a-> 13a -1a-> -1a 0.045252 + 8a-> 13a 10b-> 13b 0.036689 + 10a-> 13a 8b-> 13b 0.036689 + 10a-> 13a -1a-> -1a 0.033795 + 10b-> 13b -1b-> -1b 0.033795 + 11a-> 26a 11b-> 26b 0.030071 + 11a-> 26a -1a-> -1a 0.029131 + 11b-> 26b -1b-> -1b 0.029131 + 11a-> 13a 11b-> 13b 0.027968 + 5a-> 13a 5b-> 13b 0.025790 + 11a-> 26a 10b-> 13b 0.024203 + 10a-> 13a 11b-> 26b 0.024203 + 8a-> 22a 8b-> 13b 0.024130 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034914645 + alpha-alpha-alpha ... -0.000903405 ( 2.6%) + alpha-alpha-beta ... -0.016553918 ( 47.4%) + alpha-beta -beta ... -0.016553918 ( 47.4%) + beta -beta -beta ... -0.000903405 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034914645 + +Final correlation energy ... -0.729431801 +E(CCSD) ... -205.416975257 +E(CCSD(T)) ... -205.451889902 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210461765 sqrt= 1.100209873 +W(HF) = 0.826131010 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.259095 0.000000 + 1 N : 0.154508 -0.000000 + 2 O : -0.162216 0.000000 + 3 H : 0.266804 -0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.847519 s : 3.847519 + pz : 1.278286 p : 4.346828 + px : 1.324294 + py : 1.744247 + dz2 : 0.014623 d : 0.056278 + dxz : 0.009729 + dyz : 0.015154 + dx2y2 : 0.009062 + dxy : 0.007710 + f0 : 0.002333 f : 0.008471 + f+1 : 0.000877 + f-1 : 0.001799 + f+2 : 0.000971 + f-2 : 0.000689 + f+3 : 0.001101 + f-3 : 0.000702 + 1 N s : 3.879348 s : 3.879348 + pz : 0.919266 p : 2.762429 + px : 0.990884 + py : 0.852279 + dz2 : 0.038787 d : 0.174598 + dxz : 0.057725 + dyz : 0.025701 + dx2y2 : 0.015032 + dxy : 0.037353 + f0 : 0.008635 f : 0.029117 + f+1 : 0.003800 + f-1 : 0.006048 + f+2 : 0.004292 + f-2 : 0.001581 + f+3 : 0.001705 + f-3 : 0.003055 + 2 O s : 3.867266 s : 3.867266 + pz : 1.794788 p : 4.199470 + px : 1.156962 + py : 1.247719 + dz2 : 0.010263 d : 0.085068 + dxz : 0.024277 + dyz : 0.006666 + dx2y2 : 0.012768 + dxy : 0.031094 + f0 : 0.001647 f : 0.010413 + f+1 : 0.001555 + f-1 : 0.000853 + f+2 : 0.001763 + f-2 : 0.000664 + f+3 : 0.001355 + f-3 : 0.002576 + 3 H s : 0.632830 s : 0.632830 + pz : 0.023390 p : 0.081188 + px : 0.010130 + py : 0.047669 + dz2 : 0.000567 d : 0.019179 + dxz : 0.009535 + dyz : -0.000106 + dx2y2 : 0.000062 + dxy : 0.009121 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.617382 0.000000 + 1 N : -0.316844 0.000000 + 2 O : 0.267318 -0.000000 + 3 H : -0.567856 0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.123489 s : 3.123489 + pz : 1.224789 p : 3.842213 + px : 1.239035 + py : 1.378390 + dz2 : 0.132559 d : 0.322186 + dxz : 0.072947 + dyz : 0.050733 + dx2y2 : 0.049503 + dxy : 0.016445 + f0 : 0.033079 f : 0.094729 + f+1 : 0.023758 + f-1 : 0.015052 + f+2 : 0.009218 + f-2 : 0.007184 + f+3 : 0.005171 + f-3 : 0.001268 + 1 N s : 3.010102 s : 3.010102 + pz : 0.953143 p : 2.882424 + px : 1.164721 + py : 0.764560 + dz2 : 0.227078 d : 0.978014 + dxz : 0.327722 + dyz : 0.100613 + dx2y2 : 0.181295 + dxy : 0.141306 + f0 : 0.120298 f : 0.446304 + f+1 : 0.073204 + f-1 : 0.057785 + f+2 : 0.077812 + f-2 : 0.013786 + f+3 : 0.051301 + f-3 : 0.052119 + 2 O s : 3.318401 s : 3.318401 + pz : 1.467395 p : 3.931723 + px : 1.379980 + py : 1.084348 + dz2 : 0.050960 d : 0.356171 + dxz : 0.116727 + dyz : 0.010293 + dx2y2 : 0.110036 + dxy : 0.068154 + f0 : 0.016667 f : 0.126387 + f+1 : 0.022449 + f-1 : 0.002741 + f+2 : 0.028664 + f-2 : 0.002848 + f+3 : 0.025335 + f-3 : 0.027684 + 3 H s : 0.623120 s : 0.623120 + pz : 0.135725 p : 0.560657 + px : 0.263238 + py : 0.161694 + dz2 : 0.040260 d : 0.384080 + dxz : 0.129026 + dyz : 0.004211 + dx2y2 : 0.093449 + dxy : 0.117134 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2591 8.0000 -0.2591 2.3115 1.8487 0.4628 + 1 N 6.8455 7.0000 0.1545 2.8290 2.3523 0.4767 + 2 O 8.1622 8.0000 -0.1622 2.1321 1.6348 0.4972 + 3 H 0.7332 1.0000 0.2668 0.9591 0.8888 0.0704 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8590 B( 0-O , 2-O ) : 0.1007 B( 0-O , 3-H ) : 0.8890 +B( 1-N , 2-O ) : 1.5138 + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 46.398 sec + +Fock Matrix Formation ... 0.205 sec ( 0.4%) +Initial Guess ... 0.132 sec ( 0.3%) +DIIS Solver ... 1.264 sec ( 2.7%) +State Vector Update ... 0.065 sec ( 0.1%) +Sigma-vector construction ... 29.791 sec ( 64.2%) + <0|H|D> ... 0.003 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.018 sec ( 0.1% of sigma) + (0-ext) ... 0.055 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (2-ext) ... 0.733 sec ( 2.5% of sigma) + (4-ext) ... 16.668 sec ( 55.9% of sigma) + ... 1.061 sec ( 3.6% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.007 sec ( 0.0% of sigma) + (1-ext) ... 0.086 sec ( 0.3% of sigma) + Fock-dressing ... 1.627 sec ( 5.5% of sigma) + (ik|jl)-dressing ... 0.059 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 7.380 sec ( 24.8% of sigma) + Pair energies ... 0.004 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.802 sec ( 14.7% of ALL) + I/O of integral and amplitudes ... 0.781 sec ( 11.5% of (T)) + External N**7 contributions ... 3.916 sec ( 57.6% of (T)) + Internal N**7 contributions ... 0.319 sec ( 4.7% of (T)) + N**6 triples energy contributions ... 1.684 sec ( 24.8% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.451889902407 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.001690743 -0.002232763 0.001866293 + 2 N : -0.002396542 -0.002917411 -0.000704102 + 3 O : 0.003173148 0.002420129 -0.000762851 + 4 H : -0.002467349 0.002730044 -0.000399340 + +Norm of the cartesian gradient ... 0.007502373 +RMS gradient ... 0.002165749 +MAX gradient ... 0.003173148 + +------- +TIMINGS +------- + +Total numerical gradient time ... 318.273 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 578.41 cm**-1 + 7: 615.14 cm**-1 + 8: 811.37 cm**-1 + 9: 1306.03 cm**-1 + 10: 1704.20 cm**-1 + 11: 3738.71 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 -0.050700 -0.275339 -0.062152 0.063103 0.026850 -0.062157 + 1 -0.048210 0.069735 -0.055018 0.008243 0.016140 0.002860 + 2 0.071548 0.308730 -0.195376 0.059875 0.106412 -0.005020 + 3 0.039063 0.186369 0.000863 0.009144 -0.621161 -0.001887 + 4 -0.070095 0.061441 0.082547 0.000753 -0.057866 -0.000382 + 5 -0.018065 -0.053536 0.515544 -0.042464 -0.071584 -0.000580 + 6 0.015556 0.129082 0.061387 -0.080264 0.513710 0.001219 + 7 0.048089 -0.074884 -0.021344 -0.000100 0.039595 0.000265 + 8 -0.045599 -0.251082 -0.205911 0.038449 -0.008174 0.000169 + 9 0.015007 -0.268343 0.000152 0.145321 0.051763 0.993429 + 10 0.975958 -0.772045 0.064968 -0.139713 -0.080525 -0.044297 + 11 -0.160837 -0.171067 -0.794666 -0.970525 -0.564522 0.085058 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 578.41 0.023970 121.13 0.012932 ( 0.041672 0.090085 -0.055501) + 7: 615.14 0.021497 108.64 0.010906 ( 0.062540 -0.042025 -0.072307) + 8: 811.37 0.025890 130.84 0.009958 (-0.064740 0.015505 0.074338) + 9: 1306.03 0.031489 159.13 0.007524 ( 0.042173 -0.011759 -0.074881) + 10: 1704.20 0.022961 116.03 0.004204 (-0.052834 0.002287 0.037521) + 11: 3738.71 0.014296 72.25 0.001193 ( 0.032849 -0.003164 -0.010206) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 578.41 E(vib) ... 0.11 +freq. 615.14 E(vib) ... 0.10 +freq. 811.37 E(vib) ... 0.05 +freq. 1306.03 E(vib) ... 0.01 +freq. 1704.20 E(vib) ... 0.00 +freq. 3738.71 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.45188990 Eh +Zero point energy ... 0.01994275 Eh 12.51 kcal/mol +Thermal vibrational correction ... 0.00041228 Eh 0.26 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42870233 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00324482 Eh 2.04 kcal/mol +Non-thermal (ZPE) correction 0.01994275 Eh 12.51 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02318757 Eh 14.55 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42870233 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.42775812 Eh + + +Note: Only C1 symmetry has been detected, increase convergence thresholds + if your molecule has a higher symmetry. Symmetry factor of 1.0 is + used for the rotational entropy correction. + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: C1, Symmetry Number: 1 +Rotational constants in cm-1: 3.061437 0.416816 0.367120 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00054339 Eh 0.34 kcal/mol +Rotational entropy ... 0.00986879 Eh 6.19 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02821450 Eh 17.70 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00986879 Eh 6.19 kcal/mol| +| sn= 2 | S(rot)= 0.00921434 Eh 5.78 kcal/mol| +| sn= 3 | S(rot)= 0.00883150 Eh 5.54 kcal/mol| +| sn= 4 | S(rot)= 0.00855988 Eh 5.37 kcal/mol| +| sn= 5 | S(rot)= 0.00834919 Eh 5.24 kcal/mol| +| sn= 6 | S(rot)= 0.00817705 Eh 5.13 kcal/mol| +| sn= 7 | S(rot)= 0.00803150 Eh 5.04 kcal/mol| +| sn= 8 | S(rot)= 0.00790542 Eh 4.96 kcal/mol| +| sn= 9 | S(rot)= 0.00779422 Eh 4.89 kcal/mol| +| sn=10 | S(rot)= 0.00769474 Eh 4.83 kcal/mol| +| sn=11 | S(rot)= 0.00760475 Eh 4.77 kcal/mol| +| sn=12 | S(rot)= 0.00752259 Eh 4.72 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.42775812 Eh +Total entropy correction ... -0.02821450 Eh -17.70 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.45597262 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00408272 Eh -2.56 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.451889901 Eh +Current gradient norm .... 0.007502374 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.034635745 0.132025721 0.190768873 0.488216811 0.531466912 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999952052 +Lowest eigenvalues of augmented Hessian: + -0.000036473 0.131857458 0.190721134 0.488225469 0.531466452 +Length of the computed step .... 0.009792984 +The final length of the internal step .... 0.009792984 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0039979690 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0028758006 RMS(Int)= 0.0039979257 + Iter 1: RMS(Cart)= 0.0000005810 RMS(Int)= 0.0000005908 + Iter 2: RMS(Cart)= 0.0000000010 RMS(Int)= 0.0000000010 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0018829220 0.0001000000 NO + MAX gradient 0.0033765434 0.0003000000 NO + RMS step 0.0039979690 0.0020000000 NO + MAX step 0.0076523617 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0040 Max(Angles) 0.05 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4373 0.001683 -0.0040 1.4332 + 2. B(O 2,N 1) 1.1754 0.003377 -0.0016 1.1738 + 3. B(H 3,O 0) 0.9717 0.002617 -0.0028 0.9689 + 4. A(N 1,O 0,H 3) 102.00 0.000330 0.00 102.01 + 5. A(O 0,N 1,O 2) 110.53 0.000285 0.05 110.58 + 6. D(O 2,N 1,O 0,H 3) 171.82 -0.004692 0.00 171.82 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.259109 0.069504 0.722999 + N 0.157101 -0.130948 -0.633735 + O 1.324863 -0.052623 -0.722942 + H -1.222854 0.114067 0.633678 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.489644 0.131343 1.366269 + 1 N 7.0000 0 14.007 0.296877 -0.247455 -1.197585 + 2 O 8.0000 0 15.999 2.503629 -0.099443 -1.366162 + 3 H 1.0000 0 1.008 -2.310859 0.215555 1.197478 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.433225702932 0.00000000 0.00000000 + O 2 1 0 1.173781115001 110.58046445 0.00000000 + H 1 2 3 0.968901077768 102.00636136 171.81818196 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.708404066638 0.00000000 0.00000000 + O 2 1 0 2.218124848521 110.58046445 0.00000000 + H 1 2 3 1.830957687842 102.00636136 171.81818196 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.482472498591 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.972e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7232253583 0.000000000000 0.00022587 0.00000493 0.0008677 0.7000 + 1 -204.7232282309 -0.000002872608 0.00016974 0.00000397 0.0006480 0.7000 + ***Turning on DIIS*** + 2 -204.7232305026 -0.000002271695 0.00040599 0.00000997 0.0004777 0.0000 + 3 -204.7228277006 0.000402802010 0.00013375 0.00000288 0.0000995 0.0000 + 4 -204.7231110673 -0.000283366731 0.00003398 0.00000091 0.0000646 0.0000 + 5 -204.7234108362 -0.000299768848 0.00001706 0.00000031 0.0000300 0.0000 + 6 -204.7231984926 0.000212343572 0.00000616 0.00000013 0.0000106 0.0000 + 7 -204.7232351324 -0.000036639752 0.00000212 0.00000005 0.0000037 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + +Total Energy : -204.72323807 Eh -5570.80252 eV + Last Energy change ... -2.9334e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.4376e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.204 sec +Reference energy ... -204.723237407 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.426 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.079 sec +K-integral sorting ... 5.415 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.025 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.025 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.045 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.023 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.039 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.359 sec +AO-integral generation ... 0.253 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.151 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.253 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090610297 +EMP2(bb)= -0.090610297 +EMP2(ab)= -0.516510084 + +Initial guess performed in 0.133 sec +E(0) ... -204.723237407 +E(MP2) ... -0.697730677 +Initial E(tot) ... -205.420968084 + ... 0.187999425 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.420968084 -0.697730677 -0.000000000 0.027097787 2.74 0.000002241 + *** Turning on DIIS *** + 1 -205.391657749 -0.668420341 0.029310336 0.011887844 2.75 0.058069737 + 2 -205.411160206 -0.687922799 -0.019502457 0.005982716 2.80 0.060966673 + 3 -205.414853714 -0.691616307 -0.003693508 0.002462945 2.83 0.075393462 + 4 -205.416422074 -0.693184667 -0.001568360 0.001619156 2.84 0.082271936 + 5 -205.416981189 -0.693743781 -0.000559114 0.000858187 2.86 0.088031295 + 6 -205.417093127 -0.693855720 -0.000111939 0.000504176 2.84 0.090843754 + 7 -205.417137209 -0.693899802 -0.000044082 0.000193438 2.90 0.092068775 + 8 -205.417148811 -0.693911403 -0.000011602 0.000099885 2.90 0.092506375 + 9 -205.417144688 -0.693907281 0.000004122 0.000025842 2.82 0.092631594 + 10 -205.417148976 -0.693911569 -0.000004288 0.000008937 2.79 0.092665767 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.723237407 +E(CORR) ... -0.693911569 +E(TOT) ... -205.417148976 +Singles norm **1/2 ... 0.092665767 ( 0.046332883, 0.046332883) +T1 diagnostic ... 0.021841531 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.065650 + 10a-> 13a 10b-> 13b 0.053451 + 8b-> 13b -1b-> -1b 0.044986 + 8a-> 13a -1a-> -1a 0.044986 + 10a-> 13a 8b-> 13b 0.036367 + 8a-> 13a 10b-> 13b 0.036367 + 10a-> 13a -1a-> -1a 0.033308 + 10b-> 13b -1b-> -1b 0.033308 + 11a-> 26a 11b-> 26b 0.029851 + 11a-> 26a -1a-> -1a 0.029138 + 11b-> 26b -1b-> -1b 0.029138 + 11a-> 13a 11b-> 13b 0.027970 + 5a-> 13a 5b-> 13b 0.025486 + 10a-> 13a 11b-> 26b 0.024163 + 11a-> 26a 10b-> 13b 0.024163 + 8a-> 22a 8b-> 13b 0.024094 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034759122 + alpha-alpha-alpha ... -0.000901089 ( 2.6%) + alpha-alpha-beta ... -0.016478472 ( 47.4%) + alpha-beta -beta ... -0.016478472 ( 47.4%) + beta -beta -beta ... -0.000901089 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034759122 + +Final correlation energy ... -0.728670691 +E(CCSD) ... -205.417148976 +E(CCSD(T)) ... -205.451908098 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209547265 sqrt= 1.099794192 +W(HF) = 0.826755621 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 46.145 sec + +Fock Matrix Formation ... 0.204 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.3%) +DIIS Solver ... 1.315 sec ( 2.8%) +State Vector Update ... 0.064 sec ( 0.1%) +Sigma-vector construction ... 29.711 sec ( 64.4%) + <0|H|D> ... 0.003 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.016 sec ( 0.1% of sigma) + (0-ext) ... 0.053 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (2-ext) ... 0.725 sec ( 2.4% of sigma) + (4-ext) ... 16.713 sec ( 56.3% of sigma) + ... 1.057 sec ( 3.6% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.084 sec ( 0.3% of sigma) + Fock-dressing ... 1.631 sec ( 5.5% of sigma) + (ik|jl)-dressing ... 0.058 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 7.297 sec ( 24.6% of sigma) + Pair energies ... 0.004 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.674 sec ( 14.5% of ALL) + I/O of integral and amplitudes ... 0.622 sec ( 9.3% of (T)) + External N**7 contributions ... 3.879 sec ( 58.1% of (T)) + Internal N**7 contributions ... 0.306 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.543 sec ( 23.1% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.451908098423 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.000223784 -0.002340418 0.000255661 + 2 N : 0.000289495 -0.002512720 0.000458903 + 3 O : -0.000229499 0.002237730 -0.000375670 + 4 H : 0.000163788 0.002615408 -0.000338895 + +Norm of the cartesian gradient ... 0.004938059 +RMS gradient ... 0.001425495 +MAX gradient ... 0.002615408 + +------- +TIMINGS +------- + +Total numerical gradient time ... 307.195 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.451908098 Eh +Current gradient norm .... 0.004938059 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999993 +Lowest eigenvalues of augmented Hessian: + -0.000000005 0.132219364 0.190717819 0.487542164 0.531661236 +Length of the computed step .... 0.000114479 +The final length of the internal step .... 0.000114479 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0000467357 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0000340016 RMS(Int)= 0.0000467358 + Iter 1: RMS(Cart)= 0.0000000002 RMS(Int)= 0.0000000004 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000181978 0.0000050000 NO + RMS gradient 0.0000239611 0.0001000000 YES + MAX gradient 0.0000502184 0.0003000000 YES + RMS step 0.0000467357 0.0020000000 YES + MAX step 0.0000992508 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4332 -0.000023 0.0001 1.4333 + 2. B(O 2,N 1) 1.1738 -0.000050 0.0000 1.1738 + 3. B(H 3,O 0) 0.9689 -0.000011 0.0000 0.9689 + 4. A(N 1,O 0,H 3) 102.01 -0.000001 -0.00 102.00 + 5. A(O 0,N 1,O 2) 110.58 -0.000016 0.00 110.58 + 6. D(O 2,N 1,O 0,H 3) 171.82 -0.004733 -0.00 171.82 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.259123 0.069507 0.723033 + N 0.157109 -0.130949 -0.633748 + O 1.324893 -0.052626 -0.722969 + H -1.222878 0.114068 0.633683 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.489672 0.131350 1.366335 + 1 N 7.0000 0 14.007 0.296892 -0.247458 -1.197609 + 2 O 8.0000 0 15.999 2.503686 -0.099449 -1.366213 + 3 H 1.0000 0 1.008 -2.310904 0.215557 1.197487 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.433278224213 0.00000000 0.00000000 + O 2 1 0 1.173804119391 110.58137695 0.00000000 + H 1 2 3 0.968912732040 102.00492764 171.81818196 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.708503317475 0.00000000 0.00000000 + O 2 1 0 2.218168320517 110.58137695 0.00000000 + H 1 2 3 1.830979711225 102.00492764 171.81818196 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.480550592491 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.4805505925 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.972e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7232280872 0.000000000000 0.00000214 0.00000005 0.0000102 0.7000 + 1 -204.7232280879 -0.000000000720 0.00000171 0.00000004 0.0000077 0.7000 + ***Turning on DIIS*** + 2 -204.7232280885 -0.000000000600 0.00000407 0.00000011 0.0000058 0.0000 + 3 -204.7232325299 -0.000004441384 0.00000196 0.00000004 0.0000012 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 4 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72322884 Eh -5570.80227 eV + +Components: +Nuclear Repulsion : 69.48055059 Eh 1890.66190 eV +Electronic Energy : -274.20377943 Eh -7461.46417 eV +One Electron Energy: -418.66396869 Eh -11392.42577 eV +Two Electron Energy: 144.46018926 Eh 3930.96160 eV + +Virial components: +Potential Energy : -408.97104316 Eh -11128.66785 eV +Kinetic Energy : 204.24781432 Eh 5557.86558 eV +Virial Ratio : 2.00232764 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.6929e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.6932e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.3026e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.1821e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.666841 -562.3733 + 1 1.0000 -20.640146 -561.6469 + 2 1.0000 -15.799080 -429.9148 + 3 1.0000 -1.605081 -43.6765 + 4 1.0000 -1.400680 -38.1144 + 5 1.0000 -0.948512 -25.8103 + 6 1.0000 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0.860505 23.4155 + 47 0.0000 0.876909 23.8619 + 48 0.0000 0.926605 25.2142 + 49 0.0000 0.938879 25.5482 + 50 0.0000 0.947449 25.7814 + 51 0.0000 0.997106 27.1326 + 52 0.0000 1.048065 28.5193 + 53 0.0000 1.062157 28.9028 + 54 0.0000 1.077683 29.3252 + 55 0.0000 1.104087 30.0437 + 56 0.0000 1.160814 31.5873 + 57 0.0000 1.194350 32.4999 + 58 0.0000 1.252355 34.0783 + 59 0.0000 1.273815 34.6623 + 60 0.0000 1.364344 37.1257 + 61 0.0000 1.431540 38.9542 + 62 0.0000 1.491950 40.5980 + 63 0.0000 1.521197 41.3939 + 64 0.0000 1.525226 41.5035 + 65 0.0000 1.546206 42.0744 + 66 0.0000 1.553872 42.2830 + 67 0.0000 1.606900 43.7260 + 68 0.0000 1.660389 45.1815 + 69 0.0000 1.729229 47.0547 + 70 0.0000 1.755423 47.7675 + 71 0.0000 1.819752 49.5180 + 72 0.0000 1.857080 50.5337 + 73 0.0000 1.960513 53.3483 + 74 0.0000 1.970086 53.6088 + 75 0.0000 2.000444 54.4349 + 76 0.0000 2.075174 56.4684 + 77 0.0000 2.116872 57.6030 + 78 0.0000 2.148387 58.4606 + 79 0.0000 2.182533 59.3897 + 80 0.0000 2.275641 61.9234 + 81 0.0000 2.307738 62.7967 + 82 0.0000 2.326995 63.3208 + 83 0.0000 2.380521 64.7773 + 84 0.0000 2.449496 66.6542 + 85 0.0000 2.468990 67.1846 + 86 0.0000 2.498450 67.9863 + 87 0.0000 2.502571 68.0984 + 88 0.0000 2.520899 68.5972 + 89 0.0000 2.543743 69.2188 + 90 0.0000 2.570122 69.9366 + 91 0.0000 2.603303 70.8395 + 92 0.0000 2.620570 71.3093 + 93 0.0000 2.665926 72.5435 + 94 0.0000 2.767119 75.2971 + 95 0.0000 2.774312 75.4929 + 96 0.0000 2.845015 77.4168 + 97 0.0000 2.929464 79.7148 + 98 0.0000 2.946277 80.1723 + 99 0.0000 3.111097 84.6573 + 100 0.0000 3.150123 85.7192 + 101 0.0000 3.183814 86.6360 + 102 0.0000 3.249328 88.4187 + 103 0.0000 3.458386 94.1075 + 104 0.0000 3.819781 103.9415 + 105 0.0000 3.863907 105.1423 + 106 0.0000 4.029942 109.6603 + 107 0.0000 4.174081 113.5825 + 108 0.0000 4.180252 113.7504 + 109 0.0000 4.222401 114.8974 + 110 0.0000 4.366330 118.8139 + 111 0.0000 4.378667 119.1496 + 112 0.0000 4.579137 124.6047 + 113 0.0000 4.629827 125.9840 + 114 0.0000 4.750665 129.2722 + 115 0.0000 4.814287 131.0034 + 116 0.0000 4.863233 132.3353 + 117 0.0000 4.891440 133.1029 + 118 0.0000 4.980260 135.5198 + 119 0.0000 5.002660 136.1293 + 120 0.0000 5.073233 138.0497 + 121 0.0000 5.092193 138.5656 + 122 0.0000 5.170200 140.6883 + 123 0.0000 5.249221 142.8386 + 124 0.0000 5.256537 143.0376 + 125 0.0000 5.334914 145.1704 + 126 0.0000 5.352498 145.6489 + 127 0.0000 5.390658 146.6872 + 128 0.0000 5.573292 151.6570 + 129 0.0000 5.673816 154.3924 + 130 0.0000 5.796916 157.7421 + 131 0.0000 5.993794 163.0994 + 132 0.0000 6.111698 166.3078 + 133 0.0000 6.431343 175.0057 + 134 0.0000 6.507026 177.0652 + 135 0.0000 6.508821 177.1140 + 136 0.0000 6.676131 181.6668 + 137 0.0000 6.715211 182.7302 + 138 0.0000 6.744247 183.5203 + 139 0.0000 6.848669 186.3618 + 140 0.0000 6.915413 188.1779 + 141 0.0000 7.070250 192.3913 + 142 0.0000 7.121155 193.7765 + 143 0.0000 7.182541 195.4469 + 144 0.0000 7.229527 196.7254 + 145 0.0000 7.252622 197.3539 + 146 0.0000 7.260256 197.5616 + 147 0.0000 7.338782 199.6984 + 148 0.0000 7.384080 200.9310 + 149 0.0000 7.433857 202.2855 + 150 0.0000 7.478212 203.4925 + 151 0.0000 7.611535 207.1204 + 152 0.0000 7.646756 208.0788 + 153 0.0000 7.700676 209.5460 + 154 0.0000 7.791847 212.0269 + 155 0.0000 7.971923 216.9271 + 156 0.0000 8.068120 219.5447 + 157 0.0000 8.422931 229.1996 + 158 0.0000 14.201778 386.4500 + 159 0.0000 15.116540 411.3420 + 160 0.0000 16.049277 436.7230 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.344269 0.000000 + 1 N : 0.343914 0.000000 + 2 O : -0.277464 0.000000 + 3 H : 0.277818 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.866647 s : 3.866647 + pz : 1.286964 p : 4.449142 + px : 1.335449 + py : 1.826729 + dz2 : 0.009638 d : 0.023824 + dxz : 0.003455 + dyz : 0.007969 + dx2y2 : 0.002208 + dxy : 0.000554 + f0 : 0.002202 f : 0.004656 + f+1 : 0.000332 + f-1 : 0.001285 + f+2 : 0.000291 + f-2 : 0.000044 + f+3 : 0.000443 + f-3 : 0.000059 + 1 N s : 3.829978 s : 3.829978 + pz : 0.894063 p : 2.651562 + px : 1.012261 + py : 0.745238 + dz2 : 0.033581 d : 0.144818 + dxz : 0.046326 + dyz : 0.017023 + dx2y2 : 0.010670 + dxy : 0.037218 + f0 : 0.008895 f : 0.029728 + f+1 : 0.004088 + f-1 : 0.006180 + f+2 : 0.004006 + f-2 : 0.000915 + f+3 : 0.001660 + f-3 : 0.003985 + 2 O s : 3.877022 s : 3.877022 + pz : 1.879306 p : 4.329141 + px : 1.165663 + py : 1.284172 + dz2 : 0.005340 d : 0.063460 + dxz : 0.015810 + dyz : 0.000332 + dx2y2 : 0.010473 + dxy : 0.031506 + f0 : 0.001139 f : 0.007841 + f+1 : 0.001095 + f-1 : 0.000371 + f+2 : 0.001269 + f-2 : 0.000010 + f+3 : 0.001136 + f-3 : 0.002821 + 3 H s : 0.621744 s : 0.621744 + pz : 0.019774 p : 0.077777 + px : 0.016266 + py : 0.041737 + dz2 : 0.000223 d : 0.022661 + dxz : 0.010794 + dyz : -0.000259 + dx2y2 : 0.001071 + dxy : 0.010832 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.604507 0.000000 + 1 N : -0.268228 0.000000 + 2 O : 0.235091 0.000000 + 3 H : -0.571369 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.113177 s : 3.113177 + pz : 1.221628 p : 3.901330 + px : 1.244297 + py : 1.435405 + dz2 : 0.127084 d : 0.292450 + dxz : 0.068225 + dyz : 0.044183 + dx2y2 : 0.041867 + dxy : 0.011090 + f0 : 0.032599 f : 0.088536 + f+1 : 0.022613 + f-1 : 0.013122 + f+2 : 0.008651 + f-2 : 0.006672 + f+3 : 0.004190 + f-3 : 0.000690 + 1 N s : 3.002105 s : 3.002105 + pz : 0.949368 p : 2.833368 + px : 1.185902 + py : 0.698098 + dz2 : 0.220603 d : 0.972688 + dxz : 0.332168 + dyz : 0.099541 + dx2y2 : 0.175205 + dxy : 0.145170 + f0 : 0.122907 f : 0.460067 + f+1 : 0.073319 + f-1 : 0.061168 + f+2 : 0.084459 + f-2 : 0.014002 + f+3 : 0.050906 + f-3 : 0.053305 + 2 O s : 3.315210 s : 3.315210 + pz : 1.520398 p : 4.006617 + px : 1.387534 + py : 1.098684 + dz2 : 0.045149 d : 0.325005 + dxz : 0.115012 + dyz : 0.004052 + dx2y2 : 0.105152 + dxy : 0.055639 + f0 : 0.016456 f : 0.118078 + f+1 : 0.021775 + f-1 : 0.001973 + f+2 : 0.029071 + f-2 : 0.001918 + f+3 : 0.024304 + f-3 : 0.022580 + 3 H s : 0.621410 s : 0.621410 + pz : 0.134977 p : 0.554550 + px : 0.261365 + py : 0.158207 + dz2 : 0.039176 d : 0.395410 + dxz : 0.134063 + dyz : 0.004074 + dx2y2 : 0.093817 + dxy : 0.124280 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3443 8.0000 -0.3443 1.9445 1.9445 0.0000 + 1 N 6.6561 7.0000 0.3439 2.5341 2.5341 -0.0000 + 2 O 8.2775 8.0000 -0.2775 1.7255 1.7255 0.0000 + 3 H 0.7222 1.0000 0.2778 0.9383 0.9383 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.9241 B( 0-O , 3-H ) : 0.9638 B( 1-N , 2-O ) : 1.6522 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.098 sec +Sum of individual times .... 0.725 sec ( 66.1%) + +Fock matrix formation .... 0.483 sec ( 44.0%) +Diagonalization .... 0.056 sec ( 5.1%) +Density matrix formation .... 0.004 sec ( 0.4%) +Population analysis .... 0.135 sec ( 12.3%) +Initial guess .... 0.009 sec ( 0.9%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.5%) +DIIS solution .... 0.037 sec ( 3.4%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.203 sec +Reference energy ... -204.723228089 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.355 sec +AO-integral generation ... 0.143 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.366 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.026 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.026 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.045 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.035 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.023 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.359 sec +AO-integral generation ... 0.254 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.152 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.255 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090611480 +EMP2(bb)= -0.090611480 +EMP2(ab)= -0.516517336 + +Initial guess performed in 0.132 sec +E(0) ... -204.723228089 +E(MP2) ... -0.697740296 +Initial E(tot) ... -205.420968385 + ... 0.188008404 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.420968385 -0.697740296 -0.000000000 0.027099591 2.73 0.000000944 + *** Turning on DIIS *** + 1 -205.391653532 -0.668425443 0.029314853 0.011889146 2.77 0.058073985 + 2 -205.411157604 -0.687929515 -0.019504072 0.005983214 2.81 0.060970160 + 3 -205.414851376 -0.691623287 -0.003693773 0.002463251 2.87 0.075398200 + 4 -205.416419929 -0.693191840 -0.001568552 0.001619401 2.86 0.082277336 + 5 -205.416979156 -0.693751067 -0.000559228 0.000858343 2.87 0.088037594 + 6 -205.417091115 -0.693863026 -0.000111959 0.000504305 2.91 0.090850569 + 7 -205.417135210 -0.693907121 -0.000044095 0.000193491 2.88 0.092075969 + 8 -205.417146817 -0.693918728 -0.000011607 0.000099917 2.90 0.092513739 + 9 -205.417142694 -0.693914605 0.000004123 0.000025850 2.85 0.092639013 + 10 -205.417146984 -0.693918895 -0.000004290 0.000008941 2.78 0.092673206 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.723228089 +E(CORR) ... -0.693918895 +E(TOT) ... -205.417146984 +Singles norm **1/2 ... 0.092673206 ( 0.046336603, 0.046336603) +T1 diagnostic ... 0.021843284 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.065660 + 10a-> 13a 10b-> 13b 0.053452 + 8a-> 13a -1a-> -1a 0.044991 + 8b-> 13b -1b-> -1b 0.044991 + 8a-> 13a 10b-> 13b 0.036371 + 10a-> 13a 8b-> 13b 0.036371 + 10b-> 13b -1b-> -1b 0.033312 + 10a-> 13a -1a-> -1a 0.033312 + 11a-> 26a 11b-> 26b 0.029857 + 11b-> 26b -1b-> -1b 0.029139 + 11a-> 26a -1a-> -1a 0.029139 + 11a-> 13a 11b-> 13b 0.027971 + 5a-> 13a 5b-> 13b 0.025491 + 11a-> 26a 10b-> 13b 0.024165 + 10a-> 13a 11b-> 26b 0.024165 + 8a-> 13a 8b-> 22b 0.024094 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034761122 + alpha-alpha-alpha ... -0.000901119 ( 2.6%) + alpha-alpha-beta ... -0.016479442 ( 47.4%) + alpha-beta -beta ... -0.016479442 ( 47.4%) + beta -beta -beta ... -0.000901119 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034761122 + +Final correlation energy ... -0.728680017 +E(CCSD) ... -205.417146984 +E(CCSD(T)) ... -205.451908106 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209558291 sqrt= 1.099799205 +W(HF) = 0.826748084 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.255364 0.000000 + 1 N : 0.153742 -0.000000 + 2 O : -0.163484 0.000000 + 3 H : 0.265106 -0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: 0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.846822 s : 3.846822 + pz : 1.277819 p : 4.343881 + px : 1.323026 + py : 1.743036 + dz2 : 0.014564 d : 0.056189 + dxz : 0.009727 + dyz : 0.015225 + dx2y2 : 0.008957 + dxy : 0.007715 + f0 : 0.002349 f : 0.008472 + f+1 : 0.000872 + f-1 : 0.001804 + f+2 : 0.000969 + f-2 : 0.000687 + f+3 : 0.001091 + f-3 : 0.000700 + 1 N s : 3.879832 s : 3.879832 + pz : 0.918723 p : 2.762270 + px : 0.991471 + py : 0.852075 + dz2 : 0.038874 d : 0.174990 + dxz : 0.057777 + dyz : 0.025865 + dx2y2 : 0.015012 + dxy : 0.037463 + f0 : 0.008651 f : 0.029166 + f+1 : 0.003784 + f-1 : 0.006083 + f+2 : 0.004304 + f-2 : 0.001579 + f+3 : 0.001716 + f-3 : 0.003050 + 2 O s : 3.866736 s : 3.866736 + pz : 1.795933 p : 4.201103 + px : 1.156918 + py : 1.248252 + dz2 : 0.010286 d : 0.085221 + dxz : 0.024313 + dyz : 0.006671 + dx2y2 : 0.012763 + dxy : 0.031188 + f0 : 0.001645 f : 0.010424 + f+1 : 0.001561 + f-1 : 0.000854 + f+2 : 0.001764 + f-2 : 0.000664 + f+3 : 0.001353 + f-3 : 0.002583 + 3 H s : 0.633784 s : 0.633784 + pz : 0.023656 p : 0.081673 + px : 0.010063 + py : 0.047954 + dz2 : 0.000583 d : 0.019437 + dxz : 0.009641 + dyz : -0.000108 + dx2y2 : 0.000107 + dxy : 0.009214 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.621565 0.000000 + 1 N : -0.318679 0.000000 + 2 O : 0.268261 -0.000000 + 3 H : -0.571147 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.120589 s : 3.120589 + pz : 1.224677 p : 3.838671 + px : 1.238131 + py : 1.375863 + dz2 : 0.133022 d : 0.323682 + dxz : 0.073389 + dyz : 0.051061 + dx2y2 : 0.049648 + dxy : 0.016562 + f0 : 0.033294 f : 0.095493 + f+1 : 0.023941 + f-1 : 0.015188 + f+2 : 0.009340 + f-2 : 0.007275 + f+3 : 0.005177 + f-3 : 0.001277 + 1 N s : 3.007303 s : 3.007303 + pz : 0.953614 p : 2.882035 + px : 1.164495 + py : 0.763926 + dz2 : 0.227897 d : 0.981460 + dxz : 0.328953 + dyz : 0.101204 + dx2y2 : 0.181519 + dxy : 0.141887 + f0 : 0.120677 f : 0.447881 + f+1 : 0.073508 + f-1 : 0.058110 + f+2 : 0.078148 + f-2 : 0.013867 + f+3 : 0.051350 + f-3 : 0.052221 + 2 O s : 3.317008 s : 3.317008 + pz : 1.467103 p : 3.931335 + px : 1.380228 + py : 1.084004 + dz2 : 0.051009 d : 0.356625 + dxz : 0.117068 + dyz : 0.010347 + dx2y2 : 0.109934 + dxy : 0.068267 + f0 : 0.016721 f : 0.126771 + f+1 : 0.022539 + f-1 : 0.002745 + f+2 : 0.028803 + f-2 : 0.002883 + f+3 : 0.025343 + f-3 : 0.027737 + 3 H s : 0.623641 s : 0.623641 + pz : 0.136555 p : 0.562569 + px : 0.263697 + py : 0.162317 + dz2 : 0.040419 d : 0.384937 + dxz : 0.129494 + dyz : 0.004259 + dx2y2 : 0.093391 + dxy : 0.117374 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2554 8.0000 -0.2554 2.3109 1.8499 0.4610 + 1 N 6.8463 7.0000 0.1537 2.8249 2.3500 0.4749 + 2 O 8.1635 8.0000 -0.1635 2.1282 1.6321 0.4961 + 3 H 0.7349 1.0000 0.2651 0.9598 0.8897 0.0700 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8595 B( 0-O , 3-H ) : 0.8906 B( 1-N , 2-O ) : 1.5118 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 46.503 sec + +Fock Matrix Formation ... 0.203 sec ( 0.4%) +Initial Guess ... 0.132 sec ( 0.3%) +DIIS Solver ... 1.237 sec ( 2.7%) +State Vector Update ... 0.064 sec ( 0.1%) +Sigma-vector construction ... 29.916 sec ( 64.3%) + <0|H|D> ... 0.003 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (0-ext) ... 0.057 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (2-ext) ... 0.733 sec ( 2.4% of sigma) + (4-ext) ... 16.646 sec ( 55.6% of sigma) + ... 1.056 sec ( 3.5% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.085 sec ( 0.3% of sigma) + Fock-dressing ... 1.618 sec ( 5.4% of sigma) + (ik|jl)-dressing ... 0.059 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 7.571 sec ( 25.3% of sigma) + Pair energies ... 0.004 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.826 sec ( 14.7% of ALL) + I/O of integral and amplitudes ... 0.801 sec ( 11.7% of (T)) + External N**7 contributions ... 3.907 sec ( 57.2% of (T)) + Internal N**7 contributions ... 0.314 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.723 sec ( 25.2% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.451908105657 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.044.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.044.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.724297, -0.058249 -0.331097) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.62177 -0.11579 -0.77535 +Nuclear contribution : -1.50368 0.13654 0.76154 + ----------------------------------------- +Total Dipole Moment : -0.88191 0.02075 -0.01381 + ----------------------------------------- +Magnitude (a.u.) : 0.88226 +Magnitude (Debye) : 2.24253 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.077332 0.418446 0.368612 +Rotational constants in MHz : 92256.093293 12544.708846 11050.717062 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.637790 -0.604160 -0.081221 +x,y,z [Debye]: 1.621133 -1.535654 -0.206447 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.724297, -0.058249 -0.331097) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.79266 -0.10169 -0.72450 +Nuclear contribution : -1.50368 0.13654 0.76154 + ----------------------------------------- +Total Dipole Moment : -0.71102 0.03485 0.03704 + ----------------------------------------- +Magnitude (a.u.) : 0.71283 +Magnitude (Debye) : 1.81188 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.077332 0.418446 0.368612 +Rotational constants in MHz : 92256.093293 12544.708846 11050.717062 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.548025 -0.449575 -0.075383 +x,y,z [Debye]: 1.392969 -1.142729 -0.191607 + + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 45 * + * * + * Dihedral ( 2, 1, 0, 3) : 180.00000000 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... Z-matrix Internals +Initial Hessian InHess .... Read + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in new redundant internal coordinates +Making redundant internal coordinates ... (new redundants) done +Evaluating the initial hessian ... (Is done on the fly) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +Imposing constraints: + Iter 0: RMS(Cart)= 0.0395886917 RMS(Int)= 0.0002472701 + Iter 1: RMS(Cart)= 0.0000685513 RMS(Int)= 0.0000012840 + Iter 2: RMS(Cart)= 0.0000003560 RMS(Int)= 0.0000000067 + Iter 3: RMS(Cart)= 0.0000000019 RMS(Int)= 0.0000000000 +CONVERGED +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(N 1,O 0) 1.4333 0.000000 + 2. B(O 2,N 1) 1.1760 0.000000 + 3. B(H 3,O 0) 0.9717 0.000000 + 4. A(N 1,O 0,H 3) 101.9786 0.000000 + 5. A(O 0,N 1,O 2) 110.5334 0.000000 + 6. D(O 2,N 1,O 0,H 3) 180.0000 0.000000 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.257971 0.103858 0.718312 + N 0.155431 -0.093756 -0.639758 + O 1.328697 -0.085873 -0.719077 + H -1.226156 0.075771 0.640523 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.487494 0.196263 1.357412 + 1 N 7.0000 0 14.007 0.293722 -0.177174 -1.208967 + 2 O 8.0000 0 15.999 2.510873 -0.162276 -1.358859 + 3 H 1.0000 0 1.008 -2.317099 0.143187 1.210414 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.433278224213 0.00000000 0.00000000 + O 2 1 0 1.173804119391 110.58137695 0.00000000 + H 1 2 3 0.968912732040 102.00492764 171.81818196 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.708503317475 0.00000000 0.00000000 + O 2 1 0 2.218168320517 110.58137695 0.00000000 + H 1 2 3 1.830979711225 102.00492764 171.81818196 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2691 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.408123644635 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.4081236446 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.980e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7185685288 0.000000000000 0.00184191 0.00005285 0.0198050 0.7000 + 1 -204.7194689045 -0.000900375653 0.00174483 0.00004762 0.0163701 0.7000 + ***Turning on DIIS*** + 2 -204.7202355281 -0.000766623556 0.00474386 0.00012855 0.0132789 0.0000 + 3 -204.7237965397 -0.003561011668 0.00191675 0.00005155 0.0052359 0.0000 + 4 -204.7220670348 0.001729504912 0.00087759 0.00002263 0.0020153 0.0000 + 5 -204.7235478505 -0.001480815737 0.00074299 0.00002412 0.0009701 0.0000 + 6 -204.7229419651 0.000605885439 0.00048304 0.00001559 0.0004792 0.0000 + 7 -204.7224757021 0.000466262987 0.00029652 0.00000983 0.0002694 0.0000 + 8 -204.7233275056 -0.000851803477 0.00019468 0.00000688 0.0001924 0.0000 + 9 -204.7228833619 0.000444143700 0.00011221 0.00000337 0.0001026 0.0000 + 10 -204.7229147148 -0.000031352906 0.00005582 0.00000160 0.0000497 0.0000 + 11 -204.7230626244 -0.000147909589 0.00002791 0.00000077 0.0000195 0.0000 + 12 -204.7229853280 0.000077296374 0.00000547 0.00000015 0.0000052 0.0000 + 13 -204.7230035667 -0.000018238704 0.00000146 0.00000004 0.0000020 0.0000 + 14 -204.7229981218 0.000005444878 0.00000068 0.00000002 0.0000010 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 15 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72299844 Eh -5570.79600 eV + +Components: +Nuclear Repulsion : 69.40812364 Eh 1888.69106 eV +Electronic Energy : -274.13112208 Eh -7459.48706 eV +One Electron Energy: -418.52656938 Eh -11388.68694 eV +Two Electron Energy: 144.39544730 Eh 3929.19988 eV + +Virial components: +Potential Energy : -408.95452625 Eh -11128.21841 eV +Kinetic Energy : 204.23152782 Eh 5557.42241 eV +Virial Ratio : 2.00240644 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -3.1411e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.1011e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.2997e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.7857e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.666502 -562.3641 + 1 1.0000 -20.641140 -561.6740 + 2 1.0000 -15.799450 -429.9249 + 3 1.0000 -1.603164 -43.6243 + 4 1.0000 -1.400165 -38.1004 + 5 1.0000 -0.948551 -25.8114 + 6 1.0000 -0.783247 -21.3132 + 7 1.0000 -0.729365 -19.8470 + 8 1.0000 -0.681063 -18.5327 + 9 1.0000 -0.625215 -17.0130 + 10 1.0000 -0.528363 -14.3775 + 11 1.0000 -0.461613 -12.5611 + 12 0.0000 0.028106 0.7648 + 13 0.0000 0.080022 2.1775 + 14 0.0000 0.093837 2.5534 + 15 0.0000 0.097586 2.6554 + 16 0.0000 0.128998 3.5102 + 17 0.0000 0.143817 3.9135 + 18 0.0000 0.156819 4.2673 + 19 0.0000 0.172160 4.6847 + 20 0.0000 0.187356 5.0982 + 21 0.0000 0.196602 5.3498 + 22 0.0000 0.205479 5.5914 + 23 0.0000 0.233157 6.3445 + 24 0.0000 0.258056 7.0221 + 25 0.0000 0.296481 8.0677 + 26 0.0000 0.305655 8.3173 + 27 0.0000 0.329671 8.9708 + 28 0.0000 0.365039 9.9332 + 29 0.0000 0.382025 10.3954 + 30 0.0000 0.423844 11.5334 + 31 0.0000 0.525080 14.2882 + 32 0.0000 0.526040 14.3143 + 33 0.0000 0.547053 14.8861 + 34 0.0000 0.572839 15.5877 + 35 0.0000 0.613151 16.6847 + 36 0.0000 0.631424 17.1819 + 37 0.0000 0.648310 17.6414 + 38 0.0000 0.680073 18.5057 + 39 0.0000 0.714231 19.4352 + 40 0.0000 0.717674 19.5289 + 41 0.0000 0.748301 20.3623 + 42 0.0000 0.774908 21.0863 + 43 0.0000 0.782069 21.2812 + 44 0.0000 0.811266 22.0757 + 45 0.0000 0.811760 22.0891 + 46 0.0000 0.860610 23.4184 + 47 0.0000 0.877857 23.8877 + 48 0.0000 0.925775 25.1916 + 49 0.0000 0.939238 25.5580 + 50 0.0000 0.945616 25.7315 + 51 0.0000 0.995400 27.0862 + 52 0.0000 1.048700 28.5366 + 53 0.0000 1.061965 28.8975 + 54 0.0000 1.080608 29.4048 + 55 0.0000 1.105272 30.0760 + 56 0.0000 1.160132 31.5688 + 57 0.0000 1.194774 32.5114 + 58 0.0000 1.253316 34.1045 + 59 0.0000 1.267306 34.4852 + 60 0.0000 1.362811 37.0840 + 61 0.0000 1.434517 39.0352 + 62 0.0000 1.489641 40.5352 + 63 0.0000 1.522764 41.4365 + 64 0.0000 1.524290 41.4780 + 65 0.0000 1.543674 42.0055 + 66 0.0000 1.554541 42.3012 + 67 0.0000 1.608481 43.7690 + 68 0.0000 1.657844 45.1122 + 69 0.0000 1.727853 47.0173 + 70 0.0000 1.753045 47.7028 + 71 0.0000 1.821885 49.5760 + 72 0.0000 1.854095 50.4525 + 73 0.0000 1.961214 53.3673 + 74 0.0000 1.974436 53.7271 + 75 0.0000 1.996157 54.3182 + 76 0.0000 2.072245 56.3887 + 77 0.0000 2.132666 58.0328 + 78 0.0000 2.132829 58.0372 + 79 0.0000 2.185013 59.4572 + 80 0.0000 2.270385 61.7803 + 81 0.0000 2.308762 62.8246 + 82 0.0000 2.328321 63.3568 + 83 0.0000 2.381507 64.8041 + 84 0.0000 2.450047 66.6692 + 85 0.0000 2.468515 67.1717 + 86 0.0000 2.499712 68.0206 + 87 0.0000 2.501996 68.0828 + 88 0.0000 2.521002 68.5999 + 89 0.0000 2.543195 69.2039 + 90 0.0000 2.567953 69.8776 + 91 0.0000 2.607438 70.9520 + 92 0.0000 2.607892 70.9643 + 93 0.0000 2.662281 72.4443 + 94 0.0000 2.770571 75.3911 + 95 0.0000 2.778452 75.6055 + 96 0.0000 2.835765 77.1651 + 97 0.0000 2.936614 79.9093 + 98 0.0000 2.945702 80.1566 + 99 0.0000 3.113058 84.7106 + 100 0.0000 3.147312 85.6427 + 101 0.0000 3.183697 86.6328 + 102 0.0000 3.244910 88.2985 + 103 0.0000 3.456025 94.0432 + 104 0.0000 3.829592 104.2085 + 105 0.0000 3.851403 104.8020 + 106 0.0000 4.029330 109.6437 + 107 0.0000 4.169843 113.4672 + 108 0.0000 4.181666 113.7889 + 109 0.0000 4.211263 114.5943 + 110 0.0000 4.364530 118.7649 + 111 0.0000 4.372026 118.9689 + 112 0.0000 4.577206 124.5521 + 113 0.0000 4.631388 126.0265 + 114 0.0000 4.746194 129.1505 + 115 0.0000 4.813256 130.9753 + 116 0.0000 4.870598 132.5357 + 117 0.0000 4.887265 132.9892 + 118 0.0000 4.982061 135.5688 + 119 0.0000 5.001079 136.0863 + 120 0.0000 5.072935 138.0416 + 121 0.0000 5.085446 138.3820 + 122 0.0000 5.166767 140.5949 + 123 0.0000 5.245741 142.7439 + 124 0.0000 5.256187 143.0281 + 125 0.0000 5.330966 145.0630 + 126 0.0000 5.363422 145.9461 + 127 0.0000 5.370626 146.1422 + 128 0.0000 5.575766 151.7243 + 129 0.0000 5.668593 154.2502 + 130 0.0000 5.794096 157.6654 + 131 0.0000 5.990449 163.0084 + 132 0.0000 6.111112 166.2918 + 133 0.0000 6.432127 175.0271 + 134 0.0000 6.506227 177.0434 + 135 0.0000 6.509538 177.1335 + 136 0.0000 6.673793 181.6031 + 137 0.0000 6.715336 182.7336 + 138 0.0000 6.744350 183.5231 + 139 0.0000 6.845931 186.2873 + 140 0.0000 6.913566 188.1277 + 141 0.0000 7.067214 192.3087 + 142 0.0000 7.118765 193.7115 + 143 0.0000 7.177600 195.3124 + 144 0.0000 7.231053 196.7669 + 145 0.0000 7.254684 197.4100 + 146 0.0000 7.256670 197.4640 + 147 0.0000 7.332310 199.5223 + 148 0.0000 7.379553 200.8078 + 149 0.0000 7.431224 202.2139 + 150 0.0000 7.477557 203.4747 + 151 0.0000 7.605074 206.9446 + 152 0.0000 7.644964 208.0300 + 153 0.0000 7.698385 209.4837 + 154 0.0000 7.782576 211.7747 + 155 0.0000 7.970656 216.8926 + 156 0.0000 8.066783 219.5083 + 157 0.0000 8.421526 229.1614 + 158 0.0000 14.182701 385.9309 + 159 0.0000 15.085762 410.5045 + 160 0.0000 15.983642 434.9370 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.666502 -562.3641 + 1 1.0000 -20.641140 -561.6740 + 2 1.0000 -15.799450 -429.9249 + 3 1.0000 -1.603164 -43.6243 + 4 1.0000 -1.400165 -38.1004 + 5 1.0000 -0.948551 -25.8114 + 6 1.0000 -0.783247 -21.3132 + 7 1.0000 -0.729365 -19.8470 + 8 1.0000 -0.681063 -18.5327 + 9 1.0000 -0.625215 -17.0130 + 10 1.0000 -0.528363 -14.3775 + 11 1.0000 -0.461613 -12.5611 + 12 0.0000 0.028106 0.7648 + 13 0.0000 0.080022 2.1775 + 14 0.0000 0.093837 2.5534 + 15 0.0000 0.097586 2.6554 + 16 0.0000 0.128998 3.5102 + 17 0.0000 0.143817 3.9135 + 18 0.0000 0.156819 4.2673 + 19 0.0000 0.172160 4.6847 + 20 0.0000 0.187356 5.0982 + 21 0.0000 0.196602 5.3498 + 22 0.0000 0.205479 5.5914 + 23 0.0000 0.233157 6.3445 + 24 0.0000 0.258056 7.0221 + 25 0.0000 0.296481 8.0677 + 26 0.0000 0.305655 8.3173 + 27 0.0000 0.329671 8.9708 + 28 0.0000 0.365039 9.9332 + 29 0.0000 0.382025 10.3954 + 30 0.0000 0.423844 11.5334 + 31 0.0000 0.525080 14.2882 + 32 0.0000 0.526040 14.3143 + 33 0.0000 0.547053 14.8861 + 34 0.0000 0.572839 15.5877 + 35 0.0000 0.613151 16.6847 + 36 0.0000 0.631424 17.1819 + 37 0.0000 0.648310 17.6414 + 38 0.0000 0.680073 18.5057 + 39 0.0000 0.714231 19.4352 + 40 0.0000 0.717674 19.5289 + 41 0.0000 0.748301 20.3623 + 42 0.0000 0.774908 21.0863 + 43 0.0000 0.782069 21.2812 + 44 0.0000 0.811266 22.0757 + 45 0.0000 0.811760 22.0891 + 46 0.0000 0.860610 23.4184 + 47 0.0000 0.877857 23.8877 + 48 0.0000 0.925775 25.1916 + 49 0.0000 0.939238 25.5580 + 50 0.0000 0.945616 25.7315 + 51 0.0000 0.995400 27.0862 + 52 0.0000 1.048700 28.5366 + 53 0.0000 1.061965 28.8975 + 54 0.0000 1.080608 29.4048 + 55 0.0000 1.105272 30.0760 + 56 0.0000 1.160132 31.5688 + 57 0.0000 1.194774 32.5114 + 58 0.0000 1.253316 34.1045 + 59 0.0000 1.267306 34.4852 + 60 0.0000 1.362811 37.0840 + 61 0.0000 1.434517 39.0352 + 62 0.0000 1.489641 40.5352 + 63 0.0000 1.522764 41.4365 + 64 0.0000 1.524290 41.4780 + 65 0.0000 1.543674 42.0055 + 66 0.0000 1.554541 42.3012 + 67 0.0000 1.608481 43.7690 + 68 0.0000 1.657844 45.1122 + 69 0.0000 1.727853 47.0173 + 70 0.0000 1.753045 47.7028 + 71 0.0000 1.821885 49.5760 + 72 0.0000 1.854095 50.4525 + 73 0.0000 1.961214 53.3673 + 74 0.0000 1.974436 53.7271 + 75 0.0000 1.996157 54.3182 + 76 0.0000 2.072245 56.3887 + 77 0.0000 2.132666 58.0328 + 78 0.0000 2.132829 58.0372 + 79 0.0000 2.185013 59.4572 + 80 0.0000 2.270385 61.7803 + 81 0.0000 2.308762 62.8246 + 82 0.0000 2.328321 63.3568 + 83 0.0000 2.381507 64.8041 + 84 0.0000 2.450047 66.6692 + 85 0.0000 2.468515 67.1717 + 86 0.0000 2.499712 68.0206 + 87 0.0000 2.501996 68.0828 + 88 0.0000 2.521002 68.5999 + 89 0.0000 2.543195 69.2039 + 90 0.0000 2.567953 69.8776 + 91 0.0000 2.607438 70.9520 + 92 0.0000 2.607892 70.9643 + 93 0.0000 2.662281 72.4443 + 94 0.0000 2.770571 75.3911 + 95 0.0000 2.778452 75.6055 + 96 0.0000 2.835765 77.1651 + 97 0.0000 2.936614 79.9093 + 98 0.0000 2.945702 80.1566 + 99 0.0000 3.113058 84.7106 + 100 0.0000 3.147312 85.6427 + 101 0.0000 3.183697 86.6328 + 102 0.0000 3.244910 88.2985 + 103 0.0000 3.456025 94.0432 + 104 0.0000 3.829592 104.2085 + 105 0.0000 3.851403 104.8020 + 106 0.0000 4.029330 109.6437 + 107 0.0000 4.169843 113.4672 + 108 0.0000 4.181666 113.7889 + 109 0.0000 4.211263 114.5943 + 110 0.0000 4.364530 118.7649 + 111 0.0000 4.372026 118.9689 + 112 0.0000 4.577206 124.5521 + 113 0.0000 4.631388 126.0265 + 114 0.0000 4.746194 129.1505 + 115 0.0000 4.813256 130.9753 + 116 0.0000 4.870598 132.5357 + 117 0.0000 4.887265 132.9892 + 118 0.0000 4.982061 135.5688 + 119 0.0000 5.001079 136.0863 + 120 0.0000 5.072935 138.0416 + 121 0.0000 5.085446 138.3820 + 122 0.0000 5.166767 140.5949 + 123 0.0000 5.245741 142.7439 + 124 0.0000 5.256187 143.0281 + 125 0.0000 5.330966 145.0630 + 126 0.0000 5.363422 145.9461 + 127 0.0000 5.370626 146.1422 + 128 0.0000 5.575766 151.7243 + 129 0.0000 5.668593 154.2502 + 130 0.0000 5.794096 157.6654 + 131 0.0000 5.990449 163.0084 + 132 0.0000 6.111112 166.2918 + 133 0.0000 6.432127 175.0271 + 134 0.0000 6.506227 177.0434 + 135 0.0000 6.509538 177.1335 + 136 0.0000 6.673793 181.6031 + 137 0.0000 6.715336 182.7336 + 138 0.0000 6.744350 183.5231 + 139 0.0000 6.845931 186.2873 + 140 0.0000 6.913566 188.1277 + 141 0.0000 7.067214 192.3087 + 142 0.0000 7.118765 193.7115 + 143 0.0000 7.177600 195.3124 + 144 0.0000 7.231053 196.7669 + 145 0.0000 7.254684 197.4100 + 146 0.0000 7.256670 197.4640 + 147 0.0000 7.332310 199.5223 + 148 0.0000 7.379553 200.8078 + 149 0.0000 7.431224 202.2139 + 150 0.0000 7.477557 203.4747 + 151 0.0000 7.605074 206.9446 + 152 0.0000 7.644964 208.0300 + 153 0.0000 7.698385 209.4837 + 154 0.0000 7.782576 211.7747 + 155 0.0000 7.970656 216.8926 + 156 0.0000 8.066783 219.5083 + 157 0.0000 8.421526 229.1614 + 158 0.0000 14.182701 385.9309 + 159 0.0000 15.085762 410.5045 + 160 0.0000 15.983642 434.9370 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.346389 0.000000 + 1 N : 0.344142 0.000000 + 2 O : -0.278563 0.000000 + 3 H : 0.280810 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.867231 s : 3.867231 + pz : 1.288476 p : 4.450408 + px : 1.335967 + py : 1.825965 + dz2 : 0.009953 d : 0.024072 + dxz : 0.003239 + dyz : 0.007920 + dx2y2 : 0.002239 + dxy : 0.000721 + f0 : 0.002218 f : 0.004678 + f+1 : 0.000362 + f-1 : 0.001278 + f+2 : 0.000294 + f-2 : 0.000023 + f+3 : 0.000454 + f-3 : 0.000049 + 1 N s : 3.829596 s : 3.829596 + pz : 0.899273 p : 2.651480 + px : 1.014216 + py : 0.737990 + dz2 : 0.033686 d : 0.145091 + dxz : 0.046204 + dyz : 0.016769 + dx2y2 : 0.010466 + dxy : 0.037966 + f0 : 0.008910 f : 0.029692 + f+1 : 0.004117 + f-1 : 0.006174 + f+2 : 0.004026 + f-2 : 0.000832 + f+3 : 0.001481 + f-3 : 0.004151 + 2 O s : 3.877521 s : 3.877521 + pz : 1.886656 p : 4.330046 + px : 1.164142 + py : 1.279248 + dz2 : 0.005419 d : 0.063159 + dxz : 0.015729 + dyz : 0.000198 + dx2y2 : 0.009943 + dxy : 0.031870 + f0 : 0.001140 f : 0.007837 + f+1 : 0.001100 + f-1 : 0.000382 + f+2 : 0.001305 + f-2 : -0.000031 + f+3 : 0.001078 + f-3 : 0.002862 + 3 H s : 0.619887 s : 0.619887 + pz : 0.019459 p : 0.076869 + px : 0.016137 + py : 0.041273 + dz2 : 0.000168 d : 0.022434 + dxz : 0.010820 + dyz : -0.000336 + dx2y2 : 0.000949 + dxy : 0.010831 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.601416 0.000000 + 1 N : -0.268096 0.000000 + 2 O : 0.233276 0.000000 + 3 H : -0.566596 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.114718 s : 3.114718 + pz : 1.221966 p : 3.902429 + px : 1.243859 + py : 1.436604 + dz2 : 0.128497 d : 0.292861 + dxz : 0.068185 + dyz : 0.043167 + dx2y2 : 0.042182 + dxy : 0.010831 + f0 : 0.033068 f : 0.088575 + f+1 : 0.022664 + f-1 : 0.012701 + f+2 : 0.008383 + f-2 : 0.006767 + f+3 : 0.004252 + f-3 : 0.000740 + 1 N s : 3.003067 s : 3.003067 + pz : 0.954368 p : 2.833323 + px : 1.188696 + py : 0.690259 + dz2 : 0.219554 d : 0.971833 + dxz : 0.333126 + dyz : 0.098785 + dx2y2 : 0.177284 + dxy : 0.143084 + f0 : 0.123639 f : 0.459875 + f+1 : 0.073562 + f-1 : 0.061127 + f+2 : 0.085667 + f-2 : 0.012646 + f+3 : 0.050457 + f-3 : 0.052775 + 2 O s : 3.316536 s : 3.316536 + pz : 1.526461 p : 4.008327 + px : 1.387691 + py : 1.094175 + dz2 : 0.044373 d : 0.324194 + dxz : 0.115958 + dyz : 0.003862 + dx2y2 : 0.106887 + dxy : 0.053114 + f0 : 0.016777 f : 0.117668 + f+1 : 0.021255 + f-1 : 0.001832 + f+2 : 0.029464 + f-2 : 0.001736 + f+3 : 0.024686 + f-3 : 0.021919 + 3 H s : 0.620361 s : 0.620361 + pz : 0.133444 p : 0.551645 + px : 0.261057 + py : 0.157145 + dz2 : 0.039844 d : 0.394590 + dxz : 0.133717 + dyz : 0.002860 + dx2y2 : 0.093632 + dxy : 0.124536 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3464 8.0000 -0.3464 1.9462 1.9462 0.0000 + 1 N 6.6559 7.0000 0.3441 2.5356 2.5356 -0.0000 + 2 O 8.2786 8.0000 -0.2786 1.7251 1.7251 -0.0000 + 3 H 0.7192 1.0000 0.2808 0.9357 0.9357 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.9277 B( 0-O , 3-H ) : 0.9617 B( 1-N , 2-O ) : 1.6510 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.602 sec +Sum of individual times .... 2.201 sec ( 84.6%) + +Fock matrix formation .... 1.720 sec ( 66.1%) +Diagonalization .... 0.179 sec ( 6.9%) +Density matrix formation .... 0.013 sec ( 0.5%) +Population analysis .... 0.128 sec ( 4.9%) +Initial guess .... 0.009 sec ( 0.4%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.005 sec ( 0.2%) +DIIS solution .... 0.152 sec ( 5.8%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.203 sec +Reference energy ... -204.722998621 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.375 sec +AO-integral generation ... 0.142 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.384 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.027 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.028 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.040 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.038 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.359 sec +AO-integral generation ... 0.254 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.155 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.256 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090696996 +EMP2(bb)= -0.090696996 +EMP2(ab)= -0.516946645 + +Initial guess performed in 0.133 sec +E(0) ... -204.722998621 +E(MP2) ... -0.698340637 +Initial E(tot) ... -205.421339258 + ... 0.188515641 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.421339258 -0.698340637 -0.000000000 0.027561262 2.72 0.000001713 + *** Turning on DIIS *** + 1 -205.391745226 -0.668746604 0.029594032 0.012133605 2.73 0.058320817 + 2 -205.411340189 -0.688341568 -0.019594963 0.006109544 2.82 0.061186579 + 3 -205.415047955 -0.692049334 -0.003707766 0.002508187 2.86 0.075685264 + 4 -205.416627263 -0.693628642 -0.001579308 0.001610412 2.85 0.082601329 + 5 -205.417191399 -0.694192778 -0.000564136 0.000853036 2.87 0.088390884 + 6 -205.417303707 -0.694305085 -0.000112308 0.000502561 2.85 0.091204955 + 7 -205.417347898 -0.694349277 -0.000044191 0.000193130 2.92 0.092427911 + 8 -205.417359566 -0.694360945 -0.000011668 0.000100005 2.92 0.092865247 + 9 -205.417355448 -0.694356826 0.000004118 0.000025885 2.84 0.092990640 + 10 -205.417359764 -0.694361142 -0.000004316 0.000009011 2.83 0.093024731 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.722998621 +E(CORR) ... -0.694361142 +E(TOT) ... -205.417359764 +Singles norm **1/2 ... 0.093024731 ( 0.046512366, 0.046512366) +T1 diagnostic ... 0.021926139 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.066980 + 10a-> 13a 10b-> 13b 0.054773 + 8b-> 13b -1b-> -1b 0.046016 + 8a-> 13a -1a-> -1a 0.046016 + 8a-> 13a 10b-> 13b 0.037352 + 10a-> 13a 8b-> 13b 0.037352 + 10a-> 13a -1a-> -1a 0.033072 + 10b-> 13b -1b-> -1b 0.033072 + 11a-> 26a 11b-> 26b 0.031987 + 11b-> 26b -1b-> -1b 0.030392 + 11a-> 26a -1a-> -1a 0.030392 + 11a-> 13a 11b-> 13b 0.028008 + 5a-> 13a 5b-> 13b 0.025592 + 10a-> 13a 11b-> 26b 0.025335 + 11a-> 26a 10b-> 13b 0.025335 + 8a-> 22a 8b-> 13b 0.024478 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034873768 + alpha-alpha-alpha ... -0.000903306 ( 2.6%) + alpha-alpha-beta ... -0.016533577 ( 47.4%) + alpha-beta -beta ... -0.016533577 ( 47.4%) + beta -beta -beta ... -0.000903306 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034873768 + +Final correlation energy ... -0.729234910 +E(CCSD) ... -205.417359764 +E(CCSD(T)) ... -205.452233531 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.210108836 sqrt= 1.100049470 +W(HF) = 0.826371951 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.256487 -0.000000 + 1 N : 0.153544 0.000000 + 2 O : -0.164591 -0.000000 + 3 H : 0.267533 0.000000 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.847270 s : 3.847270 + pz : 1.279487 p : 4.344298 + px : 1.323303 + py : 1.741508 + dz2 : 0.014838 d : 0.056425 + dxz : 0.009562 + dyz : 0.015145 + dx2y2 : 0.009020 + dxy : 0.007860 + f0 : 0.002357 f : 0.008494 + f+1 : 0.000899 + f-1 : 0.001800 + f+2 : 0.000975 + f-2 : 0.000669 + f+3 : 0.001102 + f-3 : 0.000691 + 1 N s : 3.879237 s : 3.879237 + pz : 0.922127 p : 2.762807 + px : 0.992474 + py : 0.848206 + dz2 : 0.038956 d : 0.175270 + dxz : 0.057828 + dyz : 0.025678 + dx2y2 : 0.014861 + dxy : 0.037947 + f0 : 0.008682 f : 0.029142 + f+1 : 0.003806 + f-1 : 0.006073 + f+2 : 0.004335 + f-2 : 0.001512 + f+3 : 0.001608 + f-3 : 0.003127 + 2 O s : 3.867429 s : 3.867429 + pz : 1.803262 p : 4.201779 + px : 1.155852 + py : 1.242665 + dz2 : 0.010323 d : 0.084959 + dxz : 0.024361 + dyz : 0.006529 + dx2y2 : 0.012342 + dxy : 0.031404 + f0 : 0.001647 f : 0.010424 + f+1 : 0.001564 + f-1 : 0.000865 + f+2 : 0.001799 + f-2 : 0.000631 + f+3 : 0.001315 + f-3 : 0.002602 + 3 H s : 0.632382 s : 0.632382 + pz : 0.023385 p : 0.080842 + px : 0.009924 + py : 0.047532 + dz2 : 0.000534 d : 0.019244 + dxz : 0.009670 + dyz : -0.000169 + dx2y2 : -0.000010 + dxy : 0.009218 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.618733 -0.000000 + 1 N : -0.318931 0.000000 + 2 O : 0.266642 -0.000000 + 3 H : -0.566444 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.122185 s : 3.122185 + pz : 1.225245 p : 3.839399 + px : 1.237686 + py : 1.376468 + dz2 : 0.134361 d : 0.324137 + dxz : 0.073297 + dyz : 0.050200 + dx2y2 : 0.049986 + dxy : 0.016293 + f0 : 0.033659 f : 0.095546 + f+1 : 0.023994 + f-1 : 0.014894 + f+2 : 0.009083 + f-2 : 0.007345 + f+3 : 0.005247 + f-3 : 0.001325 + 1 N s : 3.008267 s : 3.008267 + pz : 0.957374 p : 2.882460 + px : 1.166529 + py : 0.758557 + dz2 : 0.226924 d : 0.980580 + dxz : 0.329735 + dyz : 0.100482 + dx2y2 : 0.183833 + dxy : 0.139605 + f0 : 0.121380 f : 0.447625 + f+1 : 0.073907 + f-1 : 0.058030 + f+2 : 0.079273 + f-2 : 0.012526 + f+3 : 0.050919 + f-3 : 0.051590 + 2 O s : 3.318325 s : 3.318325 + pz : 1.473094 p : 3.932744 + px : 1.380567 + py : 1.079083 + dz2 : 0.050275 d : 0.355906 + dxz : 0.117994 + dyz : 0.010069 + dx2y2 : 0.111524 + dxy : 0.066045 + f0 : 0.016987 f : 0.126382 + f+1 : 0.022077 + f-1 : 0.002630 + f+2 : 0.029181 + f-2 : 0.002617 + f+3 : 0.025514 + f-3 : 0.027376 + 3 H s : 0.622696 s : 0.622696 + pz : 0.134996 p : 0.559634 + px : 0.263346 + py : 0.161292 + dz2 : 0.041027 d : 0.384115 + dxz : 0.129077 + dyz : 0.003217 + dx2y2 : 0.093181 + dxy : 0.117613 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : -0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : -0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2565 8.0000 -0.2565 2.3139 1.8518 0.4620 + 1 N 6.8465 7.0000 0.1535 2.8273 2.3515 0.4759 + 2 O 8.1646 8.0000 -0.1646 2.1289 1.6318 0.4971 + 3 H 0.7325 1.0000 0.2675 0.9578 0.8876 0.0702 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8629 B( 0-O , 2-O ) : 0.1003 B( 0-O , 3-H ) : 0.8886 +B( 1-N , 2-O ) : 1.5105 + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 46.527 sec + +Fock Matrix Formation ... 0.203 sec ( 0.4%) +Initial Guess ... 0.133 sec ( 0.3%) +DIIS Solver ... 1.333 sec ( 2.9%) +State Vector Update ... 0.064 sec ( 0.1%) +Sigma-vector construction ... 29.816 sec ( 64.1%) + <0|H|D> ... 0.003 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.019 sec ( 0.1% of sigma) + (0-ext) ... 0.055 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (2-ext) ... 0.734 sec ( 2.5% of sigma) + (4-ext) ... 16.705 sec ( 56.0% of sigma) + ... 1.052 sec ( 3.5% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.085 sec ( 0.3% of sigma) + Fock-dressing ... 1.611 sec ( 5.4% of sigma) + (ik|jl)-dressing ... 0.059 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 7.375 sec ( 24.7% of sigma) + Pair energies ... 0.004 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.836 sec ( 14.7% of ALL) + I/O of integral and amplitudes ... 0.811 sec ( 11.9% of (T)) + External N**7 contributions ... 3.914 sec ( 57.3% of (T)) + Internal N**7 contributions ... 0.313 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.717 sec ( 25.1% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.452233531417 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : 0.002354464 0.000187765 0.000976555 + 2 N : -0.003079638 -0.000139198 -0.000573647 + 3 O : 0.003356719 0.000021851 -0.000231549 + 4 H : -0.002631545 -0.000070418 -0.000171360 + +Norm of the cartesian gradient ... 0.005886089 +RMS gradient ... 0.001699168 +MAX gradient ... 0.003356719 + +------- +TIMINGS +------- + +Total numerical gradient time ... 307.182 sec + + +---------------------------------------------------------------------------- + ORCA NUMERICAL FREQUENCIES + (30-process run) +---------------------------------------------------------------------------- + +Number of atoms ... 4 +Central differences ... NOT used +Number of displacements ... 12 +Numerical increment ... 5.000e-03 bohr +IR-spectrum generation ... on +Raman-spectrum generation ... off +Surface Crossing Hessian ... off + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad +Dipole moment program output ... >input.lastmom +AutoCI program output ... >input.lastautoci + + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 3 (of 13) >> + << Calculating on displaced geometry 13 (of 13) >> + << Calculating on displaced geometry 6 (of 13) >> + << Calculating on displaced geometry 7 (of 13) >> + << Calculating on displaced geometry 8 (of 13) >> + << Calculating on displaced geometry 4 (of 13) >> + << Calculating on displaced geometry 9 (of 13) >> + << Calculating on displaced geometry 1 (of 13) >> + << Calculating on displaced geometry 2 (of 13) >> + << Calculating on displaced geometry 11 (of 13) >> + << Calculating on displaced geometry 5 (of 13) >> + << Calculating on displaced geometry 10 (of 13) >> + << Calculating on displaced geometry 12 (of 13) >> + +----------------------- +VIBRATIONAL FREQUENCIES +----------------------- + +Scaling factor for frequencies = 1.000000000 (already applied!) + + 0: 0.00 cm**-1 + 1: 0.00 cm**-1 + 2: 0.00 cm**-1 + 3: 0.00 cm**-1 + 4: 0.00 cm**-1 + 5: 0.00 cm**-1 + 6: 593.33 cm**-1 + 7: 617.10 cm**-1 + 8: 816.39 cm**-1 + 9: 1311.43 cm**-1 + 10: 1703.25 cm**-1 + 11: 3737.99 cm**-1 + + +------------ +NORMAL MODES +------------ + +These modes are the cartesian displacements weighted by the diagonal matrix +M(i,i)=1/sqrt(m[i]) where m[i] is the mass of the displaced atom +Thus, these vectors are normalized but *not* orthogonal + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 2 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 3 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 4 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 5 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 7 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 8 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 9 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 10 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 11 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 + 6 7 8 9 10 11 + 0 0.000108 -0.425287 -0.059265 0.063356 0.028258 -0.062230 + 1 -0.055146 0.066616 -0.032502 0.009999 0.016505 -0.001665 + 2 0.009311 0.482857 -0.208654 0.059193 0.106298 -0.004263 + 3 0.001708 0.292707 -0.001160 0.011130 -0.615165 -0.001938 + 4 -0.068731 -0.005340 0.079464 -0.005951 -0.021806 -0.000094 + 5 0.010078 -0.077031 0.528120 -0.040832 -0.075821 -0.000643 + 6 -0.000550 0.191090 0.060854 -0.082165 0.506955 0.001239 + 7 0.053375 -0.056486 -0.029739 0.004277 0.008042 0.000025 + 8 -0.008753 -0.389571 -0.204641 0.037671 -0.003421 0.000216 + 9 -0.016712 -0.350221 -0.009092 0.143882 0.053321 0.994988 + 10 0.983193 -0.086569 -0.116327 -0.143889 -0.086595 0.027327 + 11 -0.148896 -0.410223 -0.778838 -0.970032 -0.579271 0.073163 + + +----------- +IR SPECTRUM +----------- + + Mode freq eps Int T**2 TX TY TZ + cm**-1 L/(mol*cm) km/mol a.u. +---------------------------------------------------------------------------- + 6: 593.33 0.019393 98.00 0.010200 (-0.001131 0.099775 -0.015596) + 7: 617.10 0.024437 123.49 0.012358 ( 0.071231 -0.012117 -0.084481) + 8: 816.39 0.027310 138.01 0.010439 (-0.066745 0.010473 0.076647) + 9: 1311.43 0.031960 161.51 0.007605 ( 0.042556 -0.010645 -0.075370) + 10: 1703.25 0.022258 112.48 0.004078 (-0.052329 0.004582 0.036313) + 11: 3737.99 0.014339 72.47 0.001197 ( 0.032970 -0.001035 -0.010441) + +* The epsilon (eps) is given for a Dirac delta lineshape. +** The dipole moment derivative (T) already includes vibrational overlap. + +The first frequency considered to be a vibration is 6 +The total number of vibrations considered is 6 + + +-------------------------- +THERMOCHEMISTRY AT 298.15K +-------------------------- + +Temperature ... 298.15 K +Pressure ... 1.00 atm +Total Mass ... 47.01 AMU + +Throughout the following assumptions are being made: + (1) The electronic state is orbitally nondegenerate + (2) There are no thermally accessible electronically excited states + (3) Hindered rotations indicated by low frequency modes are not + treated as such but are treated as vibrations and this may + cause some error + (4) All equations used are the standard statistical mechanics + equations for an ideal gas + (5) All vibrations are strictly harmonic + +freq. 593.33 E(vib) ... 0.10 +freq. 617.10 E(vib) ... 0.09 +freq. 816.39 E(vib) ... 0.05 +freq. 1311.43 E(vib) ... 0.01 +freq. 1703.25 E(vib) ... 0.00 +freq. 3737.99 E(vib) ... 0.00 + +------------ +INNER ENERGY +------------ + +The inner energy is: U= E(el) + E(ZPE) + E(vib) + E(rot) + E(trans) + E(el) - is the total energy from the electronic structure calculation + = E(kin-el) + E(nuc-el) + E(el-el) + E(nuc-nuc) + E(ZPE) - the the zero temperature vibrational energy from the frequency calculation + E(vib) - the the finite temperature correction to E(ZPE) due to population + of excited vibrational states + E(rot) - is the rotational thermal energy + E(trans)- is the translational thermal energy + +Summary of contributions to the inner energy U: +Electronic energy ... -205.45223353 Eh +Zero point energy ... 0.02000112 Eh 12.55 kcal/mol +Thermal vibrational correction ... 0.00040107 Eh 0.25 kcal/mol +Thermal rotational correction ... 0.00141627 Eh 0.89 kcal/mol +Thermal translational correction ... 0.00141627 Eh 0.89 kcal/mol +----------------------------------------------------------------------- +Total thermal energy -205.42899880 Eh + + +Summary of corrections to the electronic energy: +(perhaps to be used in another calculation) +Total thermal correction 0.00323361 Eh 2.03 kcal/mol +Non-thermal (ZPE) correction 0.02000112 Eh 12.55 kcal/mol +----------------------------------------------------------------------- +Total correction 0.02323473 Eh 14.58 kcal/mol + + +-------- +ENTHALPY +-------- + +The enthalpy is H = U + kB*T + kB is Boltzmann's constant +Total free energy ... -205.42899880 Eh +Thermal Enthalpy correction ... 0.00094421 Eh 0.59 kcal/mol +----------------------------------------------------------------------- +Total Enthalpy ... -205.42805459 Eh + + +Note: Rotational entropy computed according to Herzberg +Infrared and Raman Spectra, Chapter V,1, Van Nostrand Reinhold, 1945 +Point Group: Cs, Symmetry Number: 1 +Rotational constants in cm-1: 3.071463 0.418015 0.367939 + +Vibrational entropy computed according to the QRRHO of S. Grimme +Chem.Eur.J. 2012 18 9955 + + +------- +ENTROPY +------- + +The entropy contributions are T*S = T*(S(el)+S(vib)+S(rot)+S(trans)) + S(el) - electronic entropy + S(vib) - vibrational entropy + S(rot) - rotational entropy + S(trans)- translational entropy +The entropies will be listed as multiplied by the temperature to get +units of energy + +Electronic entropy ... 0.00000000 Eh 0.00 kcal/mol +Vibrational entropy ... 0.00052689 Eh 0.33 kcal/mol +Rotational entropy ... 0.00986484 Eh 6.19 kcal/mol +Translational entropy ... 0.01780232 Eh 11.17 kcal/mol +----------------------------------------------------------------------- +Final entropy term ... 0.02819405 Eh 17.69 kcal/mol + +In case the symmetry of your molecule has not been determined correctly +or in case you have a reason to use a different symmetry number we print +out the resulting rotational entropy values for sn=1,12 : + -------------------------------------------------------- +| sn= 1 | S(rot)= 0.00986484 Eh 6.19 kcal/mol| +| sn= 2 | S(rot)= 0.00921039 Eh 5.78 kcal/mol| +| sn= 3 | S(rot)= 0.00882755 Eh 5.54 kcal/mol| +| sn= 4 | S(rot)= 0.00855593 Eh 5.37 kcal/mol| +| sn= 5 | S(rot)= 0.00834524 Eh 5.24 kcal/mol| +| sn= 6 | S(rot)= 0.00817310 Eh 5.13 kcal/mol| +| sn= 7 | S(rot)= 0.00802755 Eh 5.04 kcal/mol| +| sn= 8 | S(rot)= 0.00790147 Eh 4.96 kcal/mol| +| sn= 9 | S(rot)= 0.00779026 Eh 4.89 kcal/mol| +| sn=10 | S(rot)= 0.00769078 Eh 4.83 kcal/mol| +| sn=11 | S(rot)= 0.00760079 Eh 4.77 kcal/mol| +| sn=12 | S(rot)= 0.00751864 Eh 4.72 kcal/mol| + -------------------------------------------------------- + + +------------------- +GIBBS FREE ENERGY +------------------- + +The Gibbs free energy is G = H - T*S + +Total enthalpy ... -205.42805459 Eh +Total entropy correction ... -0.02819405 Eh -17.69 kcal/mol +----------------------------------------------------------------------- +Final Gibbs free energy ... -205.45624864 Eh + +For completeness - the Gibbs free energy minus the electronic energy +G-E(el) ... -0.00401511 Eh -2.52 kcal/mol + + +Actual Hessian File stored as input.001.hess +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.452233530 Eh +Current gradient norm .... 0.005886089 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.hess The file is opened as a .hess file +done +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 6 +Lowest eigenvalues of the non projected Hessian: + 0.036133486 0.135048411 0.194023013 0.488198678 0.533342467 +done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999975147 +Lowest eigenvalues of augmented Hessian: + -0.000028924 0.135048624 0.194023042 0.488213548 0.533343152 +Length of the computed step .... 0.007050380 +The final length of the internal step .... 0.007050380 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0028783057 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0018488823 RMS(Int)= 0.0028781979 + Iter 1: RMS(Cart)= 0.0000004887 RMS(Int)= 0.0000005112 + Iter 2: RMS(Cart)= 0.0000000008 RMS(Int)= 0.0000000009 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0017806306 0.0001000000 NO + MAX gradient 0.0033648647 0.0003000000 NO + RMS step 0.0028783057 0.0020000000 NO + MAX step 0.0053491267 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0028 Max(Angles) 0.05 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4333 0.000859 -0.0012 1.4320 + 2. B(O 2,N 1) 1.1760 0.003365 -0.0020 1.1740 + 3. B(H 3,O 0) 0.9717 0.002638 -0.0028 0.9689 + 4. A(N 1,O 0,H 3) 101.98 0.000074 0.03 102.00 + 5. A(O 0,N 1,O 2) 110.53 0.000010 0.05 110.59 + 6. D(O 2,N 1,O 0,H 3) 180.00 0.000000 0.00 180.00 C + ---------------------------------------------------------------------------- + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.258530 0.103739 0.717589 + N 0.155579 -0.093638 -0.638985 + O 1.326821 -0.085789 -0.718314 + H -1.223868 0.075688 0.639710 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.488552 0.196039 1.356047 + 1 N 7.0000 0 14.007 0.294002 -0.176949 -1.207508 + 2 O 8.0000 0 15.999 2.507328 -0.162119 -1.357417 + 3 H 1.0000 0 1.008 -2.312776 0.143029 1.208877 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.432040379275 0.00000000 0.00000000 + O 2 1 0 1.173951443427 110.58512435 0.00000000 + H 1 2 3 0.968880609038 102.00411278 180.00000000 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.706164129547 0.00000000 0.00000000 + O 2 1 0 2.218446722598 110.58512435 0.00000000 + H 1 2 3 1.830919007549 102.00411278 180.00000000 + + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2692 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.501677612811 Eh + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.972e-04 +Time for diagonalization ... 0.003 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7235794863 0.000000000000 0.00018576 0.00000408 0.0007455 0.7000 + 1 -204.7235812847 -0.000001798393 0.00015643 0.00000324 0.0005691 0.7000 + ***Turning on DIIS*** + 2 -204.7235826620 -0.000001377325 0.00039959 0.00000805 0.0004252 0.0000 + 3 -204.7233425062 0.000240155769 0.00007525 0.00000195 0.0000806 0.0000 + 4 -204.7234550242 -0.000112517982 0.00002763 0.00000065 0.0000451 0.0000 + 5 -204.7237326291 -0.000277604929 0.00000911 0.00000021 0.0000247 0.0000 + 6 -204.7235661434 0.000166485767 0.00000513 0.00000011 0.0000080 0.0000 + 7 -204.7235871427 -0.000020999282 0.00000154 0.00000005 0.0000028 0.0000 + 8 -204.7235905929 -0.000003450214 0.00000068 0.00000002 0.0000010 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + +Total Energy : -204.72358517 Eh -5570.81197 eV + Last Energy change ... 5.4202e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.3241e-07 Tolerance : 1.0000e-07 + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : -0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : -0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +Total SCF time: 0 days 0 hours 0 min 1 sec + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.226 sec +Reference energy ... -204.723586599 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.396 sec +AO-integral generation ... 0.146 sec +Half transformation ... 0.081 sec +K-integral sorting ... 5.401 sec + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: : 251940 b 0 skpd 0.026 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.024 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.040 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.038 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.357 sec +AO-integral generation ... 0.250 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.052 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.155 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.253 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090622881 +EMP2(bb)= -0.090622881 +EMP2(ab)= -0.516502877 + +Initial guess performed in 0.133 sec +E(0) ... -204.723586599 +E(MP2) ... -0.697748639 +Initial E(tot) ... -205.421335238 + ... 0.187980975 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.421335238 -0.697748639 -0.000000000 0.027387540 2.72 0.000000591 + *** Turning on DIIS *** + 1 -205.391996490 -0.668409892 0.029338748 0.012034658 2.76 0.058107250 + 2 -205.411500175 -0.687913576 -0.019503685 0.006059382 2.82 0.060997240 + 3 -205.415190170 -0.691603571 -0.003689995 0.002487807 2.84 0.075430019 + 4 -205.416758438 -0.693171839 -0.001568268 0.001608968 2.83 0.082311520 + 5 -205.417317145 -0.693730546 -0.000558707 0.000849626 2.88 0.088065203 + 6 -205.417428689 -0.693842090 -0.000111544 0.000498429 2.84 0.090863753 + 7 -205.417472441 -0.693885843 -0.000043753 0.000190383 2.91 0.092075627 + 8 -205.417483915 -0.693897316 -0.000011473 0.000098373 2.92 0.092506571 + 9 -205.417479824 -0.693893226 0.000004090 0.000025365 2.83 0.092629691 + 10 -205.417484056 -0.693897457 -0.000004231 0.000008815 2.78 0.092662926 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.723586599 +E(CORR) ... -0.693897457 +E(TOT) ... -205.417484056 +Singles norm **1/2 ... 0.092662926 ( 0.046331463, 0.046331463) +T1 diagnostic ... 0.021840861 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.066632 + 10a-> 13a 10b-> 13b 0.054304 + 8a-> 13a -1a-> -1a 0.045591 + 8b-> 13b -1b-> -1b 0.045591 + 10a-> 13a 8b-> 13b 0.036996 + 8a-> 13a 10b-> 13b 0.036996 + 10a-> 13a -1a-> -1a 0.033123 + 10b-> 13b -1b-> -1b 0.033123 + 11a-> 26a 11b-> 26b 0.031623 + 11b-> 26b -1b-> -1b 0.030147 + 11a-> 26a -1a-> -1a 0.030147 + 11a-> 13a 11b-> 13b 0.027961 + 5a-> 13a 5b-> 13b 0.025406 + 10a-> 13a 11b-> 26b 0.025158 + 11a-> 26a 10b-> 13b 0.025158 + 8a-> 13a 8b-> 22b 0.024598 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034763935 + alpha-alpha-alpha ... -0.000901632 ( 2.6%) + alpha-alpha-beta ... -0.016480336 ( 47.4%) + alpha-beta -beta ... -0.016480336 ( 47.4%) + beta -beta -beta ... -0.000901632 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034763935 + +Final correlation energy ... -0.728661392 +E(CCSD) ... -205.417484056 +E(CCSD(T)) ... -205.452247991 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209474211 sqrt= 1.099760979 +W(HF) = 0.826805558 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 46.321 sec + +Fock Matrix Formation ... 0.226 sec ( 0.5%) +Initial Guess ... 0.133 sec ( 0.3%) +DIIS Solver ... 1.331 sec ( 2.9%) +State Vector Update ... 0.064 sec ( 0.1%) +Sigma-vector construction ... 29.731 sec ( 64.2%) + <0|H|D> ... 0.003 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.019 sec ( 0.1% of sigma) + (0-ext) ... 0.054 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (2-ext) ... 0.733 sec ( 2.5% of sigma) + (4-ext) ... 16.720 sec ( 56.2% of sigma) + ... 1.065 sec ( 3.6% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.084 sec ( 0.3% of sigma) + Fock-dressing ... 1.609 sec ( 5.4% of sigma) + (ik|jl)-dressing ... 0.059 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 7.343 sec ( 24.7% of sigma) + Pair energies ... 0.004 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.793 sec ( 14.7% of ALL) + I/O of integral and amplitudes ... 0.789 sec ( 11.6% of (T)) + External N**7 contributions ... 3.897 sec ( 57.4% of (T)) + Internal N**7 contributions ... 0.310 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.721 sec ( 25.3% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.452247990963 +------------------------- -------------------- + + +---------------------------------------------------------------------------- + ORCA NUMERICAL GRADIENT + (30-process run) +---------------------------------------------------------------------------- + +I state ... 1 +Number of atoms ... 4 +Derivative's order of accuracy ... 2 +Central differences ... used +Number of displacements ... 24 +Numerical increment ... 5.000e-03 bohr +Translation invariance ... used + +The output will be reduced. Please look at the following files: +SCF program output ... >input.lastscf +Integral program output ... >input.lastint +Gradient program output ... >input.lastgrad + + << Calculating on displaced geometry 6 (of 18) >> + << Calculating on displaced geometry 7 (of 18) >> + << Calculating on displaced geometry 5 (of 18) >> + << Calculating on displaced geometry 2 (of 18) >> + << Calculating on displaced geometry 1 (of 18) >> + << Calculating on displaced geometry 4 (of 18) >> + << Calculating on displaced geometry 8 (of 18) >> + << Calculating on displaced geometry 11 (of 18) >> + << Calculating on displaced geometry 10 (of 18) >> + << Calculating on displaced geometry 12 (of 18) >> + << Calculating on displaced geometry 3 (of 18) >> + << Calculating on displaced geometry 14 (of 18) >> + << Calculating on displaced geometry 9 (of 18) >> + << Calculating on displaced geometry 15 (of 18) >> + << Calculating on displaced geometry 18 (of 18) >> + << Calculating on displaced geometry 13 (of 18) >> + << Calculating on displaced geometry 16 (of 18) >> + << Calculating on displaced geometry 17 (of 18) >> + +------------------------------ +CARTESIAN GRADIENT (NUMERICAL) +------------------------------- + 1 O : -0.000014186 -0.000000446 -0.000006939 + 2 N : 0.000037164 -0.000000173 -0.000000502 + 3 O : -0.000042121 0.000000185 0.000005948 + 4 H : 0.000019143 0.000000434 0.000001493 + +Norm of the cartesian gradient ... 0.000061721 +RMS gradient ... 0.000017817 +MAX gradient ... 0.000042121 + +------- +TIMINGS +------- + +Total numerical gradient time ... 306.711 sec + +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (new redundants).... done +Validating the new internal coordinates .... (new redundants).... done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.452247991 Eh +Current gradient norm .... 0.000061721 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999998 +Lowest eigenvalues of augmented Hessian: + -0.000000003 0.135022876 0.194006178 0.489249443 0.533482816 +Length of the computed step .... 0.000063834 +The final length of the internal step .... 0.000063834 +Converting the step to cartesian space: + Initial RMS(Int)= 0.0000260600 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0000169311 RMS(Int)= 0.0000260601 + Iter 1: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000001 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000144609 0.0000050000 NO + RMS gradient 0.0000193926 0.0001000000 YES + MAX gradient 0.0000423220 0.0003000000 YES + RMS step 0.0000260600 0.0020000000 YES + MAX step 0.0000502803 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0000 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + Everything but the energy has converged. However, the energy + appears to be close enough to convergence to make sure that the + final evaluation at the new geometry represents the equilibrium energy. + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(N 1,O 0) 1.4320 -0.000007 -0.0000 1.4320 + 2. B(O 2,N 1) 1.1740 -0.000042 0.0000 1.1740 + 3. B(H 3,O 0) 0.9689 -0.000019 0.0000 0.9689 + 4. A(N 1,O 0,H 3) 102.00 -0.000000 -0.00 102.00 + 5. A(O 0,N 1,O 2) 110.59 -0.000007 0.00 110.59 + 6. D(O 2,N 1,O 0,H 3) 180.00 0.000000 -0.00 180.00 C + ---------------------------------------------------------------------------- + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 2 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O -0.258528 0.103740 0.717595 + N 0.155574 -0.093637 -0.638982 + O 1.326841 -0.085791 -0.718326 + H -1.223886 0.075688 0.639713 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 -0.488547 0.196041 1.356058 + 1 N 7.0000 0 14.007 0.293992 -0.176948 -1.207501 + 2 O 8.0000 0 15.999 2.507366 -0.162121 -1.357440 + 3 H 1.0000 0 1.008 -2.312809 0.143029 1.208883 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 1.432040376612 0.00000000 0.00000000 + O 2 1 0 1.173978050639 110.58548344 0.00000000 + H 1 2 3 0.968900844270 102.00372787 180.00000000 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + N 1 0 0 2.706164124514 0.00000000 0.00000000 + O 2 1 0 2.218497002943 110.58548344 0.00000000 + H 1 2 3 1.830957246596 102.00372787 180.00000000 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 2 Type N : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + Group 3 Type H : 6s3p2d contracted to 4s3p2d pattern {3111/111/11} + +Atom 0O basis set group => 1 +Atom 1N basis set group => 2 +Atom 2O basis set group => 1 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 179 +Number of shells ... 69 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 69 +Calculating pre-screening integrals (ORCA) ... done ( 0.0 sec) Dimension = 51 +Organizing shell pair data ... done ( 0.0 sec) +Shell pair information +Total number of shell pairs ... 2415 +Shell pairs after pre-screening ... 2226 +Total number of primitive shell pairs ... 3015 +Primitive shell pairs kept ... 2692 + la=0 lb=0: 550 shell pairs + la=1 lb=0: 536 shell pairs + la=1 lb=1: 120 shell pairs + la=2 lb=0: 390 shell pairs + la=2 lb=1: 165 shell pairs + la=2 lb=2: 66 shell pairs + la=3 lb=0: 222 shell pairs + la=3 lb=1: 90 shell pairs + la=3 lb=2: 66 shell pairs + la=3 lb=3: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.500798261884 Eh + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 17.6 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 161 + Nuclear Repulsion ENuc .... 69.5007982619 Eh + +Convergence Acceleration: + DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 16 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold I (grad. norm) .... 1.000e-05 + Converg. threshold II (energy diff.) .... 1.000e-08 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 0.010 + NR start threshold (gradient norm) .... 0.001 + Initial trust radius .... 0.800 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Orbital update algorithm .... Taylor + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Quad. conv. algorithm .... NR + SOSCF CNVSOSCF .... off + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + Fernandez-Rico CNVRico .... off + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 1 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + DIIS Error TolErr .... 5.000e-07 + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 1.972e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.002 sec +Total time needed ... 0.005 sec + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ +-------------- +SCF ITERATIONS +-------------- +ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp + *** Starting incremental Fock matrix formation *** + 0 -204.7235813455 0.000000000000 0.00000135 0.00000004 0.0000088 0.7000 + 1 -204.7235813457 -0.000000000208 0.00000113 0.00000003 0.0000067 0.7000 + ***Turning on DIIS*** + 2 -204.7235813458 -0.000000000136 0.00000285 0.00000007 0.0000050 0.0000 + 3 -204.7235839371 -0.000002591245 0.00000072 0.00000002 0.0000010 0.0000 + ***DIIS convergence achieved*** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 4 CYCLES * + ***************************************************** + + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -204.72358176 Eh -5570.81187 eV + +Components: +Nuclear Repulsion : 69.50079826 Eh 1891.21287 eV +Electronic Energy : -274.22438002 Eh -7462.02474 eV +One Electron Energy: -418.70380336 Eh -11393.50972 eV +Two Electron Energy: 144.47942334 Eh 3931.48498 eV + +Virial components: +Potential Energy : -408.97171527 Eh -11128.68614 eV +Kinetic Energy : 204.24813351 Eh 5557.87427 eV +Virial Ratio : 2.00232780 + + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.1809e-06 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.9911e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 6.8972e-09 Tolerance : 5.0000e-09 + Last DIIS Error ... 4.8897e-07 Tolerance : 5.0000e-07 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Expectation value of : 0.000000 +Ideal value S*(S+1) for S=0.0 : 0.000000 +Deviation : 0.000000 + + **** THE GBW FILE WAS UPDATED (input.gbw) **** + **** DENSITY input.scfp WAS UPDATED **** +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -20.666337 -562.3596 + 1 1.0000 -20.640664 -561.6610 + 2 1.0000 -15.799016 -429.9131 + 3 1.0000 -1.604924 -43.6722 + 4 1.0000 -1.401199 -38.1286 + 5 1.0000 -0.948467 -25.8091 + 6 1.0000 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0.861060 23.4306 + 47 0.0000 0.878319 23.9003 + 48 0.0000 0.926297 25.2058 + 49 0.0000 0.939416 25.5628 + 50 0.0000 0.946018 25.7424 + 51 0.0000 0.995884 27.0994 + 52 0.0000 1.049083 28.5470 + 53 0.0000 1.062870 28.9222 + 54 0.0000 1.081217 29.4214 + 55 0.0000 1.105815 30.0908 + 56 0.0000 1.160615 31.5819 + 57 0.0000 1.195090 32.5200 + 58 0.0000 1.253650 34.1136 + 59 0.0000 1.267959 34.5029 + 60 0.0000 1.363203 37.0946 + 61 0.0000 1.434925 39.0463 + 62 0.0000 1.490495 40.5584 + 63 0.0000 1.522710 41.4351 + 64 0.0000 1.524520 41.4843 + 65 0.0000 1.544016 42.0148 + 66 0.0000 1.555335 42.3228 + 67 0.0000 1.608977 43.7825 + 68 0.0000 1.658108 45.1194 + 69 0.0000 1.728120 47.0245 + 70 0.0000 1.753373 47.7117 + 71 0.0000 1.822116 49.5823 + 72 0.0000 1.854651 50.4676 + 73 0.0000 1.962139 53.3925 + 74 0.0000 1.975509 53.7563 + 75 0.0000 1.995651 54.3044 + 76 0.0000 2.073019 56.4097 + 77 0.0000 2.133012 58.0422 + 78 0.0000 2.133042 58.0430 + 79 0.0000 2.186643 59.5016 + 80 0.0000 2.270903 61.7944 + 81 0.0000 2.309574 62.8467 + 82 0.0000 2.328855 63.3714 + 83 0.0000 2.381917 64.8153 + 84 0.0000 2.450761 66.6886 + 85 0.0000 2.468720 67.1773 + 86 0.0000 2.499710 68.0206 + 87 0.0000 2.502268 68.0902 + 88 0.0000 2.522200 68.6326 + 89 0.0000 2.543844 69.2215 + 90 0.0000 2.569320 69.9148 + 91 0.0000 2.607703 70.9592 + 92 0.0000 2.608578 70.9830 + 93 0.0000 2.663979 72.4906 + 94 0.0000 2.772390 75.4406 + 95 0.0000 2.779703 75.6396 + 96 0.0000 2.835494 77.1577 + 97 0.0000 2.938178 79.9519 + 98 0.0000 2.946878 80.1886 + 99 0.0000 3.113873 84.7328 + 100 0.0000 3.148675 85.6798 + 101 0.0000 3.183686 86.6325 + 102 0.0000 3.247005 88.3555 + 103 0.0000 3.457522 94.0840 + 104 0.0000 3.833990 104.3282 + 105 0.0000 3.852479 104.8313 + 106 0.0000 4.030603 109.6783 + 107 0.0000 4.172714 113.5453 + 108 0.0000 4.186306 113.9152 + 109 0.0000 4.212907 114.6390 + 110 0.0000 4.368031 118.8602 + 111 0.0000 4.373793 119.0169 + 112 0.0000 4.579756 124.6215 + 113 0.0000 4.634494 126.1110 + 114 0.0000 4.750139 129.2579 + 115 0.0000 4.814760 131.0163 + 116 0.0000 4.871991 132.5736 + 117 0.0000 4.887358 132.9918 + 118 0.0000 4.984517 135.6356 + 119 0.0000 5.001492 136.0975 + 120 0.0000 5.073948 138.0691 + 121 0.0000 5.089796 138.5004 + 122 0.0000 5.169991 140.6826 + 123 0.0000 5.248385 142.8158 + 124 0.0000 5.256908 143.0477 + 125 0.0000 5.336121 145.2032 + 126 0.0000 5.369061 146.0996 + 127 0.0000 5.374960 146.2601 + 128 0.0000 5.575011 151.7038 + 129 0.0000 5.672033 154.3439 + 130 0.0000 5.796832 157.7398 + 131 0.0000 5.992227 163.0568 + 132 0.0000 6.111692 166.3076 + 133 0.0000 6.433945 175.0765 + 134 0.0000 6.506463 177.0499 + 135 0.0000 6.509692 177.1377 + 136 0.0000 6.674499 181.6224 + 137 0.0000 6.716544 182.7665 + 138 0.0000 6.744871 183.5373 + 139 0.0000 6.848287 186.3514 + 140 0.0000 6.915201 188.1722 + 141 0.0000 7.070752 192.4049 + 142 0.0000 7.119687 193.7365 + 143 0.0000 7.183323 195.4682 + 144 0.0000 7.233833 196.8426 + 145 0.0000 7.256455 197.4582 + 146 0.0000 7.259749 197.5478 + 147 0.0000 7.337685 199.6686 + 148 0.0000 7.383192 200.9069 + 149 0.0000 7.432724 202.2547 + 150 0.0000 7.478341 203.4960 + 151 0.0000 7.611058 207.1074 + 152 0.0000 7.647594 208.1016 + 153 0.0000 7.701994 209.5819 + 154 0.0000 7.788496 211.9358 + 155 0.0000 7.976042 217.0391 + 156 0.0000 8.069740 219.5888 + 157 0.0000 8.427346 229.3197 + 158 0.0000 14.212810 386.7502 + 159 0.0000 15.131494 411.7489 + 160 0.0000 16.045080 436.6088 + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 O : -0.343711 0.000000 + 1 N : 0.343800 0.000000 + 2 O : -0.278358 0.000000 + 3 H : 0.278268 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 0.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 O s : 3.866598 s : 3.866598 + pz : 1.288836 p : 4.448577 + px : 1.334463 + py : 1.825278 + dz2 : 0.009861 d : 0.023874 + dxz : 0.003249 + dyz : 0.007931 + dx2y2 : 0.002112 + dxy : 0.000721 + f0 : 0.002226 f : 0.004662 + f+1 : 0.000351 + f-1 : 0.001278 + f+2 : 0.000293 + f-2 : 0.000022 + f+3 : 0.000445 + f-3 : 0.000047 + 1 N s : 3.829947 s : 3.829947 + pz : 0.898870 p : 2.651251 + px : 1.014493 + py : 0.737888 + dz2 : 0.033715 d : 0.145304 + dxz : 0.046292 + dyz : 0.016834 + dx2y2 : 0.010441 + dxy : 0.038022 + f0 : 0.008919 f : 0.029697 + f+1 : 0.004101 + f-1 : 0.006185 + f+2 : 0.004025 + f-2 : 0.000833 + f+3 : 0.001497 + f-3 : 0.004137 + 2 O s : 3.876842 s : 3.876842 + pz : 1.886457 p : 4.330242 + px : 1.164553 + py : 1.279233 + dz2 : 0.005432 d : 0.063425 + dxz : 0.015843 + dyz : 0.000199 + dx2y2 : 0.009951 + dxy : 0.032000 + f0 : 0.001142 f : 0.007849 + f+1 : 0.001100 + f-1 : 0.000382 + f+2 : 0.001310 + f-2 : -0.000031 + f+3 : 0.001075 + f-3 : 0.002871 + 3 H s : 0.621479 s : 0.621479 + pz : 0.019769 p : 0.077558 + px : 0.016079 + py : 0.041709 + dz2 : 0.000179 d : 0.022695 + dxz : 0.010922 + dyz : -0.000337 + dx2y2 : 0.000997 + dxy : 0.010934 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 O : 0.605125 0.000000 + 1 N : -0.268822 0.000000 + 2 O : 0.234749 0.000000 + 3 H : -0.571052 0.000000 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 O s : 3.112765 s : 3.112765 + pz : 1.221776 p : 3.900193 + px : 1.243594 + py : 1.434823 + dz2 : 0.128534 d : 0.293134 + dxz : 0.068305 + dyz : 0.043192 + dx2y2 : 0.042212 + dxy : 0.010892 + f0 : 0.033120 f : 0.088783 + f+1 : 0.022690 + f-1 : 0.012716 + f+2 : 0.008440 + f-2 : 0.006815 + f+3 : 0.004256 + f-3 : 0.000747 + 1 N s : 3.001467 s : 3.001467 + pz : 0.953946 p : 2.833158 + px : 1.189001 + py : 0.690211 + dz2 : 0.219725 d : 0.973663 + dxz : 0.334078 + dyz : 0.098883 + dx2y2 : 0.177461 + dxy : 0.143516 + f0 : 0.123783 f : 0.460533 + f+1 : 0.073633 + f-1 : 0.061156 + f+2 : 0.085867 + f-2 : 0.012717 + f+3 : 0.050517 + f-3 : 0.052860 + 2 O s : 3.315138 s : 3.315138 + pz : 1.525028 p : 4.007167 + px : 1.388680 + py : 1.093459 + dz2 : 0.044430 d : 0.324877 + dxz : 0.116360 + dyz : 0.003890 + dx2y2 : 0.106904 + dxy : 0.053292 + f0 : 0.016841 f : 0.118068 + f+1 : 0.021319 + f-1 : 0.001839 + f+2 : 0.029584 + f-2 : 0.001752 + f+3 : 0.024728 + f-3 : 0.022005 + 3 H s : 0.621318 s : 0.621318 + pz : 0.134368 p : 0.554244 + px : 0.261707 + py : 0.158170 + dz2 : 0.039949 d : 0.395490 + dxz : 0.134156 + dyz : 0.002884 + dx2y2 : 0.093631 + dxy : 0.124870 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.3437 8.0000 -0.3437 1.9473 1.9473 0.0000 + 1 N 6.6562 7.0000 0.3438 2.5335 2.5335 -0.0000 + 2 O 8.2784 8.0000 -0.2784 1.7239 1.7239 0.0000 + 3 H 0.7217 1.0000 0.2783 0.9374 0.9374 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.9269 B( 0-O , 3-H ) : 0.9638 B( 1-N , 2-O ) : 1.6501 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.109 sec +Sum of individual times .... 0.712 sec ( 64.2%) + +Fock matrix formation .... 0.474 sec ( 42.8%) +Diagonalization .... 0.055 sec ( 5.0%) +Density matrix formation .... 0.004 sec ( 0.4%) +Population analysis .... 0.131 sec ( 11.8%) +Initial guess .... 0.010 sec ( 0.9%) +Orbital Transformation .... 0.000 sec ( 0.0%) +Orbital Orthonormalization .... 0.006 sec ( 0.5%) +DIIS solution .... 0.037 sec ( 3.3%) + +Maximum memory used throughout the entire SCF-calculation: 227.9 MB + + + ************************************************************ + * Program running with 30 parallel MPI-processes * + * working on a common directory * + ************************************************************ + + +-------------------------------------------------------------------------------- + ORCA-MATRIX DRIVEN CI +-------------------------------------------------------------------------------- + +-------------------------------- +AUTOMATIC CHOICE OF INCORE LEVEL +-------------------------------- + +Memory available ... 4950.00 MB +Memory needed for S+T ... 22.87 MB +Memory needed for J+K ... 45.83 MB +Memory needed for DIIS ... 320.13 MB +Memory needed for 3-ext ... 227.14 MB +Memory needed for 4-ext ... 1892.82 MB +Memory needed for triples ... 126.19 MB + -> Final InCoreLevel ... 5 + -> check shows that triples correction can be computed + + +Wavefunction type +----------------- +Correlation treatment ... CCSD +Single excitations ... ON +Orbital optimization ... OFF +Calculation of Z vector ... OFF +Calculation of Brueckner orbitals ... OFF +Perturbative triple excitations ... ON +Calculation of F12 correction ... OFF +Frozen core treatment ... chemical core (6 el) +Reference Wavefunction ... UHF + Alpha-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Beta-MOs occ : 3 ... 11 ( 9 MO's/ 9 electrons) + Alpha-MOs virt : 12 ... 160 (149 MO's ) + Beta-MOs virt : 12 ... 160 (149 MO's ) +Number of AO's ... 161 +Number of electrons ... 24 +Number of correlated electrons ... 18 + +Algorithmic settings +-------------------- +Integral transformation ... AO direct full transformation +K(C) Formation ... FULL-MO TRAFO +Maximum number of iterations ... 500 +Convergence tolerance (max. residuum) ... 1.000e-05 +Level shift for amplitude update ... 2.000e-01 +Maximum number of DIIS vectors ... 7 +DIIS turned on at iteration ... 0 +Damping before turning on DIIS ... 0.500 +Damping after turning on DIIS ... 0.000 +Pair specific amplitude update ... OFF +Natural orbital iterations ... OFF +Perturbative natural orbital generation ... OFF +Printlevel ... 2 + +Memory handling: +---------------- +Maximum memory for working arrays ... 4950 MB +Data storage in matrix containers ... UNCOMPRESSED +Data type for integral storage ... DOUBLE +In-Core Storage of quantities: + Amplitudes+Sigma Vector ... YES + J+K operators ... YES + DIIS vectors ... YES + 3-external integrals ... YES + 4-external integrals ... YES + + +Initializing the integral package ... done +Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 + +-------------------------- +UNRESTRICTED FOCK OPERATOR +-------------------------- + +Restoring SHARK [2] ... ok +Recanonicalizing the internal orbitals +Recanonicalizing the virtual orbitals +Time needed for Fock operator ... 0.204 sec +Reference energy ... -204.723581346 +Warning: for UHF the TrafoType has to be JK +Warning: for UHF the K(C)-option but must be AOX + +------------------------------- +PARTIAL EXCHANGE TRANSFORMATION +------------------------------- + +Transformation type ... two-operators +Generation of integrals (i,mue|j,nue) ... ON +Generation of integrals (mue,kappa|nue,tau)... ON +Generation of integrals (i,mue|a,nue) ... ON +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 ( 3- 11) +Number of internal beta-MOs ... 9 ( 3- 11) +Number of external alpha-MOs ... 149 ( 12- 160) +Number of external beta-MOs ... 149 ( 12- 160) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 25030 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + +Starting integral evaluation: + ... done with AO integral generation +Closing buffer AOK[aa] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[bb] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ab] ( 0.01 GB; CompressionRatio= 0.98) +Closing buffer AOK[ba] ( 0.01 GB; CompressionRatio= 0.98) +Collecting buffer AOK +Closing buffer IAAO1[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO1[ba] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[aa] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[bb] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ab] ( 0.13 GB; CompressionRatio= 1.00) +Closing buffer IAAO2[ba] ( 0.13 GB; CompressionRatio= 1.00) +Collecting buffer IAAO +Closing buffer PRQS ( 2.52 GB; CompressionRatio= 1.00) +Collecting buffer PRQS +Number of alpha/alpha MO pairs in trafo ... 45 +Number of beta /beta MO pairs in trafo ... 45 +Number of alpha/ beta MO pairs in trafo ... 81 +------------------------ +SORTING OF (i,mue|j,nue) +------------------------ + +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[aa] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[bb] ( 0.01 GB; CompressionRatio= 1.00) +Collecting buffer KAO +SORTING OF ALPHA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer KAO[ab] ( 0.02 GB; CompressionRatio= 0.999942135211) +Collecting buffer KAO[ab] +------------------------ +SORTING OF (i,mue|a,nue) +------------------------ + +Number of alpha/alpha (i,a) pairs in trafo ... 1341 +Number of beta /beta (i,a) pairs in trafo ... 1341 +Number of alpha/ beta (i,a) pairs in trafo ... 1341 +Number of beta /alpha (i,a) pairs in trafo ... 1341 +Setting up the alpha/alpha list ... done +Setting up the beta /beta list ... done +Setting up the alpha/beta list ... done +Setting up the beta /alpha list ... done + ... Now sorting (i,mue|a,nue)integrals + ... Integrals (i,b|a,c) will be made on the fly +SORTING OF ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[aa] 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA /BETA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[bb]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF ALPHA/BETA PAIRS (NMatSort_ab=45) +IBATCH = 1 of 1 +Closing buffer IPAQ[ab]( 0.22 GB; CompressionRatio= 1.00) +SORTING OF BETA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer IPAQ[ba]( 0.22 GB; CompressionRatio= 1.00) +N(AO-Batches) Done ... 57222 +N(AO-Batches) Skipped ... 0 +N(IJ)-pairs Skipped ... 0 +TOTAL TIME for half transformation ... 6.366 sec +AO-integral generation ... 0.141 sec +Half transformation ... 0.078 sec +K-integral sorting ... 5.371 sec +: +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Transformation type ... two-operators +Dimension of the basis ... 161 +Number of internal alpha-MOs ... 9 (3-11) +Number of internal beta-MOs ... 9 (3-11) +Pair cutoff ... 0.000e+00 Eh +Number of AO pairs included in the trafo ... 13041 +Total Number of distinct AO pairs ... 13041 +Memory devoted for trafo ... 4950.0 MB +Max. Number of MO pairs treated together ... 49751 +Max. Number of MOs treated per batch ... 309 +Number Format for Storage ... Double (8 Byte) +AO-integral source ... DIRECT +Integral package used ... LIBINT + +Starting integral evaluation: +: 251940 b 0 skpd 0.025 s ( 0.000 ms/b) +: 377910 b 0 skpd 0.024 s ( 0.000 ms/b) +: 277134 b 0 skpd 0.033 s ( 0.000 ms/b) +: 151164 b 0 skpd 0.040 s ( 0.000 ms/b) + 159120 b 0 skpd 0.016 s ( 0.000 ms/b) +: 218790 b 0 skpd 0.038 s ( 0.000 ms/b) +: 119340 b 0 skpd 0.029 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.022 s ( 0.000 ms/b) +: 87516 b 0 skpd 0.038 s ( 0.000 ms/b) +: 27846 b 0 skpd 0.022 s ( 0.001 ms/b) +Closing buffer AOJ[aa] ( 0.00 GB; CompressionRatio= 0.97) +Closing buffer AOJ[bb] ( 0.00 GB; CompressionRatio= 0.97) +Collecting buffer AOJ + ... done with AO integral generation +Number of Alpha-MO pairs included ... 45 +Number of Beta-MO pairs included ... 45 + ... Now sorting integrals +SORTING ALPHA/ALPHA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[aa] ( 0.00 GB; CompressionRatio= 1.00) +SORTING BETA/BETA PAIRS +IBATCH = 1 of 1 +Closing buffer JAO[bb] ( 0.00 GB; CompressionRatio= 1.00) +Collecting buffer JAO +TOTAL TIME for half transformation ... 0.353 sec +AO-integral generation ... 0.248 sec +Half transformation ... 0.041 sec +J-integral sorting ... 0.050 sec + +-------------------------- SECOND HALF TRANSFORMATION -------------------------- +Formation of (ij|kl),(ij|ka), (ij|ab) ... ok ( 0.152 sec) +Formation of (ik|jl),(ik|ja), (ia|jb) ... ok ( 0.251 sec) + + +----------------------- +SPIN UNRESTRICTED GUESS +----------------------- + +Spin-components of the MP2 energy: +EMP2(aa)= -0.090623612 +EMP2(bb)= -0.090623612 +EMP2(ab)= -0.516507026 + +Initial guess performed in 0.132 sec +E(0) ... -204.723581346 +E(MP2) ... -0.697754250 +Initial E(tot) ... -205.421335596 + ... 0.187985976 +Number of pairs included ... 153 + +------------------------------------------------ + UHF COUPLED CLUSTER ITERATIONS +------------------------------------------------ + +Number of amplitudes to be optimized ... 2598821 + +Iter E(tot) E(Corr) Delta-E Residual Time **1/2 + 0 -205.421335596 -0.697754250 -0.000000000 0.027390107 2.70 0.000000341 + *** Turning on DIIS *** + 1 -205.391994321 -0.668412975 0.029341275 0.012036049 2.72 0.058109055 + 2 -205.411498876 -0.687917529 -0.019504555 0.006060099 2.78 0.060998704 + 3 -205.415189012 -0.691607666 -0.003690137 0.002488052 2.83 0.075431946 + 4 -205.416757377 -0.693176031 -0.001568365 0.001608838 2.78 0.082313665 + 5 -205.417316125 -0.693734778 -0.000558748 0.000849594 2.90 0.088067478 + 6 -205.417427669 -0.693846323 -0.000111544 0.000498435 2.82 0.090865992 + 7 -205.417471423 -0.693890076 -0.000043753 0.000190405 2.89 0.092077854 + 8 -205.417482896 -0.693901550 -0.000011474 0.000098387 2.90 0.092508822 + 9 -205.417478806 -0.693897460 0.000004090 0.000025370 2.81 0.092631952 + 10 -205.417483038 -0.693901692 -0.000004232 0.000008817 2.79 0.092665194 + --- The Coupled-Cluster iterations have converged --- + +---------------------- +COUPLED CLUSTER ENERGY +---------------------- + +E(0) ... -204.723581346 +E(CORR) ... -0.693901692 +E(TOT) ... -205.417483038 +Singles norm **1/2 ... 0.092665194 ( 0.046332597, 0.046332597) +T1 diagnostic ... 0.021841396 + +------------------ +LARGEST AMPLITUDES +------------------ + 8a-> 13a 8b-> 13b 0.066634 + 10a-> 13a 10b-> 13b 0.054312 + 8a-> 13a -1a-> -1a 0.045597 + 8b-> 13b -1b-> -1b 0.045597 + 8a-> 13a 10b-> 13b 0.037001 + 10a-> 13a 8b-> 13b 0.037001 + 10a-> 13a -1a-> -1a 0.033118 + 10b-> 13b -1b-> -1b 0.033118 + 11a-> 26a 11b-> 26b 0.031622 + 11b-> 26b -1b-> -1b 0.030148 + 11a-> 26a -1a-> -1a 0.030148 + 11a-> 13a 11b-> 13b 0.027962 + 5a-> 13a 5b-> 13b 0.025407 + 10a-> 13a 11b-> 26b 0.025158 + 11a-> 26a 10b-> 13b 0.025158 + 8a-> 13a 8b-> 22b 0.024595 + +---------------------- +UHF TRIPLES CORRECTION (Algorithm 1) +---------------------- + +Multiplier for the singles contribution ... 1.000000000 + +SPIN-CASE Alpha-Alpha-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Alpha-Alpha-Beta: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +SPIN-CASE Beta-Beta-Alpha: +10% done +20% done +30% done +40% done +50% done +60% done +70% done +80% done +90% done + + +Triples Correction (T) ... -0.034764956 + alpha-alpha-alpha ... -0.000901648 ( 2.6%) + alpha-alpha-beta ... -0.016480830 ( 47.4%) + alpha-beta -beta ... -0.016480830 ( 47.4%) + beta -beta -beta ... -0.000901648 ( 2.6%) +Scaling of triples based on CCSD energies (Peterson et al. Molecular Physics 113, 1551 (2015)) +E(T*) = f*E(T) where f = E(F12-CCSD)/E(CCSD) +f = CCSD (with F12)/ CCSD (without F12) ... 1.000000000 +Scaled triples correction (T) ... -0.034764956 + +Final correlation energy ... -0.728666648 +E(CCSD) ... -205.417483038 +E(CCSD(T)) ... -205.452247994 + + + + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + ! Warning: Densities are linearized densities ! + !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! + +NORM = 1.209479516 sqrt= 1.099763391 +W(HF) = 0.826801931 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.mdcip +Input spin density ... input.mdcir +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.254440 -0.000000 + 1 N : 0.153531 0.000000 + 2 O : -0.164648 0.000000 + 3 H : 0.265556 0.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: -0.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.846915 s : 3.846915 + pz : 1.279703 p : 4.342786 + px : 1.322010 + py : 1.741073 + dz2 : 0.014769 d : 0.056259 + dxz : 0.009570 + dyz : 0.015154 + dx2y2 : 0.008907 + dxy : 0.007858 + f0 : 0.002365 f : 0.008479 + f+1 : 0.000889 + f-1 : 0.001800 + f+2 : 0.000974 + f-2 : 0.000668 + f+3 : 0.001093 + f-3 : 0.000690 + 1 N s : 3.879609 s : 3.879609 + pz : 0.921821 p : 2.762268 + px : 0.992849 + py : 0.847597 + dz2 : 0.038974 d : 0.175448 + dxz : 0.057894 + dyz : 0.025732 + dx2y2 : 0.014829 + dxy : 0.038019 + f0 : 0.008689 f : 0.029144 + f+1 : 0.003793 + f-1 : 0.006081 + f+2 : 0.004332 + f-2 : 0.001514 + f+3 : 0.001622 + f-3 : 0.003114 + 2 O s : 3.866805 s : 3.866805 + pz : 1.803144 p : 4.202184 + px : 1.156053 + py : 1.242987 + dz2 : 0.010339 d : 0.085223 + dxz : 0.024480 + dyz : 0.006531 + dx2y2 : 0.012351 + dxy : 0.031522 + f0 : 0.001650 f : 0.010437 + f+1 : 0.001566 + f-1 : 0.000865 + f+2 : 0.001804 + f-2 : 0.000631 + f+3 : 0.001313 + f-3 : 0.002608 + 3 H s : 0.633575 s : 0.633575 + pz : 0.023666 p : 0.081406 + px : 0.009829 + py : 0.047911 + dz2 : 0.000548 d : 0.019463 + dxz : 0.009755 + dyz : -0.000170 + dx2y2 : 0.000030 + dxy : 0.009301 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : -0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : -0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 1 N s : 0.000000 s : 0.000000 + pz : 0.000000 p : -0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : 0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : -0.000000 + f-3 : -0.000000 + 3 H s : 0.000000 s : 0.000000 + pz : -0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : 0.622312 -0.000000 + 1 N : -0.319366 0.000000 + 2 O : 0.267820 0.000000 + 3 H : -0.570766 -0.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.120230 s : 3.120230 + pz : 1.224920 p : 3.837339 + px : 1.237449 + py : 1.374970 + dz2 : 0.134391 d : 0.324379 + dxz : 0.073423 + dyz : 0.050214 + dx2y2 : 0.050002 + dxy : 0.016349 + f0 : 0.033703 f : 0.095740 + f+1 : 0.024022 + f-1 : 0.014903 + f+2 : 0.009140 + f-2 : 0.007393 + f+3 : 0.005248 + f-3 : 0.001331 + 1 N s : 3.006668 s : 3.006668 + pz : 0.957023 p : 2.882025 + px : 1.166999 + py : 0.758003 + dz2 : 0.227084 d : 0.982386 + dxz : 0.330644 + dyz : 0.100571 + dx2y2 : 0.183997 + dxy : 0.140090 + f0 : 0.121507 f : 0.448287 + f+1 : 0.073982 + f-1 : 0.058063 + f+2 : 0.079473 + f-2 : 0.012594 + f+3 : 0.050973 + f-3 : 0.051695 + 2 O s : 3.316928 s : 3.316928 + pz : 1.471847 p : 3.931909 + px : 1.381415 + py : 1.078647 + dz2 : 0.050331 d : 0.356571 + dxz : 0.118408 + dyz : 0.010096 + dx2y2 : 0.111533 + dxy : 0.066204 + f0 : 0.017052 f : 0.126771 + f+1 : 0.022139 + f-1 : 0.002636 + f+2 : 0.029302 + f-2 : 0.002635 + f+3 : 0.025553 + f-3 : 0.027454 + 3 H s : 0.623593 s : 0.623593 + pz : 0.135912 p : 0.562160 + px : 0.264001 + py : 0.162247 + dz2 : 0.041134 d : 0.385013 + dxz : 0.129514 + dyz : 0.003242 + dx2y2 : 0.093185 + dxy : 0.117938 + +SPIN + 0 O s : -0.000000 s : -0.000000 + pz : -0.000000 p : -0.000000 + px : 0.000000 + py : -0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : -0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : 0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : -0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : -0.000000 + 1 N s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : 0.000000 + py : 0.000000 + dz2 : -0.000000 d : -0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : -0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 2 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : 0.000000 + dxz : 0.000000 + dyz : 0.000000 + dx2y2 : 0.000000 + dxy : -0.000000 + f0 : -0.000000 f : 0.000000 + f+1 : -0.000000 + f-1 : 0.000000 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : -0.000000 + f-3 : 0.000000 + 3 H s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.000000 + px : -0.000000 + py : 0.000000 + dz2 : 0.000000 d : -0.000000 + dxz : -0.000000 + dyz : -0.000000 + dx2y2 : -0.000000 + dxy : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.2544 8.0000 -0.2544 2.3137 1.8527 0.4610 + 1 N 6.8465 7.0000 0.1535 2.8246 2.3500 0.4745 + 2 O 8.1646 8.0000 -0.1646 2.1270 1.6310 0.4960 + 3 H 0.7344 1.0000 0.2656 0.9589 0.8890 0.0699 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-N ) : 0.8624 B( 0-O , 3-H ) : 0.8904 B( 1-N , 2-O ) : 1.5101 + + + + +-------------------------------------------------------------------------------- + TIMINGS +-------------------------------------------------------------------------------- + + +Total execution time ... 46.203 sec + +Fock Matrix Formation ... 0.204 sec ( 0.4%) +Initial Guess ... 0.132 sec ( 0.3%) +DIIS Solver ... 1.339 sec ( 2.9%) +State Vector Update ... 0.064 sec ( 0.1%) +Sigma-vector construction ... 29.524 sec ( 63.9%) + <0|H|D> ... 0.003 sec ( 0.0% of sigma) + (0-ext Fock) ... 0.019 sec ( 0.1% of sigma) + (0-ext) ... 0.054 sec ( 0.2% of sigma) + (2-ext Fock) ... 0.020 sec ( 0.1% of sigma) + (2-ext) ... 0.734 sec ( 2.5% of sigma) + (4-ext) ... 16.452 sec ( 55.7% of sigma) + ... 1.056 sec ( 3.6% of sigma) + ... 0.002 sec ( 0.0% of sigma) + (1-ext) ... 0.006 sec ( 0.0% of sigma) + (1-ext) ... 0.088 sec ( 0.3% of sigma) + Fock-dressing ... 1.614 sec ( 5.5% of sigma) + (ik|jl)-dressing ... 0.058 sec ( 0.2% of sigma) + (ij|ab),(ia|jb)-dressing ... 7.339 sec ( 24.9% of sigma) + Pair energies ... 0.004 sec ( 0.0% of sigma) +Total Time for computing (T) ... 6.811 sec ( 14.7% of ALL) + I/O of integral and amplitudes ... 0.792 sec ( 11.6% of (T)) + External N**7 contributions ... 3.905 sec ( 57.3% of (T)) + Internal N**7 contributions ... 0.310 sec ( 4.6% of (T)) + N**6 triples energy contributions ... 1.721 sec ( 25.3% of (T)) + + +Maximum memory used throughout the entire MDCI-calculation: 3047.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.452247994122 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +Storing optimized geometry in input.045.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.045.gbw ... done + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.725028, -0.038110 -0.334312) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.61774 -0.10604 -0.77319 +Nuclear contribution : -1.50497 0.09039 0.76881 + ----------------------------------------- +Total Dipole Moment : -0.88724 -0.01566 -0.00438 + ----------------------------------------- +Magnitude (a.u.) : 0.88739 +Magnitude (Debye) : 2.25556 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.084046 0.418807 0.368733 +Rotational constants in MHz : 92457.386600 12555.506303 11054.350262 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.646166 -0.608215 -0.000000 +x,y,z [Debye]: 1.642425 -1.545959 -0.000000 + + + + *** MDCI DENSITY *** + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.mdcip +The origin for moment calculation is the CENTER OF MASS = ( 0.725028, -0.038110 -0.334312) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: 0.78892 -0.09529 -0.72099 +Nuclear contribution : -1.50497 0.09039 0.76881 + ----------------------------------------- +Total Dipole Moment : -0.71605 -0.00490 0.04782 + ----------------------------------------- +Magnitude (a.u.) : 0.71767 +Magnitude (Debye) : 1.82416 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.084046 0.418807 0.368733 +Rotational constants in MHz : 92457.386600 12555.506303 11054.350262 + + Dipole components along the rotational axes: +x,y,z [a.u.] : 0.556807 -0.452782 0.000000 +x,y,z [Debye]: 1.415290 -1.150880 0.000000 + + + **** RELAXED SURFACE SCAN DONE *** + + SUMMARY OF THE CALCULATED SURFACE + +---------------------------- +RELAXED SURFACE SCAN RESULTS +---------------------------- + +Column 1: NONAME + +The Calculated Surface using the 'Actual Energy' + -180.00000000 -205.45224799 + -171.81818182 -205.45190811 + -163.63636364 -205.45091275 + -155.45454545 -205.44933274 + -147.27272727 -205.44728671 + -139.09090909 -205.44492690 + -130.90909091 -205.44243238 + -122.72727273 -205.43999284 + -114.54545455 -205.43779528 + -106.36363636 -205.43600588 + -98.18181818 -205.43475700 + -90.00000000 -205.43414239 + -81.81818182 -205.43420969 + -73.63636364 -205.43496112 + -65.45454545 -205.43635120 + -57.27272727 -205.43828268 + -49.09090909 -205.44061138 + -40.90909091 -205.44315299 + -32.72727273 -205.44569266 + -24.54545455 -205.44800238 + -16.36363636 -205.44985630 + -8.18181818 -205.45106460 + 0.00000000 -205.45148293 + 8.18181818 -205.45106459 + 16.36363636 -205.44985629 + 24.54545455 -205.44800238 + 32.72727273 -205.44569265 + 40.90909091 -205.44315298 + 49.09090909 -205.44061136 + 57.27272727 -205.43828268 + 65.45454545 -205.43635116 + 73.63636364 -205.43496113 + 81.81818182 -205.43420969 + 90.00000000 -205.43414239 + 98.18181818 -205.43475700 + 106.36363636 -205.43600587 + 114.54545455 -205.43779528 + 122.72727273 -205.43999284 + 130.90909091 -205.44243239 + 139.09090909 -205.44492691 + 147.27272727 -205.44728671 + 155.45454545 -205.44933274 + 163.63636364 -205.45091284 + 171.81818182 -205.45190811 + 180.00000000 -205.45224799 + +The Calculated Surface using the SCF energy + -180.00000000 -204.72358091 + -171.81818182 -204.72322997 + -163.63636364 -204.72219114 + -155.45454545 -204.72055780 + -147.27272727 -204.71843969 + -139.09090909 -204.71599639 + -130.90909091 -204.71341641 + -122.72727273 -204.71087518 + -114.54545455 -204.70858706 + -106.36363636 -204.70673062 + -98.18181818 -204.70547162 + -90.00000000 -204.70490620 + -81.81818182 -204.70512069 + -73.63636364 -204.70609581 + -65.45454545 -204.70769592 + -57.27272727 -204.70999217 + -49.09090909 -204.71261905 + -40.90909091 -204.71542428 + -32.72727273 -204.71818669 + -24.54545455 -204.72066761 + -16.36363636 -204.72264771 + -8.18181818 -204.72392079 + 0.00000000 -204.72436350 + 8.18181818 -204.72392282 + 16.36363636 -204.72264887 + 24.54545455 -204.72066789 + 32.72727273 -204.71819396 + 40.90909091 -204.71542654 + 49.09090909 -204.71262233 + 57.27272727 -204.71000112 + 65.45454545 -204.70768462 + 73.63636364 -204.70609970 + 81.81818182 -204.70511891 + 90.00000000 -204.70491177 + 98.18181818 -204.70547011 + 106.36363636 -204.70673365 + 114.54545455 -204.70858680 + 122.72727273 -204.71087854 + 130.90909091 -204.71341297 + 139.09090909 -204.71599684 + 147.27272727 -204.71844417 + 155.45454545 -204.72055559 + 163.63636364 -204.72218551 + 171.81818182 -204.72322884 + 180.00000000 -204.72358176 + +The Calculated Surface using the MDCI energy + -180.00000000 -205.45224799 + -171.81818182 -205.45190811 + -163.63636364 -205.45091275 + -155.45454545 -205.44933274 + -147.27272727 -205.44728671 + -139.09090909 -205.44492690 + -130.90909091 -205.44243238 + -122.72727273 -205.43999284 + -114.54545455 -205.43779528 + -106.36363636 -205.43600588 + -98.18181818 -205.43475700 + -90.00000000 -205.43414239 + -81.81818182 -205.43420969 + -73.63636364 -205.43496112 + -65.45454545 -205.43635120 + -57.27272727 -205.43828268 + -49.09090909 -205.44061138 + -40.90909091 -205.44315299 + -32.72727273 -205.44569266 + -24.54545455 -205.44800238 + -16.36363636 -205.44985630 + -8.18181818 -205.45106460 + 0.00000000 -205.45148293 + 8.18181818 -205.45106459 + 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modules: + +Sum of individual times ... 503704.936 sec (=8395.082 min) +GTO integral calculation ... 188.487 sec (= 3.141 min) 0.0 % +SCF iterations ... 597.207 sec (= 9.953 min) 0.1 % +MDCI module ... 14103.571 sec (= 235.060 min) 2.8 % +SCF Gradient evaluation ... 68966.667 sec (=1149.444 min) 13.7 % +Geometry relaxation ... 2.857 sec (= 0.048 min) 0.0 % +Numerical frequency calculation ... 419846.147 sec (=6997.436 min) 83.4 % + ****ORCA TERMINATED NORMALLY**** +TOTAL RUN TIME: 5 days 12 hours 39 minutes 39 seconds 29 msec diff --git a/arc/testing/rotor_scans/orca/dft.txt b/arc/testing/rotor_scans/orca/dft.txt new file mode 100644 index 0000000000..8368441dc8 --- /dev/null +++ b/arc/testing/rotor_scans/orca/dft.txt @@ -0,0 +1,112016 @@ + + ***************** + * O R C A * + ***************** + + #, + ### + #### + ##### + ###### + ########, + ,,################,,,,, + ,,#################################,, + ,,##########################################,, + ,#########################################, ''#####, + ,#############################################,, '####, + ,##################################################,,,,####, + ,###########'''' ''''############################### + ,#####'' ,,,,##########,,,, '''####''' '#### + ,##' ,,,,###########################,,, '## + ' ,,###'''' '''############,,, + ,,##'' '''############,,,, ,,,,,,###'' + ,#'' '''#######################''' + ' ''''####'''' + ,#######, #######, ,#######, ## + ,#' '#, ## ## ,#' '#, #''# ,####, ,####, + ## ## ## ,#' ## #' '# #' #' '# + ## ## ####### ## ,######, #####, # # + '#, ,#' ## ## '#, ,#' ,# #, #, # #, ,# + '#######' ## ## '#######' #' '# '####' # '####' + + + + ######################################################### + # -***- # + # Department of theory and spectroscopy # + # # + # Frank Neese # + # # + # Directorship, Architecture, Infrastructure # + # SHARK, DRIVERS # + # Core code/Algorithms in most modules # + # # + # Max Planck Institute fuer Kohlenforschung # + # Kaiser Wilhelm Platz 1 # + # D-45470 Muelheim/Ruhr # + # Germany # + # # + # All rights reserved # + # -***- # + ######################################################### + + + Program Version 6.0.0 - RELEASE - + + + With contributions from (in alphabetic order): + Daniel Aravena : Magnetic Suceptibility + Michael Atanasov : Ab Initio Ligand Field Theory (pilot matlab implementation) + Alexander A. Auer : GIAO ZORA, VPT2 properties, NMR spectrum + Ute Becker : All parallelization in ORCA, NUMFREQ, NUMCALC + Giovanni Bistoni : ED, misc. LED, open-shell LED, HFLD + Martin Brehm : Molecular dynamics + Dmytro Bykov : pre 5.0 version of the SCF Hessian + Marcos Casanova-Páez : Triplet and SCS-CIS(D). UHF-(DLPNO)-IP/EA/STEOM-CCSD. UHF-CVS-IP/STEOM-CCSD + Vijay G. Chilkuri : MRCI spin determinant printing, contributions to CSF-ICE + Pauline Colinet : FMM embedding + Dipayan Datta : RHF DLPNO-CCSD density + Achintya Kumar Dutta : EOM-CC, STEOM-CC + Nicolas Foglia : Exact transition moments, OPA infrastructure, MCD improvements + Dmitry Ganyushin : Spin-Orbit,Spin-Spin,Magnetic field MRCI + Miquel Garcia : C-PCM and meta-GGA Hessian, CCSD/C-PCM, Gaussian charge scheme + Tiago L. C. Gouveia : GS-ROHF, GS-ROCIS + Yang Guo : DLPNO-NEVPT2, F12-NEVPT2, CIM, IAO-localization + Andreas Hansen : Spin unrestricted coupled pair/coupled cluster methods + Ingolf Harden : AUTO-CI MPn and infrastructure + Benjamin Helmich-Paris : MC-RPA, TRAH-(SCF,CASSCF), AVAS, COSX integrals, SCF dyn. polar. + Lee Huntington : MR-EOM, pCC + Robert Izsak : Overlap fitted RIJCOSX, COSX-SCS-MP3, EOM + Riya Kayal : Wick's Theorem for AUTO-CI, AUTO-CI UHF-CCSDT + Emily Kempfer : AUTO-CI, RHF CISDT and CCSDT + Christian Kollmar : KDIIS, OOCD, Brueckner-CCSD(T), CCSD density, CASPT2, CASPT2-K, improved NEVPT2 + Axel Koslowski : Symmetry handling + Simone Kossmann : Meta GGA functionals, TD-DFT gradient, OOMP2, (MP2 Hessian; deprecated post 5.0) + Lucas Lang : DCDCAS + Marvin Lechner : AUTO-CI (C++ implementation), FIC-MRCC + Spencer Leger : CASSCF response + Dagmar Lenk : GEPOL surface, SMD, ORCA-2-JSON + Dimitrios Liakos : Extrapolation schemes; Compound Job, initial MDCI parallelization + Dimitrios Manganas : Further ROCIS development; embedding schemes. LFT, Crystal Embedding + Dimitrios Pantazis : SARC Basis sets + Anastasios Papadopoulos: AUTO-CI, single reference methods and gradients + Taras Petrenko : pre 6.0 DFT Hessian and TD-DFT gradient, (ASA, deprecated), ECA, 1-Electron XAS/XES, NRVS + Peter Pinski : DLPNO-MP2, DLPNO-MP2 Gradient + Christoph Reimann : Effective Core Potentials + Marius Retegan : Local ZFS, SOC + Christoph Riplinger : Optimizer, TS searches, QM/MM, DLPNO-CCSD(T), (RO)-DLPNO pert. Triples + Michael Roemelt : Original ROCIS implementation + Masaaki Saitow : Open-shell DLPNO-CCSD energy and density + Barbara Sandhoefer : DKH picture change effects + Kantharuban Sivalingam : CASSCF convergence/infrastructure, NEVPT2 and variants, FIC-MRCI + Bernardo de Souza : ESD, SOC TD-DFT + Georgi Stoychev : AutoAux, RI-MP2 NMR, DLPNO-MP2 response, X2C + Van Anh Tran : RI-MP2 g-tensors + Willem Van den Heuvel : Paramagnetic NMR + Zikuan Wang : NOTCH, Electric field optimization + Frank Wennmohs : Technical directorship and infrastructure + Hang Xu : AUTO-CI-Response properties + + + We gratefully acknowledge several colleagues who have allowed us to + interface, adapt or use parts of their codes: + Stefan Grimme, W. Hujo, H. Kruse, P. Pracht, : VdW corrections, initial TS optimization, + C. Bannwarth, S. Ehlert, DFT functionals, gCP, sTDA/sTD-DF + L. Wittmann, M. Mueller + Ed Valeev, F. Pavosevic, A. Kumar : LibInt (2-el integral package), F12 methods + Garnet Chan, S. Sharma, J. Yang, R. Olivares : DMRG + Ulf Ekstrom : XCFun DFT Library + Mihaly Kallay : mrcc (arbitrary order and MRCC methods) + Frank Weinhold : gennbo (NPA and NBO analysis) + Simon Mueller : openCOSMO-RS + Christopher J. Cramer and Donald G. Truhlar : smd solvation model + Lars Goerigk : TD-DFT with DH, B97 family of functionals + V. Asgeirsson, H. Jonsson : NEB implementation + FAccTs GmbH : IRC, NEB, NEB-TS, DLPNO-Multilevel, CI-OPT + MM, QMMM, 2- and 3-layer-ONIOM, Crystal-QMMM, + LR-CPCM, SF, NACMEs, symmetry and pop. for TD-DFT, + nearIR, NL-DFT gradient (VV10), updates on ESD, + ML-optimized integration grids, MBIS, APM, + GOAT, DOCKER, SOLVATOR, interface openCOSMO-RS + S Lehtola, MJT Oliveira, MAL Marques : LibXC Library + Liviu Ungur et al : ANISO software + + + Your calculation uses the libint2 library for the computation of 2-el integrals + For citations please refer to: http://libint.valeyev.net + + Your ORCA version has been built with support for libXC version: 6.2.2 + For citations please refer to: https://libxc.gitlab.io + + This ORCA versions uses: + CBLAS interface : Fast vector & matrix operations + LAPACKE interface : Fast linear algebra routines + SCALAPACK package : Parallel linear algebra routines + Shared memory : Shared parallel matrices + BLAS/LAPACK : OpenBLAS 0.3.27 USE64BITINT DYNAMIC_ARCH NO_AFFINITY Cooperlake SINGLE_THREADED + Core in use : Cooperlake + Copyright (c) 2011-2014, The OpenBLAS Project + + +NOTE: MaxCore=5900 MB was set to SCF,MP2,MDCI,CIPSI,MRCI and CIS + => If you want to overwrite this, your respective input block should be placed after the MaxCore statement +Your calculation utilizes the geometrical counterpoise correction gCP +Please cite in your paper: +H.Kruse, S. Grimme J.Chem.Phys., 136, (2012), 154101 + + +Your calculation utilizes the atom-pairwise dispersion correction +based on EEQ partial charges (D4) + + +================================================================================ + +----- Orbital basis set information ----- +Your calculation utilizes the basis: def2-mTZVPP + Stefan Grimme, Andreas Hansen, Sebastian Ehlert, and Jan-Michael Mewes + J. Chem. Phys. 154, 064103 (2021). DOI: 10.1063/5.0040021 + +----- AuxJ basis set information ----- +Your calculation utilizes the basis: def2-mTZVPP/J + Stefan Grimme, Andreas Hansen, Sebastian Ehlert, and Jan-Michael Mewes + J. Chem. Phys. 154, 000000 (2021). DOI: 10.1063/5.0040021 + +================================================================================ + WARNINGS + Please study these warnings very carefully! +================================================================================ + +Using LibXC functional ID 497 : Re-regularized SCAN exchange by Furness et al +[ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020) +[ 2] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020) +Using LibXC functional ID 498 : Re-regularized SCAN correlation by Furness et al +[ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020) +[ 2] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020) +Using LibXC functional ID 497 : Re-regularized SCAN exchange by Furness et al +[ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020) +[ 2] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020) +Using LibXC functional ID 498 : Re-regularized SCAN correlation by Furness et al +[ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020) +[ 2] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020) + +WARNING: Geometry Optimization + ===> : Switching off AutoStart + For restart on a previous wavefunction, please use MOREAD + +================================================================================ + INPUT FILE +================================================================================ +NAME = input.in +| 1> !r2scan-3c +| 2> !Opt +| 3> +| 4> %maxcore 5900 +| 5> %pal # job parallelization settings +| 6> nprocs 50 +| 7> end +| 8> %scf # recommended SCF settings +| 9> MaxIter 1500 +| 10> end +| 11> %geom Scan +| 12> D 3 0 1 2 = -180.0, 180.0, 40.0 +| 13> end +| 14> MaxIter = 100 +| 15> end +| 16> +| 17> * xyz 0 1 +| 18> N -0.604982 -0.409253 0.021313 +| 19> O 0.475766 0.307274 -0.016252 +| 20> O 0.304442 1.594051 -0.050864 +| 21> H -0.193934 -1.354228 0.042095 +| 22> * +| 23> +| 24> +| 25> ****END OF INPUT**** +================================================================================ + + ****************************** + * Relaxed Surface Scan * + ****************************** + + Dihedral ( 2, 1, 0, 3): range= -180.00000000 .. 180.00000000 steps = 40 + +There is 1 parameter to be scanned. +There will be 40 constrained geometry optimizations. + + + ************************************************************* + * RELAXED SURFACE SCAN STEP 1 * + * * + * Dihedral ( 2, 1, 0, 3) : -180.00000000 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2972 0.704695 + 2. B(O 2,O 1) 1.2986 0.701206 + 3. B(H 3,N 0) 1.0307 0.401003 + 4. A(O 1,N 0,H 3) 100.0635 0.359568 + 5. A(N 0,O 1,O 2) 115.9878 0.442256 + 6. D(O 2,O 1,N 0,H 3) -180.0000 0.038863 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.604983 -0.409254 0.021271 + O 0.475765 0.307272 -0.016314 + O 0.304443 1.594052 -0.050815 + H -0.193933 -1.354226 0.042151 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.143252 -0.773378 0.040195 + 1 O 8.0000 0 15.999 0.899066 0.580660 -0.030830 + 2 O 8.0000 0 15.999 0.575313 3.012323 -0.096027 + 3 H 1.0000 0 1.008 -0.366480 -2.559117 0.079654 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.297242579650 0.00000000 0.00000000 + O 2 1 0 1.298593451104 115.98776376 0.00000000 + H 1 2 3 1.030713393943 100.06349274 179.98870651 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.451433204801 0.00000000 0.00000000 + O 2 1 0 2.453985981889 115.98776376 0.00000000 + H 1 2 3 1.947766037116 100.06349274 179.98870651 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1668 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.757065644581 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.732e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.001 sec +Total time needed ... 0.003 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22300 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5575 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.6 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.7570656446 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 50 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +------------------------------ +INITIAL GUESS: MODEL POTENTIAL +------------------------------ +Loading Hartree-Fock densities ... done +Calculating cut-offs ... done +Initializing the effective Hamiltonian ... done +Setting up the integral package (SHARK) ... done +Starting the Coulomb interaction ... done ( 0.0 sec) +Making the grid ... done ( 0.0 sec) +Mapping shells ... done +Starting the XC term evaluation ... done ( 0.0 sec) + promolecular density results + # of electrons = 23.999676665 + EX = -23.037230292 + EC = -0.802808331 + EX+EC = -23.840038623 +Transforming the Hamiltonian ... done ( 0.0 sec) +Diagonalizing the Hamiltonian ... done ( 0.0 sec) +Back transforming the eigenvectors ... done ( 0.1 sec) +Now organizing SCF variables ... done + ------------------ + INITIAL GUESS DONE ( 0.3 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 1.0 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.4656601293092706 0.00e+00 3.96e-03 5.78e-02 3.09e-01 0.700 0.5 +Warning: op=0 Small HOMO/LUMO gap ( 0.068) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5223623602157943 -5.67e-02 1.70e-03 1.77e-02 6.75e-02 0.700 0.6 + ***Turning on AO-DIIS*** + 3 -205.5358113936318603 -1.34e-02 8.23e-04 9.10e-03 3.65e-02 0.700 0.4 + 4 -205.5458199182110377 -1.00e-02 1.73e-03 2.27e-02 3.31e-02 0.000 0.4 + 5 -205.5704511951624056 -2.46e-02 3.19e-04 5.19e-03 5.34e-03 0.000 0.2 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 6 -205.5705750022565610 -1.24e-04 1.61e-04 2.90e-03 1.88e-03 0.2 + *** Restarting incremental Fock matrix formation *** + 7 -205.5705808048847700 -5.80e-06 3.80e-04 7.00e-03 1.88e-03 0.7 + 8 -205.5702603168219582 3.20e-04 3.18e-04 5.63e-03 1.02e-02 0.1 + 9 -205.5705925718203559 -3.32e-04 2.01e-05 4.28e-04 1.82e-04 0.3 + 10 -205.5705917732310297 7.99e-07 1.44e-05 2.80e-04 5.03e-04 0.3 + 11 -205.5705927303468741 -9.57e-07 2.36e-06 3.73e-05 1.32e-05 0.2 + 12 -205.5705927322309492 -1.88e-09 8.97e-07 1.32e-05 7.72e-06 0.2 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57059273223095 Eh -5593.86021 eV + +Components: +Nuclear Repulsion : 69.75706564458082 Eh 1898.18626 eV +Electronic Energy : -275.32765837681177 Eh -7492.04647 eV +One Electron Energy: -419.25100412843921 Eh -11408.39981 eV +Two Electron Energy: 143.92334575162741 Eh 3916.35334 eV + +Virial components: +Potential Energy : -410.38862081494483 Eh -11167.24210 eV +Kinetic Energy : 204.81802808271388 Eh 5573.38189 eV +Virial Ratio : 2.00367430863661 + +DFT components: +N(Alpha) : 11.999998343561 electrons +N(Beta) : 11.999998343561 electrons +N(Total) : 23.999996687121 electrons +E(X) : -23.343393288862 Eh +E(C) : -0.804154787067 Eh +E(XC) : -24.147548075930 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.8841e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.3198e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 8.9702e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.8818e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 7.7245e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 4.6175e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.192594 -522.2570 + 1 2.0000 -19.017887 -517.5030 + 2 2.0000 -14.270901 -388.3310 + 3 2.0000 -1.251010 -34.0417 + 4 2.0000 -0.969117 -26.3710 + 5 2.0000 -0.700313 -19.0565 + 6 2.0000 -0.565756 -15.3950 + 7 2.0000 -0.519252 -14.1296 + 8 2.0000 -0.505699 -13.7608 + 9 2.0000 -0.330352 -8.9893 + 10 2.0000 -0.287621 -7.8266 + 11 2.0000 -0.259879 -7.0717 + 12 0.0000 -0.179977 -4.8974 + 13 0.0000 0.050056 1.3621 + 14 0.0000 0.081271 2.2115 + 15 0.0000 0.138172 3.7599 + 16 0.0000 0.218392 5.9427 + 17 0.0000 0.277622 7.5545 + 18 0.0000 0.296591 8.0706 + 19 0.0000 0.324712 8.8359 + 20 0.0000 0.366368 9.9694 + 21 0.0000 0.382512 10.4087 + 22 0.0000 0.396449 10.7879 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.277563 + 1 O : 0.219483 + 2 O : -0.204584 + 3 H : 0.262665 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.887514 s : 3.887514 + pz : 1.092744 p : 3.328300 + px : 1.174396 + py : 1.061160 + dz2 : 0.007943 d : 0.061749 + dxz : 0.017764 + dyz : 0.004756 + dx2y2 : 0.010960 + dxy : 0.020327 + + 1 O s : 3.751387 s : 3.751387 + pz : 1.384551 p : 3.886034 + px : 1.446411 + py : 1.055071 + dz2 : 0.004601 d : 0.143096 + dxz : 0.013030 + dyz : 0.043972 + dx2y2 : 0.028976 + dxy : 0.052518 + + 2 O s : 3.948002 s : 3.948002 + pz : 1.421678 p : 4.229631 + px : 1.904380 + py : 0.903573 + dz2 : 0.001895 d : 0.026951 + dxz : 0.000304 + dyz : 0.013740 + dx2y2 : 0.008596 + dxy : 0.002417 + + 3 H s : 0.707571 s : 0.707571 + pz : 0.006447 p : 0.029764 + px : 0.006964 + py : 0.016353 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.055983 + 1 O : -0.189523 + 2 O : -0.032324 + 3 H : 0.277831 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.364293 s : 3.364293 + pz : 1.013678 p : 3.374656 + px : 1.271158 + py : 1.089819 + dz2 : 0.040263 d : 0.317034 + dxz : 0.043302 + dyz : 0.024952 + dx2y2 : 0.120875 + dxy : 0.087643 + + 1 O s : 3.369384 s : 3.369384 + pz : 1.277358 p : 4.037067 + px : 1.501455 + py : 1.258254 + dz2 : 0.062867 d : 0.783073 + dxz : 0.036945 + dyz : 0.182900 + dx2y2 : 0.257348 + dxy : 0.243013 + + 2 O s : 3.600364 s : 3.600364 + pz : 1.341634 p : 4.176238 + px : 1.782447 + py : 1.052157 + dz2 : 0.030226 d : 0.255722 + dxz : 0.000852 + dyz : 0.064453 + dx2y2 : 0.073521 + dxy : 0.086671 + + 3 H s : 0.647742 s : 0.647742 + pz : 0.014147 p : 0.074427 + px : 0.019130 + py : 0.041149 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2776 7.0000 -0.2776 2.7321 2.7321 -0.0000 + 1 O 7.7805 8.0000 0.2195 2.6660 2.6660 -0.0000 + 2 O 8.2046 8.0000 -0.2046 1.7479 1.7479 0.0000 + 3 H 0.7373 1.0000 0.2627 0.9185 0.9185 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3916 B( 0-N , 2-O ) : 0.4598 B( 0-N , 3-H ) : 0.8807 +B( 1-O , 2-O ) : 1.2624 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 5 sec + +Total time .... 5.428 sec +Sum of individual times .... 5.096 sec ( 93.9%) + +SCF preparation .... 0.524 sec ( 9.6%) +Fock matrix formation .... 2.437 sec ( 44.9%) + Startup .... 0.258 sec ( 10.6% of F) + Split-RI-J .... 0.063 sec ( 2.6% of F) + XC integration .... 0.512 sec ( 21.0% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.018 sec ( 3.5% of XC) + Density eval. .... 0.024 sec ( 4.6% of XC) + XC-Functional eval. .... 0.014 sec ( 2.7% of XC) + XC-Potential eval. .... 0.026 sec ( 5.1% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.896 sec ( 16.5%) +Total Energy calculation .... 0.028 sec ( 0.5%) +Population analysis .... 0.301 sec ( 5.5%) +Orbital Transformation .... 0.285 sec ( 5.2%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.413 sec ( 7.6%) +SOSCF solution .... 0.213 sec ( 3.9%) +Finished LeanSCF after 5.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 5.0 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360054 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007228054 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.563724732633 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000775 -0.000007106 0.000000217 + 2 O : 0.000000687 0.000000155 -0.000000015 + 3 O : 0.000002450 0.000009249 -0.000000306 + 4 H : -0.000002363 -0.000002298 0.000000103 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000124164 +RMS gradient ... 0.0000035843 +MAX gradient ... 0.0000092494 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.012058432 -0.005517320 0.000337861 + 2 O : 0.017523320 -0.004959746 -0.000133747 + 3 O : -0.004881204 0.008845084 -0.000169039 + 4 H : -0.000583683 0.001631983 -0.000035075 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000298404 -0.0000117938 0.0000483737 + +Norm of the Cartesian gradient ... 0.0247535852 +RMS gradient ... 0.0071457445 +MAX gradient ... 0.0175233196 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.249 sec + +Densities .... 0.001 sec ( 0.3%) +One electron gradient .... 0.008 sec ( 3.1%) +RI-J Coulomb gradient .... 0.056 sec ( 22.4%) +XC gradient .... 0.016 sec ( 6.4%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.563724733 Eh +Current gradient norm .... 0.024753585 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999532712 +Lowest eigenvalues of augmented Hessian: + -0.000544895 0.359568289 0.401010812 0.442438586 0.701324373 +Length of the computed step .... 0.030581540 +The final length of the internal step .... 0.030581540 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0124848615 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0085959531 RMS(Int)= 0.0124645584 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0074564054 0.0001000000 NO + MAX gradient 0.0126923356 0.0003000000 NO + RMS step 0.0124848615 0.0020000000 NO + MAX step 0.0203104309 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0095 Max(Angles) 1.16 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2972 0.012692 -0.0095 1.2877 + 2. B(O 2,O 1) 1.2986 0.009411 -0.0071 1.2915 + 3. B(H 3,N 0) 1.0307 -0.001733 0.0023 1.0330 + 4. A(O 1,N 0,H 3) 100.06 -0.000214 0.03 100.10 + 5. A(N 0,O 1,O 2) 115.99 -0.008993 1.16 117.15 + 6. D(O 2,O 1,N 0,H 3) -180.00 0.000012 0.00 -180.00 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.700 %) +Internal coordinates : 0.000 s ( 0.216 %) +B/P matrices and projection : 0.000 s ( 1.039 %) +Hessian update/contruction : 0.000 s ( 1.133 %) +Making the step : 0.000 s ( 0.577 %) +Converting the step to Cartesian: 0.000 s ( 0.296 %) +Storing new data : 0.000 s ( 0.209 %) +Checking convergence : 0.000 s ( 0.014 %) +Final printing : 0.013 s (95.780 %) +Total time : 0.014 s + +Time for energy+gradient : 10.465 s +Time for complete geometry iter : 11.669 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.605206 -0.408673 0.021257 + O 0.463336 0.308989 -0.016170 + O 0.311318 1.591040 -0.050836 + H -0.188157 -1.353512 0.042040 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.143673 -0.772279 0.040170 + 1 O 8.0000 0 15.999 0.875578 0.583905 -0.030556 + 2 O 8.0000 0 15.999 0.588307 3.006629 -0.096065 + 3 H 1.0000 0 1.008 -0.355564 -2.557768 0.079444 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.287718871901 0.00000000 0.00000000 + O 2 1 0 1.291497075433 117.15146554 0.00000000 + H 1 2 3 1.032997470716 100.09756847 180.00000000 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.433436005375 0.00000000 0.00000000 + O 2 1 0 2.440575775329 117.15146554 0.00000000 + H 1 2 3 1.952082316686 100.09756847 180.00000000 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1669 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.072667560589 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.651e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22296 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.8 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5706586097634272 0.00e+00 1.21e-04 9.19e-04 5.71e-03 0.700 0.5 +Warning: op=0 Small HOMO/LUMO gap ( 0.082) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5707312684983208 -7.27e-05 1.27e-04 1.19e-03 4.55e-03 0.700 0.4 + ***Turning on AO-DIIS*** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 3 -205.5707859237248272 -5.47e-05 3.11e-04 3.06e-03 3.26e-03 0.2 + *** Restarting incremental Fock matrix formation *** + 4 -205.5709102811466664 -1.24e-04 9.27e-05 1.54e-03 4.12e-04 0.3 + 5 -205.5708917517638383 1.85e-05 7.97e-05 1.37e-03 2.41e-03 0.1 + 6 -205.5709107933666928 -1.90e-05 4.48e-05 7.51e-04 2.94e-04 0.2 + 7 -205.5709079741052392 2.82e-06 2.92e-05 5.49e-04 9.01e-04 0.1 + 8 -205.5709113179638052 -3.34e-06 1.21e-05 2.01e-04 4.87e-05 0.1 + 9 -205.5709112933761844 2.46e-08 6.81e-06 1.12e-04 5.91e-05 0.1 + 10 -205.5709113637146288 -7.03e-08 1.45e-07 1.52e-06 7.16e-07 0.1 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 10 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57091136371463 Eh -5593.86889 eV + +Components: +Nuclear Repulsion : 70.07266756058915 Eh 1906.77422 eV +Electronic Energy : -275.64357892430371 Eh -7500.64311 eV +One Electron Energy: -419.84964329525127 Eh -11424.68961 eV +Two Electron Energy: 144.20606437094753 Eh 3924.04651 eV + +Virial components: +Potential Energy : -410.41917529074169 Eh -11168.07353 eV +Kinetic Energy : 204.84826392702709 Eh 5574.20465 eV +Virial Ratio : 2.00352772058124 + +DFT components: +N(Alpha) : 11.999998278253 electrons +N(Beta) : 11.999998278253 electrons +N(Total) : 23.999996556505 electrons +E(X) : -23.352548535733 Eh +E(C) : -0.804845304943 Eh +E(XC) : -24.157393840676 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 7.0338e-08 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.5208e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.4503e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.2556e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 7.1632e-07 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.6041e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 2 sec +Finished LeanSCF after 2.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 5.1 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360126 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007190091 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.564081399597 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.1 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000761 -0.000007094 0.000000217 + 2 O : 0.000000665 0.000000162 -0.000000015 + 3 O : 0.000002472 0.000009210 -0.000000305 + 4 H : -0.000002376 -0.000002278 0.000000103 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000123812 +RMS gradient ... 0.0000035741 +MAX gradient ... 0.0000092099 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.005168507 -0.001916934 0.000121436 + 2 O : 0.005657262 -0.001408592 -0.000044375 + 3 O : -0.000993744 0.003501018 -0.000077055 + 4 H : 0.000504989 -0.000175491 -0.000000006 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000328755 -0.0000218367 0.0000657133 + +Norm of the Cartesian gradient ... 0.0088277949 +RMS gradient ... 0.0025483649 +MAX gradient ... 0.0056572621 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.286 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.005 sec ( 1.8%) +RI-J Coulomb gradient .... 0.063 sec ( 21.9%) +XC gradient .... 0.022 sec ( 7.7%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.564081400 Eh +Current gradient norm .... 0.008827795 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999889724 +Lowest eigenvalues of augmented Hessian: + -0.000093609 0.348815349 0.394645655 0.420702731 0.539337954 +Length of the computed step .... 0.014852197 +The final length of the internal step .... 0.014852197 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0060633840 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0033715528 RMS(Int)= 0.0060626246 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000046815 +Previously predicted energy change .... -0.000272702 +Actually observed energy change .... -0.000356667 +Ratio of predicted to observed change .... 1.307898960 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0003566670 0.0000050000 NO + RMS gradient 0.0026126260 0.0001000000 NO + MAX gradient 0.0050464606 0.0003000000 NO + RMS step 0.0060633840 0.0020000000 NO + MAX step 0.0109822604 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0058 Max(Angles) 0.30 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2877 0.005046 -0.0058 1.2819 + 2. B(O 2,O 1) 1.2915 0.003591 -0.0042 1.2873 + 3. B(H 3,N 0) 1.0330 0.000360 -0.0006 1.0324 + 4. A(O 1,N 0,H 3) 100.10 -0.000748 0.17 100.27 + 5. A(N 0,O 1,O 2) 117.15 -0.001379 0.30 117.45 + 6. D(O 2,O 1,N 0,H 3) -180.00 0.000009 -0.00 -180.00 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.073 %) +Internal coordinates : 0.000 s ( 0.026 %) +B/P matrices and projection : 0.000 s ( 0.131 %) +Hessian update/contruction : 0.083 s (99.370 %) +Making the step : 0.000 s ( 0.094 %) +Converting the step to Cartesian: 0.000 s ( 0.050 %) +Storing new data : 0.000 s ( 0.044 %) +Checking convergence : 0.000 s ( 0.013 %) +Final printing : 0.000 s ( 0.195 %) +Total time : 0.084 s + +Time for energy+gradient : 7.136 s +Time for complete geometry iter : 8.226 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.602983 -0.407178 0.021179 + O 0.459371 0.309272 -0.016116 + O 0.312125 1.587684 -0.050751 + H -0.187221 -1.351933 0.041980 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.139473 -0.769454 0.040023 + 1 O 8.0000 0 15.999 0.868085 0.584439 -0.030455 + 2 O 8.0000 0 15.999 0.589831 3.000287 -0.095906 + 3 H 1.0000 0 1.008 -0.353796 -2.554784 0.079331 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.281907310045 0.00000000 0.00000000 + O 2 1 0 1.287329907499 117.45255388 0.00000000 + H 1 2 3 1.032402169750 100.27026334 180.00000000 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.422453745056 0.00000000 0.00000000 + O 2 1 0 2.432700969180 117.45255388 0.00000000 + H 1 2 3 1.950957360894 100.27026334 180.00000000 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1680 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.300919388389 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.606e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22295 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 1.1 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5708992571411500 0.00e+00 1.79e-04 1.74e-03 3.96e-04 0.7 + *** Restarting incremental Fock matrix formation *** + 2 -205.5709408079101763 -4.16e-05 1.15e-04 1.63e-03 5.81e-04 0.5 + 3 -205.5709361000015747 4.71e-06 4.55e-05 8.61e-04 1.42e-03 0.1 + 4 -205.5709437551014958 -7.66e-06 5.84e-05 9.07e-04 2.38e-04 0.3 + 5 -205.5709400042131847 3.75e-06 4.11e-05 7.04e-04 1.09e-03 0.2 + 6 -205.5709437341855619 -3.73e-06 5.50e-05 1.04e-03 1.98e-04 0.2 + 7 -205.5709431201040616 6.14e-07 3.35e-05 6.16e-04 2.45e-04 0.2 + 8 -205.5709443488110537 -1.23e-06 6.17e-07 5.45e-06 9.24e-06 0.2 + 9 -205.5709443491186335 -3.08e-10 2.16e-07 2.77e-06 1.47e-06 0.3 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57094434911863 Eh -5593.86978 eV + +Components: +Nuclear Repulsion : 70.30091938838940 Eh 1912.98527 eV +Electronic Energy : -275.87186373750802 Eh -7506.85505 eV +One Electron Energy: -420.28545699029752 Eh -11436.54871 eV +Two Electron Energy: 144.41359325278950 Eh 3929.69365 eV + +Virial components: +Potential Energy : -410.44242446374892 Eh -11168.70618 eV +Kinetic Energy : 204.87148011463029 Eh 5574.83639 eV +Virial Ratio : 2.00341416108331 + +DFT components: +N(Alpha) : 11.999998271598 electrons +N(Beta) : 11.999998271598 electrons +N(Total) : 23.999996543197 electrons +E(X) : -23.359170619356 Eh +E(C) : -0.805300044582 Eh +E(XC) : -24.164470663938 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.0758e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.7685e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.1571e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.0299e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.4655e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.2097e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 3 sec +Finished LeanSCF after 3.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 5.2 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360220 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007177082 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.564127487240 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000749 -0.000007074 0.000000216 + 2 O : 0.000000656 0.000000167 -0.000000015 + 3 O : 0.000002462 0.000009151 -0.000000303 + 4 H : -0.000002369 -0.000002244 0.000000102 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000123148 +RMS gradient ... 0.0000035550 +MAX gradient ... 0.0000091507 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.000465126 0.000153329 -0.000014335 + 2 O : 0.000043487 0.000193685 0.000002099 + 3 O : 0.000059719 -0.000430840 0.000017486 + 4 H : 0.000361920 0.000083826 -0.000005250 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000299232 -0.0000272841 0.0000717864 + +Norm of the Cartesian gradient ... 0.0007791034 +RMS gradient ... 0.0002249078 +MAX gradient ... 0.0004651259 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.427 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.005 sec ( 1.2%) +RI-J Coulomb gradient .... 0.058 sec ( 13.6%) +XC gradient .... 0.022 sec ( 5.1%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.564127487 Eh +Current gradient norm .... 0.000779103 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999998022 +Lowest eigenvalues of augmented Hessian: + -0.000001577 0.314928653 0.401701844 0.445410985 0.563375065 +Length of the computed step .... 0.001989202 +The final length of the internal step .... 0.001989202 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0008120884 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0007865674 RMS(Int)= 0.0008120940 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000789 +Previously predicted energy change .... -0.000046815 +Actually observed energy change .... -0.000046088 +Ratio of predicted to observed change .... 0.984466767 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000460876 0.0000050000 NO + RMS gradient 0.0003377732 0.0001000000 NO + MAX gradient 0.0006956605 0.0003000000 NO + RMS step 0.0008120884 0.0020000000 YES + MAX step 0.0019050915 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0003 Max(Angles) 0.11 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2819 -0.000040 -0.0000 1.2819 + 2. B(O 2,O 1) 1.2873 -0.000439 0.0003 1.2876 + 3. B(H 3,N 0) 1.0324 0.000064 -0.0001 1.0323 + 4. A(O 1,N 0,H 3) 100.27 -0.000696 0.11 100.38 + 5. A(N 0,O 1,O 2) 117.45 0.000050 -0.00 117.45 + 6. D(O 2,O 1,N 0,H 3) -180.00 0.000006 0.00 -180.00 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.040 %) +Internal coordinates : 0.000 s ( 0.012 %) +B/P matrices and projection : 0.000 s ( 0.068 %) +Hessian update/contruction : 0.007 s ( 3.747 %) +Making the step : 0.000 s ( 0.025 %) +Converting the step to Cartesian: 0.000 s ( 0.017 %) +Storing new data : 0.000 s ( 0.017 %) +Checking convergence : 0.000 s ( 0.006 %) +Final printing : 0.184 s (96.067 %) +Total time : 0.191 s + +Time for energy+gradient : 9.062 s +Time for complete geometry iter : 10.239 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 4 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.602318 -0.407310 0.021173 + O 0.459730 0.309566 -0.016130 + O 0.311880 1.588202 -0.050762 + H -0.188000 -1.352614 0.042012 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.138215 -0.769704 0.040011 + 1 O 8.0000 0 15.999 0.868764 0.584995 -0.030482 + 2 O 8.0000 0 15.999 0.589367 3.001267 -0.095927 + 3 H 1.0000 0 1.008 -0.355269 -2.556071 0.079391 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.281892409256 0.00000000 0.00000000 + O 2 1 0 1.287621574215 117.45038893 0.00000000 + H 1 2 3 1.032324500744 100.37941704 180.00000085 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.422425586647 0.00000000 0.00000000 + O 2 1 0 2.433252139395 117.45038893 0.00000000 + H 1 2 3 1.950810587744 100.37941704 180.00000085 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1680 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.291834426265 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.609e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22295 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.7 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5709420198655550 0.00e+00 1.94e-05 2.31e-04 3.28e-05 0.4 + *** Restarting incremental Fock matrix formation *** + 2 -205.5709424215682759 -4.02e-07 5.76e-06 5.62e-05 3.19e-05 0.2 + 3 -205.5709424429315675 -2.14e-08 1.75e-06 1.94e-05 7.17e-06 0.1 + 4 -205.5709424419930258 9.39e-10 1.10e-06 1.91e-05 1.47e-05 0.2 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 4 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57094244199303 Eh -5593.86973 eV + +Components: +Nuclear Repulsion : 70.29183442626541 Eh 1912.73806 eV +Electronic Energy : -275.86277686825844 Eh -7506.60779 eV +One Electron Energy: -420.26793506946746 Eh -11436.07191 eV +Two Electron Energy: 144.40515820120902 Eh 3929.46412 eV + +Virial components: +Potential Energy : -410.44115339299873 Eh -11168.67159 eV +Kinetic Energy : 204.87021095100570 Eh 5574.80186 eV +Virial Ratio : 2.00342036788918 + +DFT components: +N(Alpha) : 11.999998264337 electrons +N(Beta) : 11.999998264337 electrons +N(Total) : 23.999996528673 electrons +E(X) : -23.358936017954 Eh +E(C) : -0.805279052765 Eh +E(XC) : -24.164215070720 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -9.3854e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.9133e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.0974e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.9818e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.4686e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.4126e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 1.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 5.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360204 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007174172 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.564128474338 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000752 -0.000007077 0.000000216 + 2 O : 0.000000657 0.000000169 -0.000000015 + 3 O : 0.000002462 0.000009160 -0.000000303 + 4 H : -0.000002367 -0.000002252 0.000000102 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000123245 +RMS gradient ... 0.0000035578 +MAX gradient ... 0.0000091595 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.000205650 -0.000091836 -0.000011404 + 2 O : 0.000047252 0.000265565 -0.000000210 + 3 O : 0.000068011 -0.000180463 0.000010352 + 4 H : 0.000090386 0.000006734 0.000001263 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000304198 -0.0000274672 0.0000674727 + +Norm of the Cartesian gradient ... 0.0004112533 +RMS gradient ... 0.0001187186 +MAX gradient ... 0.0002655646 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.232 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.005 sec ( 2.2%) +RI-J Coulomb gradient .... 0.053 sec ( 22.9%) +XC gradient .... 0.016 sec ( 6.9%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.564128474 Eh +Current gradient norm .... 0.000411253 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999525 +Lowest eigenvalues of augmented Hessian: + -0.000000288 0.251350276 0.387776563 0.410809715 0.605818101 +Length of the computed step .... 0.000974712 +The final length of the internal step .... 0.000974712 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0003979245 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0003613845 RMS(Int)= 0.0003979311 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000144 +Previously predicted energy change .... -0.000000789 +Actually observed energy change .... -0.000000987 +Ratio of predicted to observed change .... 1.251699499 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000009871 0.0000050000 YES + RMS gradient 0.0001299885 0.0001000000 NO + MAX gradient 0.0001905824 0.0003000000 YES + RMS step 0.0003979245 0.0020000000 YES + MAX step 0.0007405852 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0002 Max(Angles) 0.04 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2819 0.000150 -0.0002 1.2817 + 2. B(O 2,O 1) 1.2876 -0.000191 0.0002 1.2878 + 3. B(H 3,N 0) 1.0323 0.000025 -0.0000 1.0323 + 4. A(O 1,N 0,H 3) 100.38 -0.000151 0.04 100.42 + 5. A(N 0,O 1,O 2) 117.45 0.000138 -0.02 117.43 + 6. D(O 2,O 1,N 0,H 3) -180.00 0.000006 0.00 -180.00 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.170 %) +Internal coordinates : 0.000 s ( 0.049 %) +B/P matrices and projection : 0.000 s ( 0.232 %) +Hessian update/contruction : 0.009 s (18.381 %) +Making the step : 0.000 s ( 0.109 %) +Converting the step to Cartesian: 0.000 s ( 0.070 %) +Storing new data : 0.000 s ( 0.072 %) +Checking convergence : 0.000 s ( 0.020 %) +Final printing : 0.039 s (80.889 %) +Total time : 0.049 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 4 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.601946 -0.407224 0.021164 + O 0.459964 0.309541 -0.016133 + O 0.311632 1.588326 -0.050762 + H -0.188358 -1.352799 0.042023 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.137513 -0.769543 0.039995 + 1 O 8.0000 0 15.999 0.869205 0.584948 -0.030487 + 2 O 8.0000 0 15.999 0.588899 3.001501 -0.095927 + 3 H 1.0000 0 1.008 -0.355944 -2.556419 0.079411 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.281716088717 0.00000000 0.00000000 + O 2 1 0 1.287824649693 117.42925182 0.00000000 + H 1 2 3 1.032279566005 100.42184945 180.00000000 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.422092389116 0.00000000 0.00000000 + O 2 1 0 2.433635896433 117.42925182 0.00000000 + H 1 2 3 1.950725673393 100.42184945 180.00000000 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1680 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.291757618817 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.611e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22295 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.2917576188 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.2 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.9 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5709421486158703 0.00e+00 1.18e-05 1.04e-04 2.80e-05 0.6 + *** Restarting incremental Fock matrix formation *** + 2 -205.5709423436576344 -1.95e-07 5.29e-06 6.45e-05 3.22e-05 0.4 + 3 -205.5709423423398903 1.32e-09 3.08e-06 4.08e-05 6.72e-05 0.3 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 3 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57094234233989 Eh -5593.86973 eV + +Components: +Nuclear Repulsion : 70.29175761881737 Eh 1912.73597 eV +Electronic Energy : -275.86269996115726 Eh -7506.60569 eV +One Electron Energy: -420.26783631929243 Eh -11436.06922 eV +Two Electron Energy: 144.40513635813517 Eh 3929.46353 eV + +Virial components: +Potential Energy : -410.44120637163530 Eh -11168.67303 eV +Kinetic Energy : 204.87026402929538 Eh 5574.80330 eV +Virial Ratio : 2.00342010743416 + +DFT components: +N(Alpha) : 11.999998265764 electrons +N(Beta) : 11.999998265764 electrons +N(Total) : 23.999996531527 electrons +E(X) : -23.358932570643 Eh +E(C) : -0.805275517389 Eh +E(XC) : -24.164208088032 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.3177e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.0810e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.0803e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.5008e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 6.7191e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 5.8298e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.193384 -522.2785 + 1 2.0000 -19.016735 -517.4717 + 2 2.0000 -14.269711 -388.2986 + 3 2.0000 -1.260792 -34.3079 + 4 2.0000 -0.977493 -26.5989 + 5 2.0000 -0.695846 -18.9349 + 6 2.0000 -0.570092 -15.5130 + 7 2.0000 -0.525023 -14.2866 + 8 2.0000 -0.507387 -13.8067 + 9 2.0000 -0.329128 -8.9560 + 10 2.0000 -0.288548 -7.8518 + 11 2.0000 -0.258057 -7.0221 + 12 0.0000 -0.175461 -4.7745 + 13 0.0000 0.057888 1.5752 + 14 0.0000 0.080797 2.1986 + 15 0.0000 0.150846 4.1047 + 16 0.0000 0.220662 6.0045 + 17 0.0000 0.276760 7.5310 + 18 0.0000 0.294787 8.0216 + 19 0.0000 0.327452 8.9104 + 20 0.0000 0.367326 9.9954 + 21 0.0000 0.381319 10.3762 + 22 0.0000 0.396428 10.7874 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.283751 + 1 O : 0.229385 + 2 O : -0.210036 + 3 H : 0.264402 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.885398 s : 3.885398 + pz : 1.093624 p : 3.335887 + px : 1.184400 + py : 1.057864 + dz2 : 0.008092 d : 0.062466 + dxz : 0.018026 + dyz : 0.004897 + dx2y2 : 0.010505 + dxy : 0.020945 + + 1 O s : 3.737962 s : 3.737962 + pz : 1.379136 p : 3.886220 + px : 1.454635 + py : 1.052450 + dz2 : 0.004775 d : 0.146433 + dxz : 0.013405 + dyz : 0.045857 + dx2y2 : 0.028555 + dxy : 0.053840 + + 2 O s : 3.945895 s : 3.945895 + pz : 1.423238 p : 4.236530 + px : 1.907588 + py : 0.905704 + dz2 : 0.002036 d : 0.027612 + dxz : 0.000199 + dyz : 0.014194 + dx2y2 : 0.008849 + dxy : 0.002334 + + 3 H s : 0.705968 s : 0.705968 + pz : 0.006382 p : 0.029630 + px : 0.006953 + py : 0.016295 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.054842 + 1 O : -0.197281 + 2 O : -0.028062 + 3 H : 0.280185 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.354839 s : 3.354839 + pz : 1.012215 p : 3.379335 + px : 1.281043 + py : 1.086077 + dz2 : 0.040051 d : 0.320669 + dxz : 0.043466 + dyz : 0.025564 + dx2y2 : 0.122328 + dxy : 0.089260 + + 1 O s : 3.356163 s : 3.356163 + pz : 1.272017 p : 4.040912 + px : 1.507463 + py : 1.261431 + dz2 : 0.063569 d : 0.800206 + dxz : 0.038600 + dyz : 0.188048 + dx2y2 : 0.262252 + dxy : 0.247738 + + 2 O s : 3.593119 s : 3.593119 + pz : 1.340776 p : 4.178063 + px : 1.781762 + py : 1.055525 + dz2 : 0.030186 d : 0.256880 + dxz : 0.000706 + dyz : 0.064886 + dx2y2 : 0.074524 + dxy : 0.086577 + + 3 H s : 0.646026 s : 0.646026 + pz : 0.013943 p : 0.073788 + px : 0.019079 + py : 0.040766 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2838 7.0000 -0.2838 2.7299 2.7299 -0.0000 + 1 O 7.7706 8.0000 0.2294 2.6678 2.6678 0.0000 + 2 O 8.2100 8.0000 -0.2100 1.7461 1.7461 -0.0000 + 3 H 0.7356 1.0000 0.2644 0.9172 0.9172 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3935 B( 0-N , 2-O ) : 0.4566 B( 0-N , 3-H ) : 0.8797 +B( 1-O , 2-O ) : 1.2632 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.279 sec +Sum of individual times .... 2.067 sec ( 90.7%) + +SCF preparation .... 0.467 sec ( 20.5%) +Fock matrix formation .... 0.733 sec ( 32.2%) + Startup .... 0.101 sec ( 13.8% of F) + Split-RI-J .... 0.013 sec ( 1.7% of F) + XC integration .... 0.202 sec ( 27.6% of F) + Basis function eval. .... 0.004 sec ( 2.0% of XC) + Density eval. .... 0.005 sec ( 2.5% of XC) + XC-Functional eval. .... 0.003 sec ( 1.6% of XC) + XC-Potential eval. .... 0.005 sec ( 2.6% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.068 sec ( 3.0%) +Total Energy calculation .... 0.006 sec ( 0.3%) +Population analysis .... 0.114 sec ( 5.0%) +Orbital Transformation .... 0.267 sec ( 11.7%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.087 sec ( 3.8%) +SOSCF solution .... 0.325 sec ( 14.3%) +Finished LeanSCF after 2.5 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 5.4 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360202 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007173913 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.564128631401 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.001.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.001.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.149667 0.936416 -0.029401 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5709423423398903 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.461272886 0.628922210 -0.025371413 +Nuclear contribution : -0.245698430 -1.725618618 0.053694313 + ----------------------------------------- +Total Dipole Moment : 0.215574456 -1.096696408 0.028322901 + ----------------------------------------- +Magnitude (a.u.) : 1.118041835 +Magnitude (Debye) : 2.841836499 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.465423 0.427310 0.380404 +Rotational constants in MHz : 103890.768624 12810.426590 11404.211091 + +Dipole components along the rotational axes: +x,y,z [a.u.] : -0.935414 0.612387 0.000005 +x,y,z [Debye]: -2.377633 1.556565 0.000013 + + + +Dipole moment calculation done in 0.0 sec + +Maximum memory used throughout the entire PROP-calculation: 2.6 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 2 * + * * + * Dihedral ( 2, 1, 0, 3) : -170.76923077 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2819 0.746058 + 2. B(O 2,O 1) 1.2911 0.729502 + 3. B(H 3,N 0) 1.0352 0.398703 + 4. A(O 1,N 0,H 3) 100.4550 0.362727 + 5. A(N 0,O 1,O 2) 117.2844 0.450065 + 6. D(O 2,O 1,N 0,H 3) -170.7692 0.044127 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.602460 -0.408175 -0.011729 + O 0.459157 0.308049 -0.067789 + O 0.312253 1.589475 -0.010991 + H -0.187658 -1.351505 0.086800 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.138484 -0.771338 -0.022164 + 1 O 8.0000 0 15.999 0.867680 0.582128 -0.128102 + 2 O 8.0000 0 15.999 0.590073 3.003673 -0.020770 + 3 H 1.0000 0 1.008 -0.354622 -2.553974 0.164029 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.281716088717 0.00000000 0.00000000 + O 2 1 0 1.287824649693 117.42925182 0.00000000 + H 1 2 3 1.032279566005 100.42184945 180.00000000 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.422092389116 0.00000000 0.00000000 + O 2 1 0 2.433635896433 117.42925182 0.00000000 + H 1 2 3 1.950725673393 100.42184945 180.00000000 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.202210679250 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.662e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22296 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.6 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.2022106793 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.3 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 1.0 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5649394532769634 0.00e+00 3.83e-04 5.02e-03 3.30e-02 0.700 0.5 +Warning: op=0 Small HOMO/LUMO gap ( 0.081) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5662538191560316 -1.31e-03 4.45e-04 5.69e-03 2.63e-02 0.700 0.2 + ***Turning on AO-DIIS*** + 3 -205.5673322664505918 -1.08e-03 3.38e-04 4.06e-03 1.88e-02 0.700 0.2 + 4 -205.5680868114785085 -7.55e-04 8.41e-04 9.62e-03 1.32e-02 0.000 0.1 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5698426809909165 -1.76e-03 6.90e-05 7.37e-04 7.38e-04 0.2 + *** Restarting incremental Fock matrix formation *** + 6 -205.5698455839590224 -2.90e-06 2.36e-04 3.37e-03 9.25e-04 0.3 + 7 -205.5697559237373753 8.97e-05 1.76e-04 3.16e-03 5.51e-03 0.1 + 8 -205.5698541644516126 -9.82e-05 2.31e-05 2.07e-04 1.14e-04 0.1 + 9 -205.5698542961173416 -1.32e-07 6.93e-06 6.33e-05 5.95e-05 0.1 + 10 -205.5698543420741089 -4.60e-08 6.37e-06 7.31e-05 6.78e-05 0.2 + 11 -205.5698543332045460 8.87e-09 4.24e-06 3.86e-05 5.97e-05 0.2 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56985433320455 Eh -5593.84012 eV + +Components: +Nuclear Repulsion : 70.20221067925014 Eh 1910.29927 eV +Electronic Energy : -275.77206501245473 Eh -7504.13939 eV +One Electron Energy: -420.09947995483714 Eh -11431.48802 eV +Two Electron Energy: 144.32741494238243 Eh 3927.34862 eV + +Virial components: +Potential Energy : -410.43004955109700 Eh -11168.36944 eV +Kinetic Energy : 204.86019521789243 Eh 5574.52932 eV +Virial Ratio : 2.00346411421974 + +DFT components: +N(Alpha) : 11.999998273015 electrons +N(Beta) : 11.999998273015 electrons +N(Total) : 23.999996546030 electrons +E(X) : -23.355773847447 Eh +E(C) : -0.805085714822 Eh +E(XC) : -24.160859562269 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -8.8696e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.8635e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.2390e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.3845e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 5.9668e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 9.2227e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.192604 -522.2573 + 1 2.0000 -19.017100 -517.4816 + 2 2.0000 -14.270064 -388.3082 + 3 2.0000 -1.259067 -34.2610 + 4 2.0000 -0.976256 -26.5653 + 5 2.0000 -0.696133 -18.9428 + 6 2.0000 -0.569327 -15.4922 + 7 2.0000 -0.523889 -14.2557 + 8 2.0000 -0.507115 -13.7993 + 9 2.0000 -0.329200 -8.9580 + 10 2.0000 -0.287583 -7.8255 + 11 2.0000 -0.258399 -7.0314 + 12 0.0000 -0.176625 -4.8062 + 13 0.0000 0.055796 1.5183 + 14 0.0000 0.079697 2.1687 + 15 0.0000 0.149820 4.0768 + 16 0.0000 0.220857 6.0098 + 17 0.0000 0.276038 7.5114 + 18 0.0000 0.295734 8.0473 + 19 0.0000 0.327482 8.9113 + 20 0.0000 0.365286 9.9399 + 21 0.0000 0.380498 10.3539 + 22 0.0000 0.397993 10.8300 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.285559 + 1 O : 0.227697 + 2 O : -0.208107 + 3 H : 0.265969 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.886886 s : 3.886886 + pz : 1.091447 p : 3.336365 + px : 1.183980 + py : 1.060938 + dz2 : 0.008034 d : 0.062307 + dxz : 0.017999 + dyz : 0.004910 + dx2y2 : 0.010536 + dxy : 0.020828 + + 1 O s : 3.740034 s : 3.740034 + pz : 1.380518 p : 3.887702 + px : 1.453326 + py : 1.053859 + dz2 : 0.004733 d : 0.144567 + dxz : 0.013500 + dyz : 0.045477 + dx2y2 : 0.027788 + dxy : 0.053069 + + 2 O s : 3.945853 s : 3.945853 + pz : 1.424301 p : 4.235087 + px : 1.904779 + py : 0.906007 + dz2 : 0.002038 d : 0.027167 + dxz : 0.000177 + dyz : 0.013837 + dx2y2 : 0.008669 + dxy : 0.002446 + + 3 H s : 0.704606 s : 0.704606 + pz : 0.006456 p : 0.029425 + px : 0.006902 + py : 0.016066 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.056323 + 1 O : -0.196795 + 2 O : -0.028417 + 3 H : 0.281535 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.355925 s : 3.355925 + pz : 1.011030 p : 3.379141 + px : 1.280636 + py : 1.087474 + dz2 : 0.039628 d : 0.321258 + dxz : 0.043918 + dyz : 0.026321 + dx2y2 : 0.122219 + dxy : 0.089171 + + 1 O s : 3.357761 s : 3.357761 + pz : 1.273526 p : 4.041236 + px : 1.506658 + py : 1.261051 + dz2 : 0.062712 d : 0.797798 + dxz : 0.039182 + dyz : 0.187486 + dx2y2 : 0.261733 + dxy : 0.246686 + + 2 O s : 3.595287 s : 3.595287 + pz : 1.342578 p : 4.177326 + px : 1.779355 + py : 1.055393 + dz2 : 0.030136 d : 0.255804 + dxz : 0.000804 + dyz : 0.064854 + dx2y2 : 0.074232 + dxy : 0.085778 + + 3 H s : 0.645185 s : 0.645185 + pz : 0.014157 p : 0.073280 + px : 0.018917 + py : 0.040207 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2856 7.0000 -0.2856 2.7265 2.7265 -0.0000 + 1 O 7.7723 8.0000 0.2277 2.6640 2.6640 -0.0000 + 2 O 8.2081 8.0000 -0.2081 1.7428 1.7428 -0.0000 + 3 H 0.7340 1.0000 0.2660 0.9161 0.9161 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3928 B( 0-N , 2-O ) : 0.4554 B( 0-N , 3-H ) : 0.8784 +B( 1-O , 2-O ) : 1.2605 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 3 sec + +Total time .... 3.145 sec +Sum of individual times .... 2.936 sec ( 93.4%) + +SCF preparation .... 0.399 sec ( 12.7%) +Fock matrix formation .... 1.419 sec ( 45.1%) + Startup .... 0.152 sec ( 10.7% of F) + Split-RI-J .... 0.079 sec ( 5.5% of F) + XC integration .... 0.361 sec ( 25.4% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.013 sec ( 3.7% of XC) + Density eval. .... 0.018 sec ( 5.0% of XC) + XC-Functional eval. .... 0.012 sec ( 3.3% of XC) + XC-Potential eval. .... 0.019 sec ( 5.4% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.307 sec ( 9.8%) +Total Energy calculation .... 0.035 sec ( 1.1%) +Population analysis .... 0.210 sec ( 6.7%) +Orbital Transformation .... 0.122 sec ( 3.9%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.270 sec ( 8.6%) +SOSCF solution .... 0.174 sec ( 5.5%) +Finished LeanSCF after 3.3 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 5.6 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360207 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007181936 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.563032604602 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000755 -0.000007071 0.000000350 + 2 O : 0.000000658 0.000000165 -0.000000079 + 3 O : 0.000002465 0.000009179 -0.000000145 + 4 H : -0.000002368 -0.000002273 -0.000000126 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000123407 +RMS gradient ... 0.0000035625 +MAX gradient ... 0.0000091789 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.000720279 0.001143428 -0.005316342 + 2 O : -0.000025839 -0.001784209 -0.008088529 + 3 O : -0.000016895 0.001771888 0.006264719 + 4 H : 0.000763013 -0.001131106 0.007140152 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000073353 -0.0000541186 0.0000556854 + +Norm of the Cartesian gradient ... 0.0139258044 +RMS gradient ... 0.0040200335 +MAX gradient ... 0.0080885288 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.308 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.005 sec ( 1.7%) +RI-J Coulomb gradient .... 0.064 sec ( 20.7%) +XC gradient .... 0.019 sec ( 6.1%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.563032605 Eh +Current gradient norm .... 0.013925804 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999982039 +Lowest eigenvalues of augmented Hessian: + -0.000016865 0.362031930 0.394457497 0.449051628 0.720863864 +Length of the computed step .... 0.005993503 +The final length of the internal step .... 0.005993503 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0024468373 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0013676600 RMS(Int)= 0.0024466010 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0011950767 0.0001000000 NO + MAX gradient 0.0020329305 0.0003000000 NO + RMS step 0.0024468373 0.0020000000 NO + MAX step 0.0051037619 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0027 Max(Angles) 0.08 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2819 0.000043 -0.0000 1.2818 + 2. B(O 2,O 1) 1.2911 0.002033 -0.0015 1.2896 + 3. B(H 3,N 0) 1.0352 0.002013 -0.0027 1.0325 + 4. A(O 1,N 0,H 3) 100.46 -0.000099 0.02 100.47 + 5. A(N 0,O 1,O 2) 117.28 -0.000610 0.08 117.36 + 6. D(O 2,O 1,N 0,H 3) -170.77 0.013412 0.00 -170.77 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 2.353 %) +Internal coordinates : 0.000 s ( 0.819 %) +B/P matrices and projection : 0.000 s ( 3.615 %) +Hessian update/contruction : 0.000 s (10.709 %) +Making the step : 0.000 s ( 1.603 %) +Converting the step to Cartesian: 0.000 s ( 1.160 %) +Storing new data : 0.000 s ( 0.921 %) +Checking convergence : 0.000 s ( 0.000 %) +Final printing : 0.002 s (78.752 %) +Total time : 0.003 s + +Time for energy+gradient : 8.053 s +Time for complete geometry iter : 9.033 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.602119 -0.409066 -0.011640 + O 0.458715 0.308265 -0.067663 + O 0.312360 1.588258 -0.011031 + H -0.187664 -1.349612 0.086626 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.137840 -0.773023 -0.021997 + 1 O 8.0000 0 15.999 0.866845 0.582536 -0.127865 + 2 O 8.0000 0 15.999 0.590274 3.001372 -0.020846 + 3 H 1.0000 0 1.008 -0.354633 -2.550397 0.163700 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.281823028391 0.00000000 0.00000000 + O 2 1 0 1.289577097781 117.36222856 0.00000000 + H 1 2 3 1.032499855604 100.47068471 189.23076912 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.422294475813 0.00000000 0.00000000 + O 2 1 0 2.436947543384 117.36222856 0.00000000 + H 1 2 3 1.951141960404 100.47068471 189.23076912 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.248655994766 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.647e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.003 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22296 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.7 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5698536590630567 0.00e+00 5.58e-05 7.95e-04 8.62e-05 0.5 + *** Restarting incremental Fock matrix formation *** + 2 -205.5698577655017800 -4.11e-06 2.68e-05 4.42e-04 9.60e-05 0.1 + 3 -205.5698573556492477 4.10e-07 2.46e-05 4.03e-04 4.18e-04 0.3 + 4 -205.5698576740713008 -3.18e-07 2.59e-05 4.01e-04 2.32e-04 0.1 + 5 -205.5698574992315741 1.75e-07 1.37e-05 2.41e-04 3.47e-04 0.3 + 6 -205.5698579767657463 -4.78e-07 1.62e-05 2.87e-04 1.03e-04 0.3 + 7 -205.5698579956651599 -1.89e-08 8.21e-06 1.58e-04 6.20e-05 0.3 + 8 -205.5698580670813556 -7.14e-08 1.08e-06 1.55e-05 7.79e-06 0.3 + 9 -205.5698580680122234 -9.31e-10 4.12e-07 5.56e-06 4.19e-06 0.2 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56985806801222 Eh -5593.84022 eV + +Components: +Nuclear Repulsion : 70.24865599476570 Eh 1911.56311 eV +Electronic Energy : -275.81851406277792 Eh -7505.40333 eV +One Electron Energy: -420.18574595964071 Eh -11433.83543 eV +Two Electron Energy: 144.36723189686279 Eh 3928.43210 eV + +Virial components: +Potential Energy : -410.43718235766670 Eh -11168.56353 eV +Kinetic Energy : 204.86732428965448 Eh 5574.72331 eV +Virial Ratio : 2.00342921342285 + +DFT components: +N(Alpha) : 11.999998241364 electrons +N(Beta) : 11.999998241364 electrons +N(Total) : 23.999996482728 electrons +E(X) : -23.357693327148 Eh +E(C) : -0.805187448439 Eh +E(XC) : -24.162880775587 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 9.3087e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.5630e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.1157e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.7491e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.1897e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 6.9948e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 3 sec +Finished LeanSCF after 3.6 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 5.7 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360225 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007175564 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.563042729238 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000751 -0.000007068 0.000000350 + 2 O : 0.000000656 0.000000167 -0.000000078 + 3 O : 0.000002462 0.000009155 -0.000000145 + 4 H : -0.000002367 -0.000002253 -0.000000127 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000123169 +RMS gradient ... 0.0000035556 +MAX gradient ... 0.0000091550 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.000391414 -0.000625040 -0.005165277 + 2 O : -0.000604486 -0.000735063 -0.008045239 + 3 O : 0.000252670 0.000714236 0.006228736 + 4 H : -0.000039598 0.000645866 0.006981779 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000038937 -0.0000470372 0.0000619185 + +Norm of the Cartesian gradient ... 0.0134681344 +RMS gradient ... 0.0038879155 +MAX gradient ... 0.0080452392 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.522 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.004 sec ( 0.9%) +RI-J Coulomb gradient .... 0.055 sec ( 10.5%) +XC gradient .... 0.018 sec ( 3.4%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.563042729 Eh +Current gradient norm .... 0.013468134 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999997711 +Lowest eigenvalues of augmented Hessian: + -0.000002087 0.353749285 0.373391365 0.454360677 0.611861940 +Length of the computed step .... 0.002139691 +The final length of the internal step .... 0.002139691 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0008735252 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0004365068 RMS(Int)= 0.0008735182 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000001044 +Previously predicted energy change .... -0.000008433 +Actually observed energy change .... -0.000010125 +Ratio of predicted to observed change .... 1.200606915 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000101246 0.0000050000 NO + RMS gradient 0.0004124095 0.0001000000 NO + MAX gradient 0.0009502842 0.0003000000 NO + RMS step 0.0008735252 0.0020000000 YES + MAX step 0.0018541813 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0010 Max(Angles) 0.05 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2818 -0.000217 0.0002 1.2820 + 2. B(O 2,O 1) 1.2896 0.000950 -0.0010 1.2886 + 3. B(H 3,N 0) 1.0325 0.000057 -0.0003 1.0322 + 4. A(O 1,N 0,H 3) 100.47 -0.000059 0.01 100.48 + 5. A(N 0,O 1,O 2) 117.36 -0.000252 0.05 117.41 + 6. D(O 2,O 1,N 0,H 3) -170.77 0.013433 0.00 -170.77 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.048 %) +Internal coordinates : 0.000 s ( 0.017 %) +B/P matrices and projection : 0.000 s ( 0.067 %) +Hessian update/contruction : 0.159 s (92.432 %) +Making the step : 0.000 s ( 0.043 %) +Converting the step to Cartesian: 0.000 s ( 0.026 %) +Storing new data : 0.000 s ( 0.023 %) +Checking convergence : 0.000 s ( 0.008 %) +Final printing : 0.013 s ( 7.335 %) +Total time : 0.172 s + +Time for energy+gradient : 8.534 s +Time for complete geometry iter : 9.680 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.602169 -0.409259 -0.011645 + O 0.458455 0.308726 -0.067600 + O 0.312571 1.587789 -0.011068 + H -0.187565 -1.349412 0.086604 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.137935 -0.773387 -0.022005 + 1 O 8.0000 0 15.999 0.866354 0.583408 -0.127746 + 2 O 8.0000 0 15.999 0.590674 3.000486 -0.020915 + 3 H 1.0000 0 1.008 -0.354447 -2.550020 0.163658 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.282012540277 0.00000000 0.00000000 + O 2 1 0 1.288595907316 117.40816841 0.00000000 + H 1 2 3 1.032200674249 100.48343297 189.23076912 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.422652601376 0.00000000 0.00000000 + O 2 1 0 2.435093362119 117.40816841 0.00000000 + H 1 2 3 1.950576589579 100.48343297 189.23076912 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.267310320854 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.638e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22296 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.5 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 1.0 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5698557170285881 0.00e+00 2.67e-05 3.02e-04 4.17e-05 0.6 + *** Restarting incremental Fock matrix formation *** + 2 -205.5698567980992379 -1.08e-06 2.46e-05 4.67e-04 1.13e-04 0.4 + 3 -205.5698556620838531 1.14e-06 1.97e-05 3.51e-04 6.10e-04 0.1 + 4 -205.5698568923584162 -1.23e-06 5.80e-06 7.84e-05 3.52e-05 0.2 + 5 -205.5698568609997210 3.14e-08 3.19e-06 5.61e-05 9.78e-05 0.2 + 6 -205.5698569019780280 -4.10e-08 2.19e-06 3.74e-05 9.41e-06 0.3 + 7 -205.5698569014598434 5.18e-10 1.19e-06 2.04e-05 1.02e-05 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56985690145984 Eh -5593.84019 eV + +Components: +Nuclear Repulsion : 70.26731032085358 Eh 1912.07072 eV +Electronic Energy : -275.83716722231350 Eh -7505.91091 eV +One Electron Energy: -420.22044669690541 Eh -11434.77969 eV +Two Electron Energy: 144.38327947459194 Eh 3928.86877 eV + +Virial components: +Potential Energy : -410.43917275083288 Eh -11168.61769 eV +Kinetic Energy : 204.86931584937304 Eh 5574.77750 eV +Virial Ratio : 2.00341945327041 + +DFT components: +N(Alpha) : 11.999998222725 electrons +N(Beta) : 11.999998222725 electrons +N(Total) : 23.999996445450 electrons +E(X) : -23.358204175358 Eh +E(C) : -0.805229616226 Eh +E(XC) : -24.163433791584 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -5.1818e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.0420e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.1920e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.1758e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.0184e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 6.6425e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 2 sec +Finished LeanSCF after 2.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 5.8 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360231 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007173142 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.563043990423 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000750 -0.000007068 0.000000350 + 2 O : 0.000000656 0.000000169 -0.000000078 + 3 O : 0.000002463 0.000009148 -0.000000145 + 4 H : -0.000002368 -0.000002250 -0.000000127 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000123110 +RMS gradient ... 0.0000035539 +MAX gradient ... 0.0000091481 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.000580567 -0.000928658 -0.005150204 + 2 O : -0.000852703 0.000096196 -0.008018071 + 3 O : 0.000441872 0.000032231 0.006199553 + 4 H : -0.000169737 0.000800231 0.006968722 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000018484 -0.0000468540 0.0000633050 + +Norm of the Cartesian gradient ... 0.0134392299 +RMS gradient ... 0.0038795715 +MAX gradient ... 0.0080180708 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.260 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.005 sec ( 2.1%) +RI-J Coulomb gradient .... 0.063 sec ( 24.1%) +XC gradient .... 0.019 sec ( 7.2%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.563043990 Eh +Current gradient norm .... 0.013439230 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999688 +Lowest eigenvalues of augmented Hessian: + -0.000000264 0.345684171 0.374661398 0.450833785 0.495715365 +Length of the computed step .... 0.000790367 +The final length of the internal step .... 0.000790367 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0003226660 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001628563 RMS(Int)= 0.0003226689 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000132 +Previously predicted energy change .... -0.000001044 +Actually observed energy change .... -0.000001261 +Ratio of predicted to observed change .... 1.208491397 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000012612 0.0000050000 YES + RMS gradient 0.0001400105 0.0001000000 NO + MAX gradient 0.0002503687 0.0003000000 YES + RMS step 0.0003226660 0.0020000000 YES + MAX step 0.0006604581 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0003 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2820 -0.000182 0.0002 1.2822 + 2. B(O 2,O 1) 1.2886 0.000250 -0.0003 1.2882 + 3. B(H 3,N 0) 1.0322 -0.000137 0.0001 1.0323 + 4. A(O 1,N 0,H 3) 100.48 0.000051 -0.01 100.47 + 5. A(N 0,O 1,O 2) 117.41 0.000017 0.00 117.41 + 6. D(O 2,O 1,N 0,H 3) -170.77 0.013437 -0.00 -170.77 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.158 %) +Internal coordinates : 0.000 s ( 0.040 %) +B/P matrices and projection : 0.000 s ( 0.151 %) +Hessian update/contruction : 0.005 s ( 7.411 %) +Making the step : 0.000 s ( 0.075 %) +Converting the step to Cartesian: 0.000 s ( 0.055 %) +Storing new data : 0.000 s ( 0.044 %) +Checking convergence : 0.000 s ( 0.025 %) +Final printing : 0.067 s (92.034 %) +Total time : 0.073 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.602301 -0.409233 -0.011656 + O 0.458444 0.308889 -0.067587 + O 0.312621 1.587607 -0.011075 + H -0.187472 -1.349419 0.086609 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.138183 -0.773338 -0.022027 + 1 O 8.0000 0 15.999 0.866333 0.583715 -0.127720 + 2 O 8.0000 0 15.999 0.590768 3.000143 -0.020928 + 3 H 1.0000 0 1.008 -0.354270 -2.550033 0.163668 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.282187466551 0.00000000 0.00000000 + O 2 1 0 1.288246407968 117.41125260 0.00000000 + H 1 2 3 1.032322310444 100.47465516 189.23076912 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.422983164128 0.00000000 0.00000000 + O 2 1 0 2.434432904068 117.41125260 0.00000000 + H 1 2 3 1.950806448677 100.47465516 189.23076912 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1680 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.271490628933 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.635e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22296 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.2714906289 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.3 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 1.0 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5698571220680719 0.00e+00 9.34e-06 1.17e-04 2.04e-05 0.7 + *** Restarting incremental Fock matrix formation *** + 2 -205.5698572623798555 -1.40e-07 1.32e-05 2.40e-04 6.23e-05 0.2 + 3 -205.5698569027510985 3.60e-07 1.08e-05 1.93e-04 3.41e-04 0.1 + 4 -205.5698572821964945 -3.79e-07 9.00e-07 1.16e-05 6.28e-06 0.1 + 5 -205.5698572817125864 4.84e-10 5.08e-07 9.47e-06 1.65e-05 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56985728171259 Eh -5593.84020 eV + +Components: +Nuclear Repulsion : 70.27149062893305 Eh 1912.18447 eV +Electronic Energy : -275.84134791064565 Eh -7506.02468 eV +One Electron Energy: -420.22888805929500 Eh -11435.00939 eV +Two Electron Energy: 144.38754014864935 Eh 3928.98471 eV + +Virial components: +Potential Energy : -410.43946025012326 Eh -11168.62552 eV +Kinetic Energy : 204.86960296841065 Eh 5574.78531 eV +Virial Ratio : 2.00341804886208 + +DFT components: +N(Alpha) : 11.999998217038 electrons +N(Beta) : 11.999998217038 electrons +N(Total) : 23.999996434076 electrons +E(X) : -23.358317412197 Eh +E(C) : -0.805240500962 Eh +E(XC) : -24.163557913159 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -4.8391e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 9.4706e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 5.0750e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.2181e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.6546e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.3047e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.193001 -522.2681 + 1 2.0000 -19.017316 -517.4875 + 2 2.0000 -14.269324 -388.2880 + 3 2.0000 -1.260359 -34.2961 + 4 2.0000 -0.977169 -26.5901 + 5 2.0000 -0.696131 -18.9427 + 6 2.0000 -0.569852 -15.5065 + 7 2.0000 -0.524529 -14.2732 + 8 2.0000 -0.507434 -13.8080 + 9 2.0000 -0.329324 -8.9614 + 10 2.0000 -0.287748 -7.8300 + 11 2.0000 -0.258331 -7.0296 + 12 0.0000 -0.176323 -4.7980 + 13 0.0000 0.057568 1.5665 + 14 0.0000 0.080904 2.2015 + 15 0.0000 0.150619 4.0985 + 16 0.0000 0.220931 6.0118 + 17 0.0000 0.276013 7.5107 + 18 0.0000 0.295893 8.0517 + 19 0.0000 0.327516 8.9122 + 20 0.0000 0.365262 9.9393 + 21 0.0000 0.380512 10.3542 + 22 0.0000 0.397886 10.8270 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.286271 + 1 O : 0.228739 + 2 O : -0.207624 + 3 H : 0.265156 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.886106 s : 3.886106 + pz : 1.093019 p : 3.338045 + px : 1.184979 + py : 1.060047 + dz2 : 0.008015 d : 0.062120 + dxz : 0.017963 + dyz : 0.004893 + dx2y2 : 0.010439 + dxy : 0.020809 + + 1 O s : 3.738778 s : 3.738778 + pz : 1.380207 p : 3.887200 + px : 1.454402 + py : 1.052591 + dz2 : 0.004762 d : 0.145284 + dxz : 0.013498 + dyz : 0.045742 + dx2y2 : 0.027930 + dxy : 0.053351 + + 2 O s : 3.945586 s : 3.945586 + pz : 1.422668 p : 4.234669 + px : 1.904382 + py : 0.907619 + dz2 : 0.002071 d : 0.027369 + dxz : 0.000174 + dyz : 0.013937 + dx2y2 : 0.008746 + dxy : 0.002441 + + 3 H s : 0.705195 s : 0.705195 + pz : 0.006529 p : 0.029648 + px : 0.006970 + py : 0.016150 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.055956 + 1 O : -0.197030 + 2 O : -0.027299 + 3 H : 0.280285 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.354786 s : 3.354786 + pz : 1.012149 p : 3.380692 + px : 1.281301 + py : 1.087242 + dz2 : 0.039557 d : 0.320478 + dxz : 0.043736 + dyz : 0.026319 + dx2y2 : 0.121628 + dxy : 0.089239 + + 1 O s : 3.356553 s : 3.356553 + pz : 1.273129 p : 4.041123 + px : 1.506943 + py : 1.261051 + dz2 : 0.062761 d : 0.799354 + dxz : 0.039185 + dyz : 0.188191 + dx2y2 : 0.261771 + dxy : 0.247447 + + 2 O s : 3.593500 s : 3.593500 + pz : 1.340822 p : 4.176995 + px : 1.778531 + py : 1.057643 + dz2 : 0.030185 d : 0.256804 + dxz : 0.000802 + dyz : 0.065157 + dx2y2 : 0.074455 + dxy : 0.086205 + + 3 H s : 0.645834 s : 0.645834 + pz : 0.014359 p : 0.073880 + px : 0.019131 + py : 0.040391 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2863 7.0000 -0.2863 2.7266 2.7266 -0.0000 + 1 O 7.7713 8.0000 0.2287 2.6643 2.6643 0.0000 + 2 O 8.2076 8.0000 -0.2076 1.7438 1.7438 0.0000 + 3 H 0.7348 1.0000 0.2652 0.9167 0.9167 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3919 B( 0-N , 2-O ) : 0.4558 B( 0-N , 3-H ) : 0.8790 +B( 1-O , 2-O ) : 1.2614 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.252 sec +Sum of individual times .... 2.068 sec ( 91.8%) + +SCF preparation .... 0.392 sec ( 17.4%) +Fock matrix formation .... 0.795 sec ( 35.3%) + Startup .... 0.230 sec ( 28.9% of F) + Split-RI-J .... 0.023 sec ( 2.9% of F) + XC integration .... 0.185 sec ( 23.2% of F) + Basis function eval. .... 0.006 sec ( 3.5% of XC) + Density eval. .... 0.009 sec ( 4.7% of XC) + XC-Functional eval. .... 0.005 sec ( 2.7% of XC) + XC-Potential eval. .... 0.009 sec ( 4.7% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.024 sec ( 1.1%) +Total Energy calculation .... 0.012 sec ( 0.5%) +Population analysis .... 0.243 sec ( 10.8%) +Orbital Transformation .... 0.216 sec ( 9.6%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.120 sec ( 5.3%) +SOSCF solution .... 0.265 sec ( 11.8%) +Finished LeanSCF after 2.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 5.9 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360234 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007173364 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.563044152210 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.002.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.002.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.149161 0.934541 -0.053640 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5698572817125864 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.462187994 0.630514750 -0.072839789 +Nuclear contribution : -0.244616996 -1.721513370 0.107653472 + ----------------------------------------- +Total Dipole Moment : 0.217570997 -1.090998620 0.034813683 + ----------------------------------------- +Magnitude (a.u.) : 1.113026110 +Magnitude (Debye) : 2.829087539 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.451924 0.427087 0.380456 +Rotational constants in MHz : 103486.067460 12803.756446 11405.790705 + +Dipole components along the rotational axes: +x,y,z [a.u.] : 0.928741 0.608946 0.073841 +x,y,z [Debye]: 2.360672 1.547817 0.187689 + + + +Dipole moment calculation done in 0.0 sec + +Maximum memory used throughout the entire PROP-calculation: 3.1 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 3 * + * * + * Dihedral ( 2, 1, 0, 3) : -161.53846154 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2823 0.744767 + 2. B(O 2,O 1) 1.2915 0.728373 + 3. B(H 3,N 0) 1.0353 0.398640 + 4. A(O 1,N 0,H 3) 100.5052 0.362610 + 5. A(N 0,O 1,O 2) 117.2678 0.449797 + 6. D(O 2,O 1,N 0,H 3) -161.5385 0.043956 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.602880 -0.411891 -0.044582 + O 0.455258 0.308647 -0.118907 + O 0.314295 1.583895 0.028667 + H -0.185381 -1.342806 0.131114 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.139279 -0.778361 -0.084247 + 1 O 8.0000 0 15.999 0.860313 0.583257 -0.224701 + 2 O 8.0000 0 15.999 0.593932 2.993127 0.054172 + 3 H 1.0000 0 1.008 -0.350319 -2.537536 0.247769 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.282187466551 0.00000000 0.00000000 + O 2 1 0 1.288246407968 117.41125260 0.00000000 + H 1 2 3 1.032322310444 100.47465516 189.23076912 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.422983164128 0.00000000 0.00000000 + O 2 1 0 2.434432904068 117.41125260 0.00000000 + H 1 2 3 1.950806448677 100.47465516 189.23076912 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1670 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.187107171508 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.716e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22297 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.1871071715 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.5 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 1.3 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5617365109624757 0.00e+00 3.83e-04 4.92e-03 3.28e-02 0.700 0.5 +Warning: op=0 Small HOMO/LUMO gap ( 0.079) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5630421425650525 -1.31e-03 4.48e-04 5.59e-03 2.61e-02 0.700 0.4 + ***Turning on AO-DIIS*** + 3 -205.5641140716516020 -1.07e-03 3.40e-04 3.99e-03 1.86e-02 0.700 0.2 + 4 -205.5648637490260739 -7.50e-04 8.46e-04 9.44e-03 1.31e-02 0.000 0.1 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5666093052441283 -1.75e-03 7.51e-05 9.33e-04 8.95e-04 0.4 + *** Restarting incremental Fock matrix formation *** + 6 -205.5666113332526379 -2.03e-06 2.73e-04 3.87e-03 1.04e-03 0.4 + 7 -205.5664804839261137 1.31e-04 2.10e-04 3.71e-03 6.30e-03 0.1 + 8 -205.5666215303417630 -1.41e-04 1.85e-05 1.70e-04 1.14e-04 0.1 + 9 -205.5666215693145205 -3.90e-08 8.00e-06 1.48e-04 1.48e-04 0.1 + 10 -205.5666216399346808 -7.06e-08 8.72e-06 7.22e-05 9.53e-05 0.2 + 11 -205.5666216751595243 -3.52e-08 4.36e-06 4.13e-05 3.53e-05 0.2 + 12 -205.5666216975332077 -2.24e-08 1.12e-06 1.53e-05 6.38e-06 0.1 + 13 -205.5666216981445586 -6.11e-10 4.88e-07 5.57e-06 4.04e-06 0.2 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 13 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56662169814456 Eh -5593.75216 eV + +Components: +Nuclear Repulsion : 70.18710717150844 Eh 1909.88828 eV +Electronic Energy : -275.75372886965295 Eh -7503.64044 eV +One Electron Energy: -420.06785972159969 Eh -11430.62758 eV +Two Electron Energy: 144.31413085194671 Eh 3926.98714 eV + +Virial components: +Potential Energy : -410.42941750393254 Eh -11168.35224 eV +Kinetic Energy : 204.86279580578798 Eh 5574.60008 eV +Virial Ratio : 2.00343559644194 + +DFT components: +N(Alpha) : 11.999998379746 electrons +N(Beta) : 11.999998379746 electrons +N(Total) : 23.999996759493 electrons +E(X) : -23.355056280702 Eh +E(C) : -0.805069508674 Eh +E(XC) : -24.160125789377 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 6.1135e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.5730e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.8796e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.9510e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.0448e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 8.5804e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.192180 -522.2458 + 1 2.0000 -19.018483 -517.5192 + 2 2.0000 -14.268786 -388.2734 + 3 2.0000 -1.258745 -34.2522 + 4 2.0000 -0.975940 -26.5567 + 5 2.0000 -0.696665 -18.9572 + 6 2.0000 -0.569022 -15.4839 + 7 2.0000 -0.523087 -14.2339 + 8 2.0000 -0.507372 -13.8063 + 9 2.0000 -0.329817 -8.9748 + 10 2.0000 -0.285259 -7.7623 + 11 2.0000 -0.259102 -7.0505 + 12 0.0000 -0.178982 -4.8703 + 13 0.0000 0.055644 1.5142 + 14 0.0000 0.079919 2.1747 + 15 0.0000 0.149756 4.0751 + 16 0.0000 0.221719 6.0333 + 17 0.0000 0.274157 7.4602 + 18 0.0000 0.298514 8.1230 + 19 0.0000 0.327866 8.9217 + 20 0.0000 0.359745 9.7891 + 21 0.0000 0.379897 10.3375 + 22 0.0000 0.400175 10.8893 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.292592 + 1 O : 0.226101 + 2 O : -0.201466 + 3 H : 0.267957 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.888621 s : 3.888621 + pz : 1.091028 p : 3.342552 + px : 1.186125 + py : 1.065399 + dz2 : 0.007772 d : 0.061419 + dxz : 0.017789 + dyz : 0.004967 + dx2y2 : 0.010336 + dxy : 0.020555 + + 1 O s : 3.741609 s : 3.741609 + pz : 1.380917 p : 3.890560 + px : 1.453306 + py : 1.056337 + dz2 : 0.005270 d : 0.141730 + dxz : 0.014121 + dyz : 0.044343 + dx2y2 : 0.026443 + dxy : 0.051553 + + 2 O s : 3.944976 s : 3.944976 + pz : 1.413530 p : 4.229940 + px : 1.896956 + py : 0.919454 + dz2 : 0.002353 d : 0.026550 + dxz : 0.000108 + dyz : 0.013008 + dx2y2 : 0.008391 + dxy : 0.002690 + + 3 H s : 0.702549 s : 0.702549 + pz : 0.006811 p : 0.029494 + px : 0.006946 + py : 0.015738 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.059509 + 1 O : -0.196643 + 2 O : -0.025767 + 3 H : 0.281919 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.355337 s : 3.355337 + pz : 1.011466 p : 3.383225 + px : 1.282058 + py : 1.089701 + dz2 : 0.038475 d : 0.320947 + dxz : 0.044324 + dyz : 0.028059 + dx2y2 : 0.120724 + dxy : 0.089365 + + 1 O s : 3.358142 s : 3.358142 + pz : 1.275795 p : 4.042093 + px : 1.505962 + py : 1.260335 + dz2 : 0.061801 d : 0.796409 + dxz : 0.041929 + dyz : 0.188023 + dx2y2 : 0.259832 + dxy : 0.244824 + + 2 O s : 3.595801 s : 3.595801 + pz : 1.335526 p : 4.174177 + px : 1.771374 + py : 1.067277 + dz2 : 0.030532 d : 0.255789 + dxz : 0.001716 + dyz : 0.065905 + dx2y2 : 0.073325 + dxy : 0.084310 + + 3 H s : 0.644551 s : 0.644551 + pz : 0.015166 p : 0.073530 + px : 0.019046 + py : 0.039318 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2926 7.0000 -0.2926 2.7172 2.7172 -0.0000 + 1 O 7.7739 8.0000 0.2261 2.6544 2.6544 0.0000 + 2 O 8.2015 8.0000 -0.2015 1.7366 1.7366 -0.0000 + 3 H 0.7320 1.0000 0.2680 0.9148 0.9148 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3882 B( 0-N , 2-O ) : 0.4527 B( 0-N , 3-H ) : 0.8763 +B( 1-O , 2-O ) : 1.2559 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 4 sec + +Total time .... 4.042 sec +Sum of individual times .... 3.813 sec ( 94.3%) + +SCF preparation .... 0.428 sec ( 10.6%) +Fock matrix formation .... 2.048 sec ( 50.7%) + Startup .... 0.314 sec ( 15.3% of F) + Split-RI-J .... 0.060 sec ( 2.9% of F) + XC integration .... 0.470 sec ( 22.9% of F) + Basis function eval. .... 0.020 sec ( 4.2% of XC) + Density eval. .... 0.028 sec ( 6.0% of XC) + XC-Functional eval. .... 0.017 sec ( 3.5% of XC) + XC-Potential eval. .... 0.031 sec ( 6.6% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.395 sec ( 9.8%) +Total Energy calculation .... 0.030 sec ( 0.7%) +Population analysis .... 0.318 sec ( 7.9%) +Orbital Transformation .... 0.143 sec ( 3.5%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.261 sec ( 6.5%) +SOSCF solution .... 0.190 sec ( 4.7%) +Finished LeanSCF after 4.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 6.1 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360336 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007182300 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.559799734324 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000745 -0.000007040 0.000000483 + 2 O : 0.000000652 0.000000168 -0.000000142 + 3 O : 0.000002464 0.000009104 0.000000016 + 4 H : -0.000002372 -0.000002232 -0.000000357 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000122683 +RMS gradient ... 0.0000035416 +MAX gradient ... 0.0000091039 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.001477091 -0.000271521 -0.010511286 + 2 O : -0.003225720 -0.000695209 -0.015769659 + 3 O : 0.001261012 0.000211300 0.012319706 + 4 H : 0.000487616 0.000755430 0.013961240 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000534002 -0.0000451087 0.0000662065 + +Norm of the Cartesian gradient ... 0.0268597840 +RMS gradient ... 0.0077537518 +MAX gradient ... 0.0157696590 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.254 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.005 sec ( 2.0%) +RI-J Coulomb gradient .... 0.061 sec ( 23.9%) +XC gradient .... 0.019 sec ( 7.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.559799734 Eh +Current gradient norm .... 0.026859784 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999981094 +Lowest eigenvalues of augmented Hessian: + -0.000018047 0.361911379 0.394360037 0.448789473 0.719788952 +Length of the computed step .... 0.006149266 +The final length of the internal step .... 0.006149266 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0025104273 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0011786762 RMS(Int)= 0.0025106216 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0012540193 0.0001000000 NO + MAX gradient 0.0018840306 0.0003000000 NO + RMS step 0.0025104273 0.0020000000 NO + MAX step 0.0047773284 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0025 Max(Angles) 0.11 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2823 -0.001686 0.0012 1.2835 + 2. B(O 2,O 1) 1.2915 0.001474 -0.0011 1.2904 + 3. B(H 3,N 0) 1.0353 0.001884 -0.0025 1.0327 + 4. A(O 1,N 0,H 3) 100.51 -0.000710 0.11 100.62 + 5. A(N 0,O 1,O 2) 117.27 -0.000605 0.08 117.34 + 6. D(O 2,O 1,N 0,H 3) -161.54 0.026661 0.00 -161.54 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 2.881 %) +Internal coordinates : 0.000 s ( 1.017 %) +B/P matrices and projection : 0.000 s ( 4.873 %) +Hessian update/contruction : 0.002 s (80.636 %) +Making the step : 0.000 s ( 1.822 %) +Converting the step to Cartesian: 0.000 s ( 1.356 %) +Storing new data : 0.000 s ( 1.186 %) +Checking convergence : 0.000 s ( 0.000 %) +Final printing : 0.000 s ( 6.102 %) +Total time : 0.002 s + +Time for energy+gradient : 9.181 s +Time for complete geometry iter : 10.201 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.602399 -0.413344 -0.044258 + O 0.455537 0.309593 -0.118855 + O 0.314373 1.583742 0.028546 + H -0.186219 -1.342148 0.130859 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.138370 -0.781106 -0.083636 + 1 O 8.0000 0 15.999 0.860839 0.585047 -0.224604 + 2 O 8.0000 0 15.999 0.594080 2.992839 0.053945 + 3 H 1.0000 0 1.008 -0.351902 -2.536292 0.247288 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.283522965085 0.00000000 0.00000000 + O 2 1 0 1.290391005365 117.34499466 0.00000000 + H 1 2 3 1.032738983224 100.61768476 198.46153860 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.425506890610 0.00000000 0.00000000 + O 2 1 0 2.438485605815 117.34499466 0.00000000 + H 1 2 3 1.951593846118 100.61768476 198.46153860 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.189673009730 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.706e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.003 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22297 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.7 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5666178588375033 0.00e+00 5.35e-05 7.54e-04 9.39e-05 0.6 + *** Restarting incremental Fock matrix formation *** + 2 -205.5666227197265812 -4.86e-06 2.98e-05 3.81e-04 2.01e-04 0.5 + 3 -205.5666217810110652 9.39e-07 2.22e-05 3.78e-04 4.99e-04 0.2 + 4 -205.5666228967716052 -1.12e-06 3.73e-05 6.47e-04 2.52e-04 0.2 + 5 -205.5666199962845440 2.90e-06 2.90e-05 4.85e-04 6.94e-04 0.1 + 6 -205.5666231583086869 -3.16e-06 1.89e-06 1.76e-05 1.01e-05 0.4 + 7 -205.5666231593858129 -1.08e-09 6.81e-07 8.12e-06 6.03e-06 0.2 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56662315938581 Eh -5593.75220 eV + +Components: +Nuclear Repulsion : 70.18967300972993 Eh 1909.95810 eV +Electronic Energy : -275.75629616911579 Eh -7503.71030 eV +One Electron Energy: -420.07061880980899 Eh -11430.70266 eV +Two Electron Energy: 144.31432264069323 Eh 3926.99236 eV + +Virial components: +Potential Energy : -410.43153229885365 Eh -11168.40978 eV +Kinetic Energy : 204.86490913946781 Eh 5574.65759 eV +Virial Ratio : 2.00342525239127 + +DFT components: +N(Alpha) : 11.999998342957 electrons +N(Beta) : 11.999998342957 electrons +N(Total) : 23.999996685915 electrons +E(X) : -23.355753899122 Eh +E(C) : -0.805088387998 Eh +E(XC) : -24.160842287120 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.0771e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.1242e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 6.8085e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.1475e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 6.0287e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 6.2584e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 2 sec +Finished LeanSCF after 3.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 6.2 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360318 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007172821 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.559810655994 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000747 -0.000007045 0.000000483 + 2 O : 0.000000653 0.000000174 -0.000000142 + 3 O : 0.000002466 0.000009100 0.000000015 + 4 H : -0.000002372 -0.000002229 -0.000000357 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000122688 +RMS gradient ... 0.0000035417 +MAX gradient ... 0.0000091005 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.002001633 -0.002788686 -0.010178420 + 2 O : -0.002987610 0.000804649 -0.015739946 + 3 O : 0.001571010 -0.000245190 0.012233074 + 4 H : -0.000585033 0.002229227 0.013685292 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000530026 -0.0000450831 0.0000628815 + +Norm of the Cartesian gradient ... 0.0267857789 +RMS gradient ... 0.0077323883 +MAX gradient ... 0.0157399464 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.352 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.006 sec ( 1.7%) +RI-J Coulomb gradient .... 0.065 sec ( 18.5%) +XC gradient .... 0.020 sec ( 5.6%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.559810656 Eh +Current gradient norm .... 0.026785779 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999997023 +Lowest eigenvalues of augmented Hessian: + -0.000002775 0.364275306 0.367627728 0.448112347 0.606128819 +Length of the computed step .... 0.002439966 +The final length of the internal step .... 0.002439966 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0009961121 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0004583228 RMS(Int)= 0.0009961018 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000001387 +Previously predicted energy change .... -0.000009024 +Actually observed energy change .... -0.000010922 +Ratio of predicted to observed change .... 1.210323984 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000109217 0.0000050000 NO + RMS gradient 0.0004790695 0.0001000000 NO + MAX gradient 0.0009787923 0.0003000000 NO + RMS step 0.0009961121 0.0020000000 YES + MAX step 0.0019204286 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0010 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2835 -0.000642 0.0007 1.2842 + 2. B(O 2,O 1) 1.2904 0.000979 -0.0010 1.2894 + 3. B(H 3,N 0) 1.0327 0.000077 -0.0004 1.0324 + 4. A(O 1,N 0,H 3) 100.62 0.000023 0.01 100.62 + 5. A(N 0,O 1,O 2) 117.34 0.000016 0.01 117.35 + 6. D(O 2,O 1,N 0,H 3) -161.54 0.026625 0.00 -161.54 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.028 %) +Internal coordinates : 0.000 s ( 0.010 %) +B/P matrices and projection : 0.000 s ( 0.043 %) +Hessian update/contruction : 0.317 s (91.427 %) +Making the step : 0.000 s ( 0.035 %) +Converting the step to Cartesian: 0.000 s ( 0.016 %) +Storing new data : 0.000 s ( 0.018 %) +Checking convergence : 0.000 s ( 0.004 %) +Final printing : 0.029 s ( 8.418 %) +Total time : 0.347 s + +Time for energy+gradient : 7.776 s +Time for complete geometry iter : 9.107 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.602523 -0.413570 -0.044202 + O 0.455737 0.310125 -0.118821 + O 0.314361 1.583231 0.028495 + H -0.186283 -1.341942 0.130819 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.138603 -0.781534 -0.083529 + 1 O 8.0000 0 15.999 0.861218 0.586052 -0.224539 + 2 O 8.0000 0 15.999 0.594056 2.991873 0.053848 + 3 H 1.0000 0 1.008 -0.352024 -2.535903 0.247213 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.284218097626 0.00000000 0.00000000 + O 2 1 0 1.289374758328 117.35010087 0.00000000 + H 1 2 3 1.032357822192 100.62423200 198.46153860 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.426820500739 0.00000000 0.00000000 + O 2 1 0 2.436565177231 117.35010087 0.00000000 + H 1 2 3 1.950873556154 100.62423200 198.46153860 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.200335252884 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.698e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.003 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22297 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.8 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5666222964624694 0.00e+00 2.78e-05 3.16e-04 5.60e-05 0.4 + *** Restarting incremental Fock matrix formation *** + 2 -205.5666237589797447 -1.46e-06 3.03e-05 5.55e-04 1.33e-04 0.3 + 3 -205.5666219855773988 1.77e-06 2.45e-05 4.33e-04 7.16e-04 0.2 + 4 -205.5666238868145115 -1.90e-06 8.04e-06 1.41e-04 6.75e-05 0.2 + 5 -205.5666237683608415 1.18e-07 5.60e-06 1.06e-04 1.85e-04 0.2 + 6 -205.5666239082406719 -1.40e-07 5.93e-07 6.72e-06 3.81e-06 0.3 + 7 -205.5666239077544333 4.86e-10 2.48e-07 3.44e-06 2.64e-06 0.3 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56662390775443 Eh -5593.75222 eV + +Components: +Nuclear Repulsion : 70.20033525288409 Eh 1910.24824 eV +Electronic Energy : -275.76695916063852 Eh -7504.00045 eV +One Electron Energy: -420.09071315353719 Eh -11431.24946 eV +Two Electron Energy: 144.32375399289867 Eh 3927.24900 eV + +Virial components: +Potential Energy : -410.43267162252369 Eh -11168.44079 eV +Kinetic Energy : 204.86604771476925 Eh 5574.68857 eV +Virial Ratio : 2.00341967935048 + +DFT components: +N(Alpha) : 11.999998321723 electrons +N(Beta) : 11.999998321723 electrons +N(Total) : 23.999996643446 electrons +E(X) : -23.356071722703 Eh +E(C) : -0.805114594211 Eh +E(XC) : -24.161186316914 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -4.8624e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.4426e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.4818e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.5905e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.6375e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.5884e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 2 sec +Finished LeanSCF after 2.7 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 6.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360323 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007171801 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.559812430006 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000746 -0.000007045 0.000000484 + 2 O : 0.000000653 0.000000177 -0.000000142 + 3 O : 0.000002465 0.000009093 0.000000015 + 4 H : -0.000002373 -0.000002226 -0.000000357 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000122622 +RMS gradient ... 0.0000035398 +MAX gradient ... 0.0000090928 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.001859125 -0.003262886 -0.010105460 + 2 O : -0.002745807 0.001727589 -0.015701318 + 3 O : 0.001639118 -0.000901391 0.012163599 + 4 H : -0.000752436 0.002436688 0.013643180 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000516571 -0.0000434911 0.0000597284 + +Norm of the Cartesian gradient ... 0.0267837792 +RMS gradient ... 0.0077318111 +MAX gradient ... 0.0157013183 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.285 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.005 sec ( 1.6%) +RI-J Coulomb gradient .... 0.053 sec ( 18.7%) +XC gradient .... 0.016 sec ( 5.7%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.559812430 Eh +Current gradient norm .... 0.026783779 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999174 +Lowest eigenvalues of augmented Hessian: + -0.000000580 0.311612929 0.387832697 0.448010532 0.487736404 +Length of the computed step .... 0.001285223 +The final length of the internal step .... 0.001285223 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0005246902 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0002794320 RMS(Int)= 0.0005247030 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000290 +Previously predicted energy change .... -0.000001387 +Actually observed energy change .... -0.000001774 +Ratio of predicted to observed change .... 1.278599249 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000017740 0.0000050000 YES + RMS gradient 0.0001879008 0.0001000000 NO + MAX gradient 0.0003155675 0.0003000000 NO + RMS step 0.0005246902 0.0020000000 YES + MAX step 0.0009250778 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0005 Max(Angles) 0.03 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2842 -0.000235 0.0004 1.2846 + 2. B(O 2,O 1) 1.2894 0.000316 -0.0005 1.2889 + 3. B(H 3,N 0) 1.0324 -0.000184 0.0002 1.0325 + 4. A(O 1,N 0,H 3) 100.62 0.000153 -0.03 100.60 + 5. A(N 0,O 1,O 2) 117.35 0.000000 0.01 117.36 + 6. D(O 2,O 1,N 0,H 3) -161.54 0.026615 -0.00 -161.54 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.089 %) +Internal coordinates : 0.000 s ( 0.029 %) +B/P matrices and projection : 0.000 s ( 0.143 %) +Hessian update/contruction : 0.003 s ( 3.716 %) +Making the step : 0.000 s ( 0.055 %) +Converting the step to Cartesian: 0.000 s ( 0.039 %) +Storing new data : 0.000 s ( 0.033 %) +Checking convergence : 0.000 s ( 0.013 %) +Final printing : 0.076 s (95.877 %) +Total time : 0.080 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.602823 -0.413588 -0.044248 + O 0.455732 0.310348 -0.118763 + O 0.314467 1.582980 0.028468 + H -0.186084 -1.341895 0.130835 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.139170 -0.781568 -0.083616 + 1 O 8.0000 0 15.999 0.861209 0.586472 -0.224429 + 2 O 8.0000 0 15.999 0.594257 2.991398 0.053796 + 3 H 1.0000 0 1.008 -0.351649 -2.535814 0.247242 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.284590771175 0.00000000 0.00000000 + O 2 1 0 1.288885228230 117.35512523 0.00000000 + H 1 2 3 1.032510827370 100.59805278 198.46153860 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.427524751683 0.00000000 0.00000000 + O 2 1 0 2.435640099411 117.35512523 0.00000000 + H 1 2 3 1.951162694038 100.59805278 198.46153860 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.203379342677 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.693e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.003 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22297 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.2033793427 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5666243632932719 0.00e+00 1.50e-05 1.81e-04 3.52e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5666247323441667 -3.69e-07 2.03e-05 3.65e-04 8.90e-05 0.0 + 3 -205.5666239017583052 8.31e-07 1.65e-05 2.91e-04 4.92e-04 0.0 + 4 -205.5666247816307646 -8.80e-07 3.34e-06 6.15e-05 2.88e-05 0.0 + 5 -205.5666247609102584 2.07e-08 2.35e-06 4.47e-05 7.75e-05 0.0 + 6 -205.5666247854906032 -2.46e-08 1.89e-07 1.73e-06 1.14e-06 0.0 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 6 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56662478549060 Eh -5593.75224 eV + +Components: +Nuclear Repulsion : 70.20337934267729 Eh 1910.33107 eV +Electronic Energy : -275.77000412816790 Eh -7504.08331 eV +One Electron Energy: -420.09651281249239 Eh -11431.40728 eV +Two Electron Energy: 144.32650868432449 Eh 3927.32396 eV + +Virial components: +Potential Energy : -410.43278057713582 Eh -11168.44375 eV +Kinetic Energy : 204.86615579164521 Eh 5574.69151 eV +Virial Ratio : 2.00341915428216 + +DFT components: +N(Alpha) : 11.999998312357 electrons +N(Beta) : 11.999998312357 electrons +N(Total) : 23.999996624714 electrons +E(X) : -23.356083859865 Eh +E(C) : -0.805123607785 Eh +E(XC) : -24.161207467650 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.4580e-08 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.7330e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.8916e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.1632e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.1362e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.0849e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.192285 -522.2486 + 1 2.0000 -19.019051 -517.5347 + 2 2.0000 -14.268088 -388.2544 + 3 2.0000 -1.259163 -34.2636 + 4 2.0000 -0.976118 -26.5615 + 5 2.0000 -0.697005 -18.9665 + 6 2.0000 -0.569052 -15.4847 + 7 2.0000 -0.523143 -14.2354 + 8 2.0000 -0.507591 -13.8122 + 9 2.0000 -0.330025 -8.9804 + 10 2.0000 -0.285406 -7.7663 + 11 2.0000 -0.259162 -7.0522 + 12 0.0000 -0.179013 -4.8712 + 13 0.0000 0.056832 1.5465 + 14 0.0000 0.081207 2.2098 + 15 0.0000 0.149573 4.0701 + 16 0.0000 0.221505 6.0274 + 17 0.0000 0.274266 7.4631 + 18 0.0000 0.298859 8.1324 + 19 0.0000 0.327587 8.9141 + 20 0.0000 0.359736 9.7889 + 21 0.0000 0.379873 10.3369 + 22 0.0000 0.400157 10.8888 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.293685 + 1 O : 0.226685 + 2 O : -0.200117 + 3 H : 0.267116 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.888201 s : 3.888201 + pz : 1.093012 p : 3.344459 + px : 1.187026 + py : 1.064420 + dz2 : 0.007739 d : 0.061025 + dxz : 0.017700 + dyz : 0.004921 + dx2y2 : 0.010190 + dxy : 0.020475 + + 1 O s : 3.741166 s : 3.741166 + pz : 1.381117 p : 3.890028 + px : 1.454291 + py : 1.054620 + dz2 : 0.005293 d : 0.142121 + dxz : 0.014080 + dyz : 0.044463 + dx2y2 : 0.026562 + dxy : 0.051722 + + 2 O s : 3.944852 s : 3.944852 + pz : 1.411492 p : 4.228547 + px : 1.896135 + py : 0.920920 + dz2 : 0.002386 d : 0.026718 + dxz : 0.000110 + dyz : 0.013082 + dx2y2 : 0.008462 + dxy : 0.002677 + + 3 H s : 0.703178 s : 0.703178 + pz : 0.006885 p : 0.029706 + px : 0.006998 + py : 0.015823 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.059542 + 1 O : -0.196367 + 2 O : -0.024584 + 3 H : 0.280494 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.355256 s : 3.355256 + pz : 1.013145 p : 3.384879 + px : 1.282156 + py : 1.089579 + dz2 : 0.038384 d : 0.319407 + dxz : 0.044009 + dyz : 0.027973 + dx2y2 : 0.119756 + dxy : 0.089286 + + 1 O s : 3.357934 s : 3.357934 + pz : 1.275880 p : 4.041688 + px : 1.505849 + py : 1.259959 + dz2 : 0.061799 d : 0.796745 + dxz : 0.041755 + dyz : 0.188488 + dx2y2 : 0.259308 + dxy : 0.245395 + + 2 O s : 3.594269 s : 3.594269 + pz : 1.333555 p : 4.173412 + px : 1.770378 + py : 1.069479 + dz2 : 0.030588 d : 0.256904 + dxz : 0.001727 + dyz : 0.066248 + dx2y2 : 0.073541 + dxy : 0.084799 + + 3 H s : 0.645349 s : 0.645349 + pz : 0.015379 p : 0.074157 + px : 0.019230 + py : 0.039547 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2937 7.0000 -0.2937 2.7172 2.7172 0.0000 + 1 O 7.7733 8.0000 0.2267 2.6541 2.6541 0.0000 + 2 O 8.2001 8.0000 -0.2001 1.7381 1.7381 -0.0000 + 3 H 0.7329 1.0000 0.2671 0.9153 0.9153 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3865 B( 0-N , 2-O ) : 0.4537 B( 0-N , 3-H ) : 0.8770 +B( 1-O , 2-O ) : 1.2569 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.722 sec +Sum of individual times .... 0.702 sec ( 97.2%) + +SCF preparation .... 0.393 sec ( 54.4%) +Fock matrix formation .... 0.187 sec ( 26.0%) + Startup .... 0.014 sec ( 7.4% of F) + Split-RI-J .... 0.027 sec ( 14.6% of F) + XC integration .... 0.119 sec ( 63.7% of F) + Basis function eval. .... 0.010 sec ( 8.8% of XC) + Density eval. .... 0.014 sec ( 11.7% of XC) + XC-Functional eval. .... 0.009 sec ( 7.7% of XC) + XC-Potential eval. .... 0.017 sec ( 14.0% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.011 sec ( 1.5%) +Total Energy calculation .... 0.014 sec ( 2.0%) +Population analysis .... 0.036 sec ( 5.0%) +Orbital Transformation .... 0.010 sec ( 1.5%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.012 sec ( 1.7%) +SOSCF solution .... 0.039 sec ( 5.4%) +Finished LeanSCF after 0.7 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 6.4 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360328 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007172347 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.559812766389 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.003.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.003.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.148367 0.930356 -0.077679 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5666247854906032 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.467124144 0.640821208 -0.119175102 +Nuclear contribution : -0.242921955 -1.712369960 0.161174084 + ----------------------------------------- +Total Dipole Moment : 0.224202189 -1.071548751 0.041998983 + ----------------------------------------- +Magnitude (a.u.) : 1.095557968 +Magnitude (Debye) : 2.784687053 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.410599 0.426359 0.380517 +Rotational constants in MHz : 102247.187188 12781.924549 11407.611764 + +Dipole components along the rotational axes: +x,y,z [a.u.] : 0.905632 0.598441 -0.148145 +x,y,z [Debye]: 2.301933 1.521116 -0.376554 + + + +Dipole moment calculation done in 0.0 sec + +Maximum memory used throughout the entire PROP-calculation: 3.6 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 4 * + * * + * Dihedral ( 2, 1, 0, 3) : -152.30769231 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2847 0.738220 + 2. B(O 2,O 1) 1.2921 0.726666 + 3. B(H 3,N 0) 1.0355 0.398364 + 4. A(O 1,N 0,H 3) 100.6212 0.362021 + 5. A(N 0,O 1,O 2) 117.2150 0.448885 + 6. D(O 2,O 1,N 0,H 3) -152.3077 0.043097 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.603343 -0.417983 -0.077310 + O 0.450296 0.311358 -0.169142 + O 0.317099 1.574496 0.067894 + H -0.182760 -1.330027 0.174850 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.140153 -0.789874 -0.146094 + 1 O 8.0000 0 15.999 0.850936 0.588382 -0.319633 + 2 O 8.0000 0 15.999 0.599231 2.975367 0.128301 + 3 H 1.0000 0 1.008 -0.345367 -2.513388 0.330419 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.284590771175 0.00000000 0.00000000 + O 2 1 0 1.288885228230 117.35512523 0.00000000 + H 1 2 3 1.032510827370 100.59805278 198.46153860 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.427524751683 0.00000000 0.00000000 + O 2 1 0 2.435640099411 117.35512523 0.00000000 + H 1 2 3 1.951162694038 100.59805278 198.46153860 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1670 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.124674470506 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.778e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22306 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.1246744705 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.5 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5564762678627631 0.00e+00 3.84e-04 4.72e-03 3.22e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.076) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5577648664099115 -1.29e-03 4.52e-04 5.37e-03 2.56e-02 0.700 0.1 + ***Turning on AO-DIIS*** + 3 -205.5588236588110362 -1.06e-03 3.44e-04 3.83e-03 1.83e-02 0.700 0.0 + 4 -205.5595637448643629 -7.40e-04 8.55e-04 9.05e-03 1.29e-02 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5612881608226985 -1.72e-03 7.86e-05 1.03e-03 9.53e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -205.5612899074943130 -1.75e-06 2.93e-04 4.14e-03 1.01e-03 0.0 + 7 -205.5611386549345525 1.51e-04 2.25e-04 3.86e-03 6.28e-03 0.0 + 8 -205.5613010621052581 -1.62e-04 1.82e-05 1.62e-04 1.15e-04 0.0 + 9 -205.5613010257840756 3.63e-08 9.41e-06 1.76e-04 1.99e-04 0.0 + 10 -205.5613011877661052 -1.62e-07 9.16e-06 7.60e-05 7.15e-05 0.0 + 11 -205.5613012162272639 -2.85e-08 4.45e-06 4.89e-05 3.76e-05 0.0 + 12 -205.5613012429829496 -2.68e-08 1.00e-06 1.31e-05 5.10e-06 0.0 + 13 -205.5613012431483071 -1.65e-10 4.25e-07 4.93e-06 3.77e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 13 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56130124314831 Eh -5593.60738 eV + +Components: +Nuclear Repulsion : 70.12467447050624 Eh 1908.18940 eV +Electronic Energy : -275.68597571365456 Eh -7501.79678 eV +One Electron Energy: -419.94461941145960 Eh -11427.27405 eV +Two Electron Energy: 144.25864369780504 Eh 3925.47726 eV + +Virial components: +Potential Energy : -410.42367052741668 Eh -11168.19586 eV +Kinetic Energy : 204.86236928426834 Eh 5574.58847 eV +Virial Ratio : 2.00341171471033 + +DFT components: +N(Alpha) : 11.999998878620 electrons +N(Beta) : 11.999998878620 electrons +N(Total) : 23.999997757239 electrons +E(X) : -23.352780612875 Eh +E(C) : -0.804974460000 Eh +E(XC) : -24.157755072875 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.6536e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.9301e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.2546e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.5260e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.7659e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 5.5943e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.191180 -522.2186 + 1 2.0000 -19.021116 -517.5909 + 2 2.0000 -14.266659 -388.2155 + 3 2.0000 -1.257592 -34.2208 + 4 2.0000 -0.974893 -26.5282 + 5 2.0000 -0.697720 -18.9859 + 6 2.0000 -0.568089 -15.4585 + 7 2.0000 -0.521446 -14.1893 + 8 2.0000 -0.507635 -13.8135 + 9 2.0000 -0.330838 -9.0026 + 10 2.0000 -0.281589 -7.6624 + 11 2.0000 -0.260322 -7.0837 + 12 0.0000 -0.183059 -4.9813 + 13 0.0000 0.055145 1.5006 + 14 0.0000 0.080340 2.1862 + 15 0.0000 0.148848 4.0504 + 16 0.0000 0.222832 6.0636 + 17 0.0000 0.271975 7.4008 + 18 0.0000 0.302470 8.2306 + 19 0.0000 0.328340 8.9346 + 20 0.0000 0.352758 9.5990 + 21 0.0000 0.380318 10.3490 + 22 0.0000 0.401370 10.9218 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.303121 + 1 O : 0.223031 + 2 O : -0.190553 + 3 H : 0.270643 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.891029 s : 3.891029 + pz : 1.091067 p : 3.352246 + px : 1.189601 + py : 1.071579 + dz2 : 0.007312 d : 0.059847 + dxz : 0.017374 + dyz : 0.005056 + dx2y2 : 0.009989 + dxy : 0.020115 + + 1 O s : 3.744264 s : 3.744264 + pz : 1.381295 p : 3.895194 + px : 1.453456 + py : 1.060444 + dz2 : 0.006290 d : 0.137511 + dxz : 0.015232 + dyz : 0.042129 + dx2y2 : 0.024537 + dxy : 0.049323 + + 2 O s : 3.944008 s : 3.944008 + pz : 1.393262 p : 4.220930 + px : 1.883582 + py : 0.944086 + dz2 : 0.002866 d : 0.025615 + dxz : 0.000033 + dyz : 0.011756 + dx2y2 : 0.007960 + dxy : 0.002999 + + 3 H s : 0.699751 s : 0.699751 + pz : 0.007361 p : 0.029606 + px : 0.006998 + py : 0.015248 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.065130 + 1 O : -0.196051 + 2 O : -0.021262 + 3 H : 0.282444 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.355273 s : 3.355273 + pz : 1.012981 p : 3.390111 + px : 1.284173 + py : 1.092956 + dz2 : 0.036774 d : 0.319746 + dxz : 0.044699 + dyz : 0.030544 + dx2y2 : 0.118128 + dxy : 0.089601 + + 1 O s : 3.359527 s : 3.359527 + pz : 1.279584 p : 4.043194 + px : 1.504669 + py : 1.258940 + dz2 : 0.060928 d : 0.793331 + dxz : 0.046420 + dyz : 0.188603 + dx2y2 : 0.256062 + dxy : 0.241317 + + 2 O s : 3.596643 s : 3.596643 + pz : 1.322112 p : 4.168671 + px : 1.758349 + py : 1.088211 + dz2 : 0.031377 d : 0.255948 + dxz : 0.003402 + dyz : 0.067651 + dx2y2 : 0.071619 + dxy : 0.081899 + + 3 H s : 0.643618 s : 0.643618 + pz : 0.016722 p : 0.073938 + px : 0.019212 + py : 0.038004 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3031 7.0000 -0.3031 2.7024 2.7024 -0.0000 + 1 O 7.7770 8.0000 0.2230 2.6403 2.6403 0.0000 + 2 O 8.1906 8.0000 -0.1906 1.7282 1.7282 0.0000 + 3 H 0.7294 1.0000 0.2706 0.9128 0.9128 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3805 B( 0-N , 2-O ) : 0.4488 B( 0-N , 3-H ) : 0.8731 +B( 1-O , 2-O ) : 1.2497 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 1.000 sec +Sum of individual times .... 0.985 sec ( 98.5%) + +SCF preparation .... 0.403 sec ( 40.3%) +Fock matrix formation .... 0.372 sec ( 37.2%) + Startup .... 0.015 sec ( 4.0% of F) + Split-RI-J .... 0.051 sec ( 13.8% of F) + XC integration .... 0.255 sec ( 68.5% of F) + Basis function eval. .... 0.014 sec ( 5.3% of XC) + Density eval. .... 0.021 sec ( 8.1% of XC) + XC-Functional eval. .... 0.012 sec ( 4.8% of XC) + XC-Potential eval. .... 0.020 sec ( 7.9% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.022 sec ( 2.2%) +Total Energy calculation .... 0.028 sec ( 2.8%) +Population analysis .... 0.024 sec ( 2.4%) +Orbital Transformation .... 0.014 sec ( 1.4%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.071 sec ( 7.1%) +SOSCF solution .... 0.050 sec ( 5.0%) +Finished LeanSCF after 1.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 6.6 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360522 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007182404 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.554479360746 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000734 -0.000006996 0.000000617 + 2 O : 0.000000647 0.000000179 -0.000000206 + 3 O : 0.000002464 0.000008988 0.000000178 + 4 H : -0.000002376 -0.000002171 -0.000000589 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000121633 +RMS gradient ... 0.0000035112 +MAX gradient ... 0.0000089881 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.004208185 -0.003148274 -0.015483704 + 2 O : -0.007223563 0.001738217 -0.022581822 + 3 O : 0.003237098 -0.002027521 0.017774098 + 4 H : -0.000221720 0.003437579 0.020291428 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000476219 -0.0000447508 0.0000517693 + +Norm of the Cartesian gradient ... 0.0398324221 +RMS gradient ... 0.0114986298 +MAX gradient ... 0.0225818223 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.139 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.9%) +RI-J Coulomb gradient .... 0.064 sec ( 46.1%) +XC gradient .... 0.020 sec ( 14.6%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.554479361 Eh +Current gradient norm .... 0.039832422 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999972562 +Lowest eigenvalues of augmented Hessian: + -0.000027835 0.361312751 0.393995211 0.447893026 0.718213942 +Length of the computed step .... 0.007407980 +The final length of the internal step .... 0.007407980 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0030242953 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0018399689 RMS(Int)= 0.0030246744 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0016165378 0.0001000000 NO + MAX gradient 0.0030846007 0.0003000000 NO + RMS step 0.0030242953 0.0020000000 NO + MAX step 0.0046256374 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0024 Max(Angles) 0.21 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2847 -0.003085 0.0022 1.2869 + 2. B(O 2,O 1) 1.2921 0.000940 -0.0007 1.2914 + 3. B(H 3,N 0) 1.0355 0.001823 -0.0024 1.0331 + 4. A(O 1,N 0,H 3) 100.62 -0.001301 0.21 100.83 + 5. A(N 0,O 1,O 2) 117.22 -0.000515 0.07 117.28 + 6. D(O 2,O 1,N 0,H 3) -152.31 0.039412 0.00 -152.31 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.741 %) +Internal coordinates : 0.000 s ( 4.539 %) +B/P matrices and projection : 0.000 s (18.306 %) +Hessian update/contruction : 0.000 s (25.265 %) +Making the step : 0.000 s ( 7.564 %) +Converting the step to Cartesian: 0.000 s ( 5.295 %) +Storing new data : 0.000 s ( 4.236 %) +Checking convergence : 0.000 s ( 0.000 %) +Final printing : 0.000 s (23.752 %) +Total time : 0.001 s + +Time for energy+gradient : 4.451 s +Time for complete geometry iter : 5.410 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.602659 -0.419868 -0.076615 + O 0.451206 0.312928 -0.169316 + O 0.317117 1.575262 0.067724 + H -0.184372 -1.330479 0.174500 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.138861 -0.793435 -0.144782 + 1 O 8.0000 0 15.999 0.852656 0.591349 -0.319962 + 2 O 8.0000 0 15.999 0.599264 2.976815 0.127979 + 3 H 1.0000 0 1.008 -0.348413 -2.514241 0.329757 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.286940441018 0.00000000 0.00000000 + O 2 1 0 1.291377468431 117.28083549 0.00000000 + H 1 2 3 1.033070808234 100.82759289 207.69230751 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.431964984192 0.00000000 0.00000000 + O 2 1 0 2.440349750850 117.28083549 0.00000000 + H 1 2 3 1.952220904511 100.82759289 207.69230751 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.090641467407 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.772e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22306 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5612972319921425 0.00e+00 6.43e-05 7.33e-04 1.17e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5613049343251362 -7.70e-06 5.17e-05 6.38e-04 2.90e-04 0.0 + 3 -205.5613013807576124 3.55e-06 4.03e-05 7.31e-04 7.09e-04 0.0 + 4 -205.5613049739482392 -3.59e-06 6.04e-05 9.46e-04 3.87e-04 0.0 + 5 -205.5612976735943960 7.30e-06 4.55e-05 7.70e-04 1.24e-03 0.0 + 6 -205.5613058131342825 -8.14e-06 3.61e-06 5.03e-05 1.67e-05 0.0 + 7 -205.5613058137081168 -5.74e-10 1.77e-06 2.72e-05 1.57e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56130581370812 Eh -5593.60750 eV + +Components: +Nuclear Repulsion : 70.09064146740687 Eh 1907.26332 eV +Electronic Energy : -275.65194728111499 Eh -7500.87082 eV +One Electron Energy: -419.87812484961142 Eh -11425.46464 eV +Two Electron Energy: 144.22617756849647 Eh 3924.59381 eV + +Virial components: +Potential Energy : -410.42174970567930 Eh -11168.14359 eV +Kinetic Energy : 204.86044389197119 Eh 5574.53608 eV +Virial Ratio : 2.00342116764184 + +DFT components: +N(Alpha) : 11.999998840005 electrons +N(Beta) : 11.999998840005 electrons +N(Total) : 23.999997680010 electrons +E(X) : -23.352549562829 Eh +E(C) : -0.804923774416 Eh +E(XC) : -24.157473337245 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 5.7383e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.7216e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.7725e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.1194e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.5651e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.8581e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.7 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 6.8 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360473 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007170270 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.554496016859 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000741 -0.000007008 0.000000616 + 2 O : 0.000000649 0.000000188 -0.000000207 + 3 O : 0.000002469 0.000009002 0.000000176 + 4 H : -0.000002377 -0.000002182 -0.000000586 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000121844 +RMS gradient ... 0.0000035173 +MAX gradient ... 0.0000090023 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.004306497 -0.006251555 -0.014939290 + 2 O : -0.006315098 0.003543542 -0.022629164 + 3 O : 0.003550582 -0.001952653 0.017680570 + 4 H : -0.001541981 0.004660666 0.019887884 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000421873 -0.0000420084 0.0000520958 + +Norm of the Cartesian gradient ... 0.0399246278 +RMS gradient ... 0.0115252473 +MAX gradient ... 0.0226291637 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.130 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.9%) +RI-J Coulomb gradient .... 0.063 sec ( 48.8%) +XC gradient .... 0.020 sec ( 15.7%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.554496017 Eh +Current gradient norm .... 0.039924628 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999995752 +Lowest eigenvalues of augmented Hessian: + -0.000004011 0.361412765 0.373010932 0.468335297 0.564406303 +Length of the computed step .... 0.002914683 +The final length of the internal step .... 0.002914683 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0011899143 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0005915613 RMS(Int)= 0.0011898187 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000002005 +Previously predicted energy change .... -0.000013918 +Actually observed energy change .... -0.000016656 +Ratio of predicted to observed change .... 1.196714169 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000166561 0.0000050000 NO + RMS gradient 0.0005764113 0.0001000000 NO + MAX gradient 0.0009961325 0.0003000000 NO + RMS step 0.0011899143 0.0020000000 YES + MAX step 0.0020818542 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0011 Max(Angles) 0.03 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2869 -0.000996 0.0011 1.2880 + 2. B(O 2,O 1) 1.2914 0.000963 -0.0009 1.2904 + 3. B(H 3,N 0) 1.0331 0.000101 -0.0004 1.0327 + 4. A(O 1,N 0,H 3) 100.83 0.000048 0.01 100.84 + 5. A(N 0,O 1,O 2) 117.28 0.000246 -0.03 117.25 + 6. D(O 2,O 1,N 0,H 3) -152.31 0.039280 0.00 -152.31 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 8.397 %) +Internal coordinates : 0.000 s ( 2.958 %) +B/P matrices and projection : 0.000 s (13.836 %) +Hessian update/contruction : 0.000 s (39.122 %) +Making the step : 0.000 s ( 5.534 %) +Converting the step to Cartesian: 0.000 s ( 4.389 %) +Storing new data : 0.000 s ( 2.958 %) +Checking convergence : 0.000 s ( 1.336 %) +Final printing : 0.000 s (21.183 %) +Total time : 0.001 s + +Time for energy+gradient : 4.130 s +Time for complete geometry iter : 4.938 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.602800 -0.420105 -0.076439 + O 0.451807 0.313526 -0.169403 + O 0.316905 1.574793 0.067685 + H -0.184621 -1.330369 0.174449 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.139127 -0.793884 -0.144448 + 1 O 8.0000 0 15.999 0.853792 0.592477 -0.320126 + 2 O 8.0000 0 15.999 0.598864 2.975928 0.127905 + 3 H 1.0000 0 1.008 -0.348882 -2.514034 0.329661 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.288042110826 0.00000000 0.00000000 + O 2 1 0 1.290428362028 117.24810544 0.00000000 + H 1 2 3 1.032666134276 100.83804989 207.69230751 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.434046838419 0.00000000 0.00000000 + O 2 1 0 2.438556199678 117.24810544 0.00000000 + H 1 2 3 1.951456181557 100.83804989 207.69230751 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.092477075896 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.764e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22306 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5613060675410111 0.00e+00 3.27e-05 3.31e-04 6.67e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5613082581194249 -2.19e-06 3.55e-05 5.67e-04 1.34e-04 0.0 + 3 -205.5613060915799792 2.17e-06 2.76e-05 4.75e-04 7.32e-04 0.0 + 4 -205.5613084379138513 -2.35e-06 1.23e-05 2.21e-04 9.57e-05 0.0 + 5 -205.5613081778708988 2.60e-07 8.49e-06 1.60e-04 2.60e-04 0.0 + 6 -205.5613084840748002 -3.06e-07 1.13e-06 1.32e-05 5.26e-06 0.0 + 7 -205.5613084841176033 -4.28e-11 5.14e-07 7.41e-06 4.56e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56130848411760 Eh -5593.60758 eV + +Components: +Nuclear Repulsion : 70.09247707589621 Eh 1907.31327 eV +Electronic Energy : -275.65378556001383 Eh -7500.92084 eV +One Electron Energy: -419.88089036679457 Eh -11425.53989 eV +Two Electron Energy: 144.22710480678074 Eh 3924.61905 eV + +Virial components: +Potential Energy : -410.42196478920465 Eh -11168.14944 eV +Kinetic Energy : 204.86065630508705 Eh 5574.54186 eV +Virial Ratio : 2.00342014026347 + +DFT components: +N(Alpha) : 11.999998813605 electrons +N(Beta) : 11.999998813605 electrons +N(Total) : 23.999997627211 electrons +E(X) : -23.352514741033 Eh +E(C) : -0.804929240119 Eh +E(XC) : -24.157443981152 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 4.2803e-11 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.4149e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 5.1425e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.3127e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.5565e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 5.7669e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.7 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 6.9 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360477 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007170351 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.554498610195 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000741 -0.000007007 0.000000616 + 2 O : 0.000000650 0.000000192 -0.000000207 + 3 O : 0.000002468 0.000008995 0.000000176 + 4 H : -0.000002377 -0.000002180 -0.000000585 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000121786 +RMS gradient ... 0.0000035156 +MAX gradient ... 0.0000089953 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.003915880 -0.006828952 -0.014791241 + 2 O : -0.005689119 0.004477609 -0.022602780 + 3 O : 0.003513174 -0.002516306 0.017584058 + 4 H : -0.001739934 0.004867649 0.019809964 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000410048 -0.0000387785 0.0000470487 + +Norm of the Cartesian gradient ... 0.0398883385 +RMS gradient ... 0.0115147715 +MAX gradient ... 0.0226027803 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.131 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.0%) +RI-J Coulomb gradient .... 0.059 sec ( 45.0%) +XC gradient .... 0.020 sec ( 15.4%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.554498610 Eh +Current gradient norm .... 0.039888338 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999998560 +Lowest eigenvalues of augmented Hessian: + -0.000000966 0.308786055 0.391524542 0.450807570 0.471206949 +Length of the computed step .... 0.001696795 +The final length of the internal step .... 0.001696795 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0006927137 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0003565613 RMS(Int)= 0.0006927320 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000483 +Previously predicted energy change .... -0.000002005 +Actually observed energy change .... -0.000002593 +Ratio of predicted to observed change .... 1.293258987 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000025933 0.0000050000 YES + RMS gradient 0.0002369259 0.0001000000 NO + MAX gradient 0.0003998320 0.0003000000 NO + RMS step 0.0006927137 0.0020000000 YES + MAX step 0.0010868464 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0006 Max(Angles) 0.04 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2880 -0.000297 0.0006 1.2886 + 2. B(O 2,O 1) 1.2904 0.000400 -0.0006 1.2899 + 3. B(H 3,N 0) 1.0327 -0.000183 0.0002 1.0328 + 4. A(O 1,N 0,H 3) 100.84 0.000234 -0.04 100.80 + 5. A(N 0,O 1,O 2) 117.25 -0.000002 -0.00 117.25 + 6. D(O 2,O 1,N 0,H 3) -152.31 0.039241 -0.00 -152.31 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (11.336 %) +Internal coordinates : 0.000 s ( 3.479 %) +B/P matrices and projection : 0.000 s (16.049 %) +Hessian update/contruction : 0.000 s (24.804 %) +Making the step : 0.000 s ( 5.836 %) +Converting the step to Cartesian: 0.000 s ( 4.265 %) +Storing new data : 0.000 s ( 3.143 %) +Checking convergence : 0.000 s ( 1.459 %) +Final printing : 0.000 s (29.405 %) +Total time : 0.001 s + +Time for energy+gradient : 4.102 s +Time for complete geometry iter : 4.949 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 4 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.603211 -0.420160 -0.076512 + O 0.451884 0.313785 -0.169314 + O 0.317003 1.574492 0.067642 + H -0.184384 -1.330273 0.174476 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.139904 -0.793987 -0.144587 + 1 O 8.0000 0 15.999 0.853937 0.592968 -0.319957 + 2 O 8.0000 0 15.999 0.599049 2.975358 0.127825 + 3 H 1.0000 0 1.008 -0.348435 -2.513852 0.329712 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.288609089622 0.00000000 0.00000000 + O 2 1 0 1.289853227688 117.24795967 0.00000000 + H 1 2 3 1.032820462944 100.79898583 207.69230751 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.435118273068 0.00000000 0.00000000 + O 2 1 0 2.437469353285 117.24795967 0.00000000 + H 1 2 3 1.951747820475 100.79898583 207.69230751 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.093669168906 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.759e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22306 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5613093087656864 0.00e+00 1.95e-05 2.25e-04 4.65e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5613099416611078 -6.33e-07 2.56e-05 4.41e-04 1.01e-04 0.0 + 3 -205.5613086620407159 1.28e-06 2.06e-05 3.52e-04 5.63e-04 0.0 + 4 -205.5613100207201853 -1.36e-06 5.73e-06 1.06e-04 4.57e-05 0.0 + 5 -205.5613099594255289 6.13e-08 4.06e-06 7.63e-05 1.25e-04 0.0 + 6 -205.5613100309264780 -7.15e-08 3.70e-07 4.16e-06 1.70e-06 0.0 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 6 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56131003092648 Eh -5593.60762 eV + +Components: +Nuclear Repulsion : 70.09366916890573 Eh 1907.34571 eV +Electronic Energy : -275.65497919983221 Eh -7500.95333 eV +One Electron Energy: -419.88282187813860 Eh -11425.59245 eV +Two Electron Energy: 144.22784267830639 Eh 3924.63912 eV + +Virial components: +Potential Energy : -410.42195728692457 Eh -11168.14924 eV +Kinetic Energy : 204.86064725599812 Eh 5574.54162 eV +Virial Ratio : 2.00342019213701 + +DFT components: +N(Alpha) : 11.999998799875 electrons +N(Beta) : 11.999998799875 electrons +N(Total) : 23.999997599749 electrons +E(X) : -23.352429338395 Eh +E(C) : -0.804934378862 Eh +E(XC) : -24.157363717257 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 7.1501e-08 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.1626e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.7000e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.7248e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.7049e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.9702e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.7 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 6.9 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360481 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007171332 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.554499180308 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000740 -0.000007007 0.000000617 + 2 O : 0.000000650 0.000000193 -0.000000206 + 3 O : 0.000002468 0.000008991 0.000000175 + 4 H : -0.000002379 -0.000002178 -0.000000586 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000121754 +RMS gradient ... 0.0000035147 +MAX gradient ... 0.0000089915 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.003554053 -0.006859775 -0.014784074 + 2 O : -0.005439270 0.004940630 -0.022567969 + 3 O : 0.003534502 -0.002860715 0.017525896 + 4 H : -0.001649284 0.004779860 0.019826147 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000407243 -0.0000370764 0.0000440100 + +Norm of the Cartesian gradient ... 0.0398502459 +RMS gradient ... 0.0115037751 +MAX gradient ... 0.0225679692 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.132 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 4.1%) +RI-J Coulomb gradient .... 0.062 sec ( 46.7%) +XC gradient .... 0.018 sec ( 13.7%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.554499180 Eh +Current gradient norm .... 0.039850246 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999847 +Lowest eigenvalues of augmented Hessian: + -0.000000087 0.248135027 0.409403836 0.441170108 0.474046597 +Length of the computed step .... 0.000552806 +The final length of the internal step .... 0.000552806 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0002256821 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001835215 RMS(Int)= 0.0002256886 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000043 +Previously predicted energy change .... -0.000000483 +Actually observed energy change .... -0.000000570 +Ratio of predicted to observed change .... 1.179896190 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000005701 0.0000050000 YES + RMS gradient 0.0000666585 0.0001000000 YES + MAX gradient 0.0001373153 0.0003000000 YES + RMS step 0.0002256821 0.0020000000 YES + MAX step 0.0004592402 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.03 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2886 -0.000007 0.0001 1.2887 + 2. B(O 2,O 1) 1.2899 0.000050 -0.0001 1.2897 + 3. B(H 3,N 0) 1.0328 -0.000064 0.0001 1.0329 + 4. A(O 1,N 0,H 3) 100.80 0.000137 -0.03 100.77 + 5. A(N 0,O 1,O 2) 117.25 -0.000035 0.01 117.25 + 6. D(O 2,O 1,N 0,H 3) -152.31 0.039230 -0.00 -152.31 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (12.844 %) +Internal coordinates : 0.000 s ( 3.058 %) +B/P matrices and projection : 0.000 s (14.985 %) +Hessian update/contruction : 0.000 s (27.115 %) +Making the step : 0.000 s ( 5.199 %) +Converting the step to Cartesian: 0.000 s ( 4.077 %) +Storing new data : 0.000 s ( 3.160 %) +Checking convergence : 0.000 s ( 1.427 %) +Final printing : 0.000 s (27.829 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 4 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.603407 -0.420163 -0.076580 + O 0.451810 0.313772 -0.169247 + O 0.317089 1.574404 0.067630 + H -0.184200 -1.330169 0.174488 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.140273 -0.793994 -0.144716 + 1 O 8.0000 0 15.999 0.853796 0.592944 -0.319830 + 2 O 8.0000 0 15.999 0.599212 2.975193 0.127803 + 3 H 1.0000 0 1.008 -0.348088 -2.513655 0.329735 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.288693226022 0.00000000 0.00000000 + O 2 1 0 1.289748993157 117.25330315 0.00000000 + H 1 2 3 1.032898803947 100.77267331 207.69230751 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.435277267822 0.00000000 0.00000000 + O 2 1 0 2.437272378567 117.25330315 0.00000000 + H 1 2 3 1.951895863516 100.77267331 207.69230751 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.094114426354 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.758e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22306 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.0941144264 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5613105624218804 0.00e+00 6.01e-06 6.23e-05 1.10e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5613106128118659 -5.04e-08 5.35e-06 8.58e-05 1.75e-05 0.0 + 3 -205.5613105752937315 3.75e-08 3.98e-06 6.21e-05 9.99e-05 0.0 + 4 -205.5613106182657077 -4.30e-08 2.21e-06 3.12e-05 1.29e-05 0.0 + 5 -205.5613106131480379 5.12e-09 1.27e-06 2.35e-05 3.74e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56131061314804 Eh -5593.60764 eV + +Components: +Nuclear Repulsion : 70.09411442635374 Eh 1907.35782 eV +Electronic Energy : -275.65542503950178 Eh -7500.96546 eV +One Electron Energy: -419.88336035291400 Eh -11425.60710 eV +Two Electron Energy: 144.22793531341222 Eh 3924.64164 eV + +Virial components: +Potential Energy : -410.42191567987635 Eh -11168.14810 eV +Kinetic Energy : 204.86060506672831 Eh 5574.54047 eV +Virial Ratio : 2.00342040162476 + +DFT components: +N(Alpha) : 11.999998797608 electrons +N(Beta) : 11.999998797608 electrons +N(Total) : 23.999997595217 electrons +E(X) : -23.352401587574 Eh +E(C) : -0.804936376121 Eh +E(XC) : -24.157337963696 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -5.1177e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.3543e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.2722e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.4294e-05 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.7352e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.9253e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.191351 -522.2232 + 1 2.0000 -19.021882 -517.6117 + 2 2.0000 -14.265958 -388.1964 + 3 2.0000 -1.257361 -34.2145 + 4 2.0000 -0.974411 -26.5151 + 5 2.0000 -0.698366 -19.0035 + 6 2.0000 -0.567754 -15.4494 + 7 2.0000 -0.521116 -14.1803 + 8 2.0000 -0.507793 -13.8177 + 9 2.0000 -0.331106 -9.0098 + 10 2.0000 -0.281697 -7.6654 + 11 2.0000 -0.260490 -7.0883 + 12 0.0000 -0.183399 -4.9905 + 13 0.0000 0.055733 1.5166 + 14 0.0000 0.081697 2.2231 + 15 0.0000 0.147703 4.0192 + 16 0.0000 0.222350 6.0505 + 17 0.0000 0.272243 7.4081 + 18 0.0000 0.302891 8.2421 + 19 0.0000 0.327831 8.9207 + 20 0.0000 0.352869 9.6020 + 21 0.0000 0.380134 10.3440 + 22 0.0000 0.401392 10.9224 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.304407 + 1 O : 0.223159 + 2 O : -0.188524 + 3 H : 0.269772 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.890880 s : 3.890880 + pz : 1.093386 p : 3.354236 + px : 1.190281 + py : 1.070569 + dz2 : 0.007270 d : 0.059291 + dxz : 0.017236 + dyz : 0.004981 + dx2y2 : 0.009816 + dxy : 0.019987 + + 1 O s : 3.744623 s : 3.744623 + pz : 1.381975 p : 3.894607 + px : 1.454237 + py : 1.058394 + dz2 : 0.006315 d : 0.137611 + dxz : 0.015163 + dyz : 0.042112 + dx2y2 : 0.024632 + dxy : 0.049388 + + 2 O s : 3.944024 s : 3.944024 + pz : 1.391257 p : 4.218741 + px : 1.882183 + py : 0.945301 + dz2 : 0.002904 d : 0.025759 + dxz : 0.000039 + dyz : 0.011807 + dx2y2 : 0.008022 + dxy : 0.002987 + + 3 H s : 0.700422 s : 0.700422 + pz : 0.007434 p : 0.029806 + px : 0.007038 + py : 0.015334 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.065490 + 1 O : -0.195281 + 2 O : -0.020090 + 3 H : 0.280861 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.356147 s : 3.356147 + pz : 1.015151 p : 3.391771 + px : 1.283710 + py : 1.092911 + dz2 : 0.036669 d : 0.317571 + dxz : 0.044284 + dyz : 0.030370 + dx2y2 : 0.116863 + dxy : 0.089386 + + 1 O s : 3.360245 s : 3.360245 + pz : 1.280167 p : 4.042518 + px : 1.504116 + py : 1.258236 + dz2 : 0.060872 d : 0.792518 + dxz : 0.046126 + dyz : 0.188813 + dx2y2 : 0.255035 + dxy : 0.241672 + + 2 O s : 3.595368 s : 3.595368 + pz : 1.320352 p : 4.167568 + px : 1.756996 + py : 1.090220 + dz2 : 0.031451 d : 0.257154 + dxz : 0.003439 + dyz : 0.068037 + dx2y2 : 0.071819 + dxy : 0.082407 + + 3 H s : 0.644557 s : 0.644557 + pz : 0.016940 p : 0.074582 + px : 0.019371 + py : 0.038271 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3044 7.0000 -0.3044 2.7024 2.7024 0.0000 + 1 O 7.7768 8.0000 0.2232 2.6396 2.6396 -0.0000 + 2 O 8.1885 8.0000 -0.1885 1.7302 1.7302 -0.0000 + 3 H 0.7302 1.0000 0.2698 0.9134 0.9134 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3783 B( 0-N , 2-O ) : 0.4503 B( 0-N , 3-H ) : 0.8738 +B( 1-O , 2-O ) : 1.2508 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.650 sec +Sum of individual times .... 0.635 sec ( 97.7%) + +SCF preparation .... 0.395 sec ( 60.8%) +Fock matrix formation .... 0.143 sec ( 22.0%) + Startup .... 0.008 sec ( 5.2% of F) + Split-RI-J .... 0.022 sec ( 15.3% of F) + XC integration .... 0.095 sec ( 66.3% of F) + Basis function eval. .... 0.006 sec ( 6.2% of XC) + Density eval. .... 0.008 sec ( 8.9% of XC) + XC-Functional eval. .... 0.005 sec ( 4.8% of XC) + XC-Potential eval. .... 0.008 sec ( 8.6% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.008 sec ( 1.2%) +Total Energy calculation .... 0.011 sec ( 1.6%) +Population analysis .... 0.033 sec ( 5.0%) +Orbital Transformation .... 0.007 sec ( 1.0%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.010 sec ( 1.6%) +SOSCF solution .... 0.028 sec ( 4.4%) +Finished LeanSCF after 0.7 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 7.0 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360484 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007171873 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.554499223470 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.004.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.004.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.147278 0.923816 -0.101395 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5613106131480379 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.475907204 0.659154785 -0.162927110 +Nuclear contribution : -0.240615886 -1.698113360 0.213997691 + ----------------------------------------- +Total Dipole Moment : 0.235291318 -1.038958575 0.051070582 + ----------------------------------------- +Magnitude (a.u.) : 1.066491973 +Magnitude (Debye) : 2.710807164 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.344641 0.425262 0.380618 +Rotational constants in MHz : 100269.820133 12749.044525 11410.635351 + +Dipole components along the rotational axes: +x,y,z [a.u.] : -0.866746 0.579979 0.223116 +x,y,z [Debye]: -2.203093 1.474190 0.567116 + + + +Dipole moment calculation done in 0.0 sec + +Maximum memory used throughout the entire PROP-calculation: 4.2 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 5 * + * * + * Dihedral ( 2, 1, 0, 3) : -143.07692308 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2888 0.727178 + 2. B(O 2,O 1) 1.2929 0.724363 + 3. B(H 3,N 0) 1.0360 0.397797 + 4. A(O 1,N 0,H 3) 100.7844 0.361004 + 5. A(N 0,O 1,O 2) 117.1173 0.447402 + 6. D(O 2,O 1,N 0,H 3) -143.0769 0.041673 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.603634 -0.426341 -0.109776 + O 0.444333 0.316029 -0.218195 + O 0.320521 1.561328 0.106482 + H -0.179928 -1.313172 0.217780 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.140703 -0.805668 -0.207446 + 1 O 8.0000 0 15.999 0.839667 0.597208 -0.412328 + 2 O 8.0000 0 15.999 0.605697 2.950483 0.201223 + 3 H 1.0000 0 1.008 -0.340014 -2.481535 0.411544 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.288693226022 0.00000000 0.00000000 + O 2 1 0 1.289748993157 117.25330315 0.00000000 + H 1 2 3 1.032898803947 100.77267331 207.69230751 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.435277267822 0.00000000 0.00000000 + O 2 1 0 2.437272378567 117.25330315 0.00000000 + H 1 2 3 1.951895863516 100.77267331 207.69230751 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1670 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.021435411911 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.823e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22305 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.0214354119 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5492538784935164 0.00e+00 3.88e-04 4.42e-03 3.14e-02 0.700 0.4 +Warning: op=0 Small HOMO/LUMO gap ( 0.072) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5505216177795660 -1.27e-03 4.60e-04 5.04e-03 2.50e-02 0.700 0.7 + ***Turning on AO-DIIS*** + 3 -205.5515647121264351 -1.04e-03 3.50e-04 3.60e-03 1.78e-02 0.700 0.4 + 4 -205.5522934056647273 -7.29e-04 8.71e-04 8.48e-03 1.25e-02 0.000 0.2 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5539927587649913 -1.70e-03 8.13e-05 1.05e-03 9.51e-04 0.4 + *** Restarting incremental Fock matrix formation *** + 6 -205.5539947193490775 -1.96e-06 3.05e-04 4.26e-03 8.82e-04 0.5 + 7 -205.5538361898784956 1.59e-04 2.31e-04 3.77e-03 5.81e-03 0.1 + 8 -205.5540066150194320 -1.70e-04 1.75e-05 1.39e-04 1.16e-04 0.1 + 9 -205.5540066890066555 -7.40e-08 8.97e-06 1.55e-04 1.17e-04 0.2 + 10 -205.5540067419320280 -5.29e-08 7.78e-06 6.69e-05 8.22e-05 0.1 + 11 -205.5540067840190659 -4.21e-08 4.11e-06 5.46e-05 2.99e-05 0.2 + 12 -205.5540068036671073 -1.96e-08 1.23e-06 1.62e-05 7.34e-06 0.1 + 13 -205.5540068046154829 -9.48e-10 4.49e-07 4.20e-06 4.23e-06 0.2 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 13 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.55400680461548 Eh -5593.40889 eV + +Components: +Nuclear Repulsion : 70.02143541191150 Eh 1905.38013 eV +Electronic Energy : -275.57544221652699 Eh -7498.78901 eV +One Electron Energy: -419.74121968791889 Eh -11421.73926 eV +Two Electron Energy: 144.16577747139186 Eh 3922.95024 eV + +Virial components: +Potential Energy : -410.41347988902112 Eh -11167.91855 eV +Kinetic Energy : 204.85947308440561 Eh 5574.50967 eV +Virial Ratio : 2.00339029340334 + +DFT components: +N(Alpha) : 11.999999480830 electrons +N(Beta) : 11.999999480830 electrons +N(Total) : 23.999998961660 electrons +E(X) : -23.349054490030 Eh +E(C) : -0.804803429588 Eh +E(XC) : -24.153857919618 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 9.4838e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.2008e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.4890e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.5125e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.2288e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 5.1075e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.189887 -522.1834 + 1 2.0000 -19.024907 -517.6940 + 2 2.0000 -14.263690 -388.1347 + 3 2.0000 -1.255841 -34.1732 + 4 2.0000 -0.973214 -26.4825 + 5 2.0000 -0.699202 -19.0263 + 6 2.0000 -0.566647 -15.4193 + 7 2.0000 -0.519362 -14.1326 + 8 2.0000 -0.507793 -13.8177 + 9 2.0000 -0.332155 -9.0384 + 10 2.0000 -0.276910 -7.5351 + 11 2.0000 -0.261864 -7.1257 + 12 0.0000 -0.188716 -5.1352 + 13 0.0000 0.054287 1.4772 + 14 0.0000 0.080962 2.2031 + 15 0.0000 0.147033 4.0010 + 16 0.0000 0.224076 6.0974 + 17 0.0000 0.269906 7.3445 + 18 0.0000 0.306987 8.3535 + 19 0.0000 0.329175 8.9573 + 20 0.0000 0.346000 9.4151 + 21 0.0000 0.381216 10.3734 + 22 0.0000 0.401280 10.9194 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.315825 + 1 O : 0.218379 + 2 O : -0.176140 + 3 H : 0.273585 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.893271 s : 3.893271 + pz : 1.091394 p : 3.364800 + px : 1.194359 + py : 1.079047 + dz2 : 0.006686 d : 0.057754 + dxz : 0.016749 + dyz : 0.005175 + dx2y2 : 0.009578 + dxy : 0.019565 + + 1 O s : 3.747671 s : 3.747671 + pz : 1.381906 p : 3.901294 + px : 1.453663 + py : 1.065726 + dz2 : 0.007700 d : 0.132656 + dxz : 0.016844 + dyz : 0.039010 + dx2y2 : 0.022312 + dxy : 0.046789 + + 2 O s : 3.943215 s : 3.943215 + pz : 1.365844 p : 4.208486 + px : 1.863828 + py : 0.978813 + dz2 : 0.003451 d : 0.024440 + dxz : -0.000004 + dyz : 0.010324 + dx2y2 : 0.007366 + dxy : 0.003302 + + 3 H s : 0.696652 s : 0.696652 + pz : 0.008079 p : 0.029763 + px : 0.007056 + py : 0.014627 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.073147 + 1 O : -0.194987 + 2 O : -0.015050 + 3 H : 0.283184 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.355595 s : 3.355595 + pz : 1.015638 p : 3.399796 + px : 1.287132 + py : 1.097027 + dz2 : 0.034726 d : 0.317756 + dxz : 0.045030 + dyz : 0.033545 + dx2y2 : 0.114612 + dxy : 0.089843 + + 1 O s : 3.361881 s : 3.361881 + pz : 1.284785 p : 4.044388 + px : 1.502638 + py : 1.256965 + dz2 : 0.060376 d : 0.788718 + dxz : 0.052356 + dyz : 0.189010 + dx2y2 : 0.250673 + dxy : 0.236305 + + 2 O s : 3.597777 s : 3.597777 + pz : 1.304360 p : 4.161022 + px : 1.739858 + py : 1.116803 + dz2 : 0.032744 d : 0.256251 + dxz : 0.005786 + dyz : 0.069901 + dx2y2 : 0.069187 + dxy : 0.078633 + + 3 H s : 0.642349 s : 0.642349 + pz : 0.018735 p : 0.074467 + px : 0.019403 + py : 0.036329 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3158 7.0000 -0.3158 2.6831 2.6831 0.0000 + 1 O 7.7816 8.0000 0.2184 2.6235 2.6235 0.0000 + 2 O 8.1761 8.0000 -0.1761 1.7183 1.7183 -0.0000 + 3 H 0.7264 1.0000 0.2736 0.9107 0.9107 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3706 B( 0-N , 2-O ) : 0.4437 B( 0-N , 3-H ) : 0.8688 +B( 1-O , 2-O ) : 1.2428 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 4 sec + +Total time .... 4.385 sec +Sum of individual times .... 4.349 sec ( 99.2%) + +SCF preparation .... 0.371 sec ( 8.5%) +Fock matrix formation .... 1.994 sec ( 45.5%) + Startup .... 0.033 sec ( 1.6% of F) + Split-RI-J .... 0.052 sec ( 2.6% of F) + XC integration .... 0.459 sec ( 23.0% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.017 sec ( 3.7% of XC) + Density eval. .... 0.025 sec ( 5.4% of XC) + XC-Functional eval. .... 0.014 sec ( 3.1% of XC) + XC-Potential eval. .... 0.025 sec ( 5.5% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.642 sec ( 14.6%) +Total Energy calculation .... 0.029 sec ( 0.7%) +Population analysis .... 0.311 sec ( 7.1%) +Orbital Transformation .... 0.269 sec ( 6.1%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.577 sec ( 13.2%) +SOSCF solution .... 0.158 sec ( 3.6%) +Finished LeanSCF after 4.6 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 7.2 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360762 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007183359 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.547184207552 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000723 -0.000006936 0.000000750 + 2 O : 0.000000640 0.000000196 -0.000000270 + 3 O : 0.000002462 0.000008830 0.000000341 + 4 H : -0.000002379 -0.000002089 -0.000000820 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000120232 +RMS gradient ... 0.0000034708 +MAX gradient ... 0.0000088296 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.007538613 -0.007073885 -0.020142468 + 2 O : -0.012028801 0.005134970 -0.028171305 + 3 O : 0.005798803 -0.004829954 0.022396135 + 4 H : -0.001308616 0.006768869 0.025917638 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000039687 -0.0000507106 0.0000545327 + +Norm of the Cartesian gradient ... 0.0524887364 +RMS gradient ... 0.0151521930 +MAX gradient ... 0.0281713052 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.330 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.005 sec ( 1.5%) +RI-J Coulomb gradient .... 0.058 sec ( 17.6%) +XC gradient .... 0.020 sec ( 6.0%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.547184208 Eh +Current gradient norm .... 0.052488736 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999954540 +Lowest eigenvalues of augmented Hessian: + -0.000047102 0.360282690 0.393305384 0.446430504 0.716103290 +Length of the computed step .... 0.009535523 +The final length of the internal step .... 0.009535523 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0038928609 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0028417011 RMS(Int)= 0.0038933249 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0021264624 0.0001000000 NO + MAX gradient 0.0043992153 0.0003000000 NO + RMS step 0.0038928609 0.0020000000 NO + MAX step 0.0060525218 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0032 Max(Angles) 0.32 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2888 -0.004399 0.0032 1.2920 + 2. B(O 2,O 1) 1.2929 0.000412 -0.0003 1.2926 + 3. B(H 3,N 0) 1.0360 0.001865 -0.0025 1.0335 + 4. A(O 1,N 0,H 3) 100.78 -0.002002 0.32 101.10 + 5. A(N 0,O 1,O 2) 117.12 -0.000351 0.05 117.16 + 6. D(O 2,O 1,N 0,H 3) -143.08 0.051400 0.00 -143.08 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.632 %) +Internal coordinates : 0.000 s ( 0.223 %) +B/P matrices and projection : 0.000 s ( 0.883 %) +Hessian update/contruction : 0.003 s (29.378 %) +Making the step : 0.000 s ( 0.381 %) +Converting the step to Cartesian: 0.000 s ( 0.307 %) +Storing new data : 0.000 s ( 0.251 %) +Checking convergence : 0.000 s ( 0.000 %) +Final printing : 0.007 s (67.909 %) +Total time : 0.011 s + +Time for energy+gradient : 8.258 s +Time for complete geometry iter : 9.199 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.602651 -0.428630 -0.108541 + O 0.445853 0.318269 -0.218763 + O 0.320471 1.563000 0.106280 + H -0.182382 -1.314795 0.217316 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.138845 -0.809994 -0.205113 + 1 O 8.0000 0 15.999 0.842540 0.601442 -0.413403 + 2 O 8.0000 0 15.999 0.605603 2.953641 0.200840 + 3 H 1.0000 0 1.008 -0.344651 -2.484602 0.410668 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.292040344255 0.00000000 0.00000000 + O 2 1 0 1.292566382030 117.16229611 0.00000000 + H 1 2 3 1.033487516983 101.10274937 216.92307700 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.441602404619 0.00000000 0.00000000 + O 2 1 0 2.442596471950 117.16229611 0.00000000 + H 1 2 3 1.953008369925 101.10274937 216.92307700 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1669 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.952768355854 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.822e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22306 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.8 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5540045262386002 0.00e+00 8.44e-05 8.05e-04 1.46e-04 0.6 + *** Restarting incremental Fock matrix formation *** + 2 -205.5540179426541272 -1.34e-05 7.55e-05 8.42e-04 3.58e-04 0.3 + 3 -205.5540113891161127 6.55e-06 5.58e-05 1.01e-03 8.92e-04 0.1 + 4 -205.5540180193726769 -6.63e-06 8.38e-05 1.33e-03 4.95e-04 0.2 + 5 -205.5540048555812973 1.32e-05 6.22e-05 1.06e-03 1.56e-03 0.1 + 6 -205.5540196809844815 -1.48e-05 7.69e-06 1.21e-04 2.83e-05 0.2 + 7 -205.5540196810604243 -7.59e-11 3.86e-06 6.39e-05 2.94e-05 0.2 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.55401968106042 Eh -5593.40924 eV + +Components: +Nuclear Repulsion : 69.95276835585365 Eh 1903.51160 eV +Electronic Energy : -275.50678803691414 Eh -7496.92084 eV +One Electron Energy: -419.60923809677632 Eh -11418.14786 eV +Two Electron Energy: 144.10245005986221 Eh 3921.22702 eV + +Virial components: +Potential Energy : -410.40794877262277 Eh -11167.76804 eV +Kinetic Energy : 204.85392909156235 Eh 5574.35881 eV +Virial Ratio : 2.00341751116321 + +DFT components: +N(Alpha) : 11.999999463735 electrons +N(Beta) : 11.999999463735 electrons +N(Total) : 23.999998927471 electrons +E(X) : -23.347991717490 Eh +E(C) : -0.804685565814 Eh +E(XC) : -24.152677283304 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 7.5943e-11 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.3940e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.8553e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.3045e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.9387e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.3842e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 2 sec +Finished LeanSCF after 2.7 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 7.4 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360682 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007168187 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.547212176797 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000735 -0.000006956 0.000000748 + 2 O : 0.000000644 0.000000208 -0.000000273 + 3 O : 0.000002471 0.000008862 0.000000339 + 4 H : -0.000002380 -0.000002114 -0.000000814 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000120647 +RMS gradient ... 0.0000034828 +MAX gradient ... 0.0000088616 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.007315116 -0.010769740 -0.019334925 + 2 O : -0.010505725 0.007217962 -0.028351767 + 3 O : 0.006105060 -0.004237303 0.022330885 + 4 H : -0.002914450 0.007789080 0.025355807 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000052168 -0.0000447499 0.0000662210 + +Norm of the Cartesian gradient ... 0.0526840123 +RMS gradient ... 0.0152085643 +MAX gradient ... 0.0283517672 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.344 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.005 sec ( 1.6%) +RI-J Coulomb gradient .... 0.064 sec ( 18.5%) +XC gradient .... 0.018 sec ( 5.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.547212177 Eh +Current gradient norm .... 0.052684012 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999993526 +Lowest eigenvalues of augmented Hessian: + -0.000005985 0.351267574 0.379416571 0.475252156 0.555452154 +Length of the computed step .... 0.003598369 +The final length of the internal step .... 0.003598369 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0014690280 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0008377859 RMS(Int)= 0.0014688451 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000002992 +Previously predicted energy change .... -0.000023553 +Actually observed energy change .... -0.000027969 +Ratio of predicted to observed change .... 1.187486495 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000279692 0.0000050000 NO + RMS gradient 0.0006969644 0.0001000000 NO + MAX gradient 0.0013283728 0.0003000000 NO + RMS step 0.0014690280 0.0020000000 YES + MAX step 0.0027568852 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0015 Max(Angles) 0.08 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2920 -0.001328 0.0015 1.2935 + 2. B(O 2,O 1) 1.2926 0.000938 -0.0009 1.2917 + 3. B(H 3,N 0) 1.0335 0.000129 -0.0004 1.0331 + 4. A(O 1,N 0,H 3) 101.10 0.000002 0.03 101.13 + 5. A(N 0,O 1,O 2) 117.16 0.000503 -0.08 117.09 + 6. D(O 2,O 1,N 0,H 3) -143.08 0.051123 0.00 -143.08 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.052 %) +Internal coordinates : 0.000 s ( 0.019 %) +B/P matrices and projection : 0.000 s ( 0.073 %) +Hessian update/contruction : 0.121 s (97.753 %) +Making the step : 0.000 s ( 0.053 %) +Converting the step to Cartesian: 0.000 s ( 0.032 %) +Storing new data : 0.000 s ( 0.028 %) +Checking convergence : 0.000 s ( 0.010 %) +Final printing : 0.002 s ( 1.979 %) +Total time : 0.123 s + +Time for energy+gradient : 7.199 s +Time for complete geometry iter : 8.438 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.602744 -0.428836 -0.108171 + O 0.446844 0.318963 -0.219080 + O 0.320041 1.562555 0.106281 + H -0.182849 -1.314838 0.217262 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.139022 -0.810382 -0.204413 + 1 O 8.0000 0 15.999 0.844414 0.602753 -0.414001 + 2 O 8.0000 0 15.999 0.604790 2.952800 0.200842 + 3 H 1.0000 0 1.008 -0.345535 -2.484684 0.410565 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.293499225071 0.00000000 0.00000000 + O 2 1 0 1.291688489234 117.08672578 0.00000000 + H 1 2 3 1.033062872559 101.12913421 216.92307700 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.444359289823 0.00000000 0.00000000 + O 2 1 0 2.440937494991 117.08672578 0.00000000 + H 1 2 3 1.952205908258 101.12913421 216.92307700 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1669 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.947158429149 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.815e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22305 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 1.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5540206568866211 0.00e+00 4.15e-05 3.37e-04 7.84e-05 1.5 + *** Restarting incremental Fock matrix formation *** + 2 -205.5540242034755352 -3.55e-06 4.19e-05 5.13e-04 1.18e-04 0.8 + 3 -205.5540219005434324 2.30e-06 3.03e-05 5.06e-04 6.93e-04 0.2 + 4 -205.5540244925346087 -2.59e-06 1.85e-05 3.05e-04 1.22e-04 0.4 + 5 -205.5540240598901960 4.33e-07 1.16e-05 2.15e-04 3.11e-04 0.3 + 6 -205.5540245896240208 -5.30e-07 3.53e-06 4.93e-05 1.13e-05 0.2 + 7 -205.5540245903817436 -7.58e-10 1.65e-06 2.59e-05 1.18e-05 0.3 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.55402459038174 Eh -5593.40937 eV + +Components: +Nuclear Repulsion : 69.94715842914904 Eh 1903.35895 eV +Electronic Energy : -275.50118301953080 Eh -7496.76832 eV +One Electron Energy: -419.59747602868254 Eh -11417.82779 eV +Two Electron Energy: 144.09629300915176 Eh 3921.05948 eV + +Virial components: +Potential Energy : -410.40734135666878 Eh -11167.75152 eV +Kinetic Energy : 204.85331676628707 Eh 5574.34214 eV +Virial Ratio : 2.00342053443486 + +DFT components: +N(Alpha) : 11.999999452067 electrons +N(Beta) : 11.999999452067 electrons +N(Total) : 23.999998904135 electrons +E(X) : -23.347656886820 Eh +E(C) : -0.804671980000 Eh +E(XC) : -24.152328866820 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 7.5772e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.5866e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.6485e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.9151e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.1796e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.4393e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 4 sec +Finished LeanSCF after 4.7 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 7.4 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360684 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007169254 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.547216021017 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000735 -0.000006956 0.000000748 + 2 O : 0.000000646 0.000000213 -0.000000274 + 3 O : 0.000002469 0.000008855 0.000000338 + 4 H : -0.000002380 -0.000002113 -0.000000812 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000120594 +RMS gradient ... 0.0000034812 +MAX gradient ... 0.0000088551 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.006740767 -0.011408979 -0.019095129 + 2 O : -0.009551945 0.008148128 -0.028358365 + 3 O : 0.005961379 -0.004714696 0.022217665 + 4 H : -0.003150201 0.007975547 0.025235829 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000038486 -0.0000401967 0.0000582766 + +Norm of the Cartesian gradient ... 0.0525721068 +RMS gradient ... 0.0151762600 +MAX gradient ... 0.0283583652 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.414 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.005 sec ( 1.2%) +RI-J Coulomb gradient .... 0.059 sec ( 14.2%) +XC gradient .... 0.019 sec ( 4.7%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.547216021 Eh +Current gradient norm .... 0.052572107 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999998032 +Lowest eigenvalues of augmented Hessian: + -0.000001355 0.317289610 0.385638864 0.434981179 0.487108853 +Length of the computed step .... 0.001983969 +The final length of the internal step .... 0.001983969 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0008099520 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0003919560 RMS(Int)= 0.0008099598 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000677 +Previously predicted energy change .... -0.000002992 +Actually observed energy change .... -0.000003844 +Ratio of predicted to observed change .... 1.284688123 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000038442 0.0000050000 YES + RMS gradient 0.0002848387 0.0001000000 NO + MAX gradient 0.0004678430 0.0003000000 NO + RMS step 0.0008099520 0.0020000000 YES + MAX step 0.0013874050 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0007 Max(Angles) 0.04 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2935 -0.000397 0.0007 1.2942 + 2. B(O 2,O 1) 1.2917 0.000468 -0.0006 1.2911 + 3. B(H 3,N 0) 1.0331 -0.000172 0.0001 1.0332 + 4. A(O 1,N 0,H 3) 101.13 0.000284 -0.04 101.08 + 5. A(N 0,O 1,O 2) 117.09 0.000011 -0.01 117.08 + 6. D(O 2,O 1,N 0,H 3) -143.08 0.051038 -0.00 -143.08 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.200 %) +Internal coordinates : 0.000 s ( 0.066 %) +B/P matrices and projection : 0.000 s ( 0.306 %) +Hessian update/contruction : 0.007 s (16.627 %) +Making the step : 0.000 s ( 0.116 %) +Converting the step to Cartesian: 0.000 s ( 0.083 %) +Storing new data : 0.000 s ( 0.081 %) +Checking convergence : 0.000 s ( 0.030 %) +Final printing : 0.033 s (82.487 %) +Total time : 0.040 s + +Time for energy+gradient : 9.823 s +Time for complete geometry iter : 10.764 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 4 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.603202 -0.428912 -0.108242 + O 0.447046 0.319254 -0.219002 + O 0.320086 1.562233 0.106235 + H -0.182638 -1.314731 0.217300 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.139887 -0.810526 -0.204547 + 1 O 8.0000 0 15.999 0.844794 0.603302 -0.413853 + 2 O 8.0000 0 15.999 0.604876 2.952193 0.200756 + 3 H 1.0000 0 1.008 -0.345136 -2.484482 0.410637 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.294233408201 0.00000000 0.00000000 + O 2 1 0 1.291083496012 117.07666506 0.00000000 + H 1 2 3 1.033211866824 101.08497319 216.92307700 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.445746694872 0.00000000 0.00000000 + O 2 1 0 2.439794223489 117.07666506 0.00000000 + H 1 2 3 1.952487466615 101.08497319 216.92307700 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.946001779076 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.810e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.003 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22305 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.7 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5540258334187911 0.00e+00 2.24e-05 2.46e-04 5.14e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5540266933229532 -8.60e-07 2.89e-05 4.63e-04 9.87e-05 0.0 + 3 -205.5540250942685248 1.60e-06 2.33e-05 3.76e-04 5.63e-04 0.0 + 4 -205.5540267947506550 -1.70e-06 7.59e-06 1.38e-04 5.38e-05 0.0 + 5 -205.5540266899149060 1.05e-07 5.38e-06 9.91e-05 1.47e-04 0.0 + 6 -205.5540268117793516 -1.22e-07 5.98e-07 8.56e-06 2.52e-06 0.0 + 7 -205.5540268113962270 3.83e-10 2.85e-07 4.65e-06 2.31e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.55402681139623 Eh -5593.40943 eV + +Components: +Nuclear Repulsion : 69.94600177907648 Eh 1903.32747 eV +Electronic Energy : -275.50002859047271 Eh -7496.73690 eV +One Electron Energy: -419.59467902554121 Eh -11417.75168 eV +Two Electron Energy: 144.09465043506850 Eh 3921.01478 eV + +Virial components: +Potential Energy : -410.40707104154171 Eh -11167.74416 eV +Kinetic Energy : 204.85304423014546 Eh 5574.33473 eV +Virial Ratio : 2.00342188022582 + +DFT components: +N(Alpha) : 11.999999438665 electrons +N(Beta) : 11.999999438665 electrons +N(Total) : 23.999998877329 electrons +E(X) : -23.347469655104 Eh +E(C) : -0.804671348437 Eh +E(XC) : -24.152141003540 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -3.8312e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.6474e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.8519e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.8834e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.3137e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.7401e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 7.5 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360689 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007170640 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.547216860194 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000734 -0.000006955 0.000000749 + 2 O : 0.000000647 0.000000215 -0.000000273 + 3 O : 0.000002469 0.000008851 0.000000337 + 4 H : -0.000002382 -0.000002111 -0.000000813 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000120560 +RMS gradient ... 0.0000034803 +MAX gradient ... 0.0000088509 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.006296659 -0.011474513 -0.019068408 + 2 O : -0.009188122 0.008633128 -0.028320700 + 3 O : 0.005953897 -0.005051949 0.022139686 + 4 H : -0.003062434 0.007893335 0.025249423 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000028953 -0.0000356612 0.0000539909 + +Norm of the Cartesian gradient ... 0.0525003284 +RMS gradient ... 0.0151555394 +MAX gradient ... 0.0283207004 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.144 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.5%) +RI-J Coulomb gradient .... 0.063 sec ( 43.9%) +XC gradient .... 0.022 sec ( 15.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.547216860 Eh +Current gradient norm .... 0.052500328 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999612 +Lowest eigenvalues of augmented Hessian: + -0.000000209 0.238024809 0.403482633 0.435311941 0.484389661 +Length of the computed step .... 0.000880571 +The final length of the internal step .... 0.000880571 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0003594915 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0002779022 RMS(Int)= 0.0003595061 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000104 +Previously predicted energy change .... -0.000000677 +Actually observed energy change .... -0.000000839 +Ratio of predicted to observed change .... 1.238950397 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000008392 0.0000050000 YES + RMS gradient 0.0001018717 0.0001000000 NO + MAX gradient 0.0001891583 0.0003000000 YES + RMS step 0.0003594915 0.0020000000 YES + MAX step 0.0006800745 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0002 Max(Angles) 0.04 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2942 -0.000020 0.0002 1.2944 + 2. B(O 2,O 1) 1.2911 0.000124 -0.0002 1.2909 + 3. B(H 3,N 0) 1.0332 -0.000060 0.0001 1.0333 + 4. A(O 1,N 0,H 3) 101.08 0.000189 -0.04 101.05 + 5. A(N 0,O 1,O 2) 117.08 -0.000084 0.01 117.09 + 6. D(O 2,O 1,N 0,H 3) -143.08 0.051014 -0.00 -143.08 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.670 %) +Internal coordinates : 0.000 s ( 3.474 %) +B/P matrices and projection : 0.000 s (16.129 %) +Hessian update/contruction : 0.000 s (28.040 %) +Making the step : 0.000 s ( 5.831 %) +Converting the step to Cartesian: 0.000 s ( 4.342 %) +Storing new data : 0.000 s ( 3.598 %) +Checking convergence : 0.000 s ( 1.489 %) +Final printing : 0.000 s (25.186 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 4 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.603491 -0.428956 -0.108362 + O 0.446954 0.319263 -0.218867 + O 0.320211 1.562092 0.106205 + H -0.182382 -1.314556 0.217316 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.140433 -0.810609 -0.204775 + 1 O 8.0000 0 15.999 0.844620 0.603320 -0.413599 + 2 O 8.0000 0 15.999 0.605112 2.951927 0.200698 + 3 H 1.0000 0 1.008 -0.344652 -2.484150 0.410668 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.294402113210 0.00000000 0.00000000 + O 2 1 0 1.290875638545 117.08747946 0.00000000 + H 1 2 3 1.033289195035 101.04600779 216.92307700 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.446065501135 0.00000000 0.00000000 + O 2 1 0 2.439401429800 117.08747946 0.00000000 + H 1 2 3 1.952633595756 101.04600779 216.92307700 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.946954720771 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.808e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22305 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.9469547208 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5540273761802723 0.00e+00 1.01e-05 9.75e-05 2.02e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5540275272024928 -1.51e-07 9.74e-06 1.60e-04 3.30e-05 0.0 + 3 -205.5540273957506088 1.31e-07 7.52e-06 1.10e-04 1.65e-04 0.0 + 4 -205.5540275453376466 -1.50e-07 4.45e-06 6.56e-05 2.57e-05 0.0 + 5 -205.5540275189856061 2.64e-08 2.80e-06 4.99e-05 7.46e-05 0.0 + 6 -205.5540275514068753 -3.24e-08 5.96e-07 4.52e-06 2.48e-06 0.0 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 6 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.55402755140688 Eh -5593.40945 eV + +Components: +Nuclear Repulsion : 69.94695472077125 Eh 1903.35340 eV +Electronic Energy : -275.50098227217813 Eh -7496.76286 eV +One Electron Energy: -419.59625672612776 Eh -11417.79461 eV +Two Electron Energy: 144.09527445394963 Eh 3921.03176 eV + +Virial components: +Potential Energy : -410.40715674002979 Eh -11167.74649 eV +Kinetic Energy : 204.85312918862289 Eh 5574.33704 eV +Virial Ratio : 2.00342146769034 + +DFT components: +N(Alpha) : 11.999999432162 electrons +N(Beta) : 11.999999432162 electrons +N(Total) : 23.999998864324 electrons +E(X) : -23.347461896235 Eh +E(C) : -0.804675124464 Eh +E(XC) : -24.152137020700 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.2421e-08 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.5218e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 5.9610e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.2804e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.4773e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.7489e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.189889 -522.1834 + 1 2.0000 -19.025898 -517.7210 + 2 2.0000 -14.263040 -388.1171 + 3 2.0000 -1.254948 -34.1489 + 4 2.0000 -0.972016 -26.4499 + 5 2.0000 -0.700186 -19.0530 + 6 2.0000 -0.565983 -15.4012 + 7 2.0000 -0.518647 -14.1131 + 8 2.0000 -0.507859 -13.8195 + 9 2.0000 -0.332406 -9.0452 + 10 2.0000 -0.277000 -7.5376 + 11 2.0000 -0.262128 -7.1329 + 12 0.0000 -0.189304 -5.1512 + 13 0.0000 0.054237 1.4759 + 14 0.0000 0.082547 2.2462 + 15 0.0000 0.144907 3.9431 + 16 0.0000 0.223398 6.0790 + 17 0.0000 0.270350 7.3566 + 18 0.0000 0.307383 8.3643 + 19 0.0000 0.328516 8.9394 + 20 0.0000 0.346306 9.4235 + 21 0.0000 0.380840 10.3632 + 22 0.0000 0.401342 10.9211 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.317093 + 1 O : 0.218052 + 2 O : -0.173540 + 3 H : 0.272580 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.893123 s : 3.893123 + pz : 1.094028 p : 3.366930 + px : 1.194837 + py : 1.078064 + dz2 : 0.006639 d : 0.057040 + dxz : 0.016555 + dyz : 0.005066 + dx2y2 : 0.009399 + dxy : 0.019381 + + 1 O s : 3.748871 s : 3.748871 + pz : 1.383114 p : 3.900610 + px : 1.454129 + py : 1.063367 + dz2 : 0.007743 d : 0.132466 + dxz : 0.016760 + dyz : 0.038845 + dx2y2 : 0.022370 + dxy : 0.046748 + + 2 O s : 3.943370 s : 3.943370 + pz : 1.364461 p : 4.205597 + px : 1.861382 + py : 0.979754 + dz2 : 0.003500 d : 0.024573 + dxz : 0.000004 + dyz : 0.010348 + dx2y2 : 0.007415 + dxy : 0.003306 + + 3 H s : 0.697456 s : 0.697456 + pz : 0.008153 p : 0.029963 + px : 0.007084 + py : 0.014727 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.073786 + 1 O : -0.193561 + 2 O : -0.013962 + 3 H : 0.281310 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.357188 s : 3.357188 + pz : 1.018291 p : 3.401568 + px : 1.286159 + py : 1.097119 + dz2 : 0.034603 d : 0.315030 + dxz : 0.044525 + dyz : 0.033292 + dx2y2 : 0.113133 + dxy : 0.089477 + + 1 O s : 3.363516 s : 3.363516 + pz : 1.285980 p : 4.043390 + px : 1.501531 + py : 1.255880 + dz2 : 0.060247 d : 0.786655 + dxz : 0.051981 + dyz : 0.188948 + dx2y2 : 0.249103 + dxy : 0.236375 + + 2 O s : 3.596780 s : 3.596780 + pz : 1.303397 p : 4.159643 + px : 1.737681 + py : 1.118566 + dz2 : 0.032852 d : 0.257539 + dxz : 0.005874 + dyz : 0.070346 + dx2y2 : 0.069349 + dxy : 0.079118 + + 3 H s : 0.643516 s : 0.643516 + pz : 0.018962 p : 0.075175 + px : 0.019536 + py : 0.036677 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3171 7.0000 -0.3171 2.6834 2.6834 -0.0000 + 1 O 7.7819 8.0000 0.2181 2.6226 2.6226 -0.0000 + 2 O 8.1735 8.0000 -0.1735 1.7208 1.7208 -0.0000 + 3 H 0.7274 1.0000 0.2726 0.9113 0.9113 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3681 B( 0-N , 2-O ) : 0.4457 B( 0-N , 3-H ) : 0.8696 +B( 1-O , 2-O ) : 1.2439 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.684 sec +Sum of individual times .... 0.668 sec ( 97.7%) + +SCF preparation .... 0.378 sec ( 55.3%) +Fock matrix formation .... 0.167 sec ( 24.4%) + Startup .... 0.008 sec ( 5.0% of F) + Split-RI-J .... 0.026 sec ( 15.5% of F) + XC integration .... 0.109 sec ( 65.3% of F) + Basis function eval. .... 0.007 sec ( 6.5% of XC) + Density eval. .... 0.010 sec ( 9.0% of XC) + XC-Functional eval. .... 0.006 sec ( 5.4% of XC) + XC-Potential eval. .... 0.009 sec ( 8.6% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.010 sec ( 1.5%) +Total Energy calculation .... 0.013 sec ( 1.9%) +Population analysis .... 0.048 sec ( 7.1%) +Orbital Transformation .... 0.006 sec ( 0.9%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.010 sec ( 1.5%) +SOSCF solution .... 0.035 sec ( 5.0%) +Finished LeanSCF after 0.7 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 7.6 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360692 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007171263 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.547216980652 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.005.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.005.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.146190 0.915112 -0.124657 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5540275514068753 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.489041934 0.685074839 -0.203051342 +Nuclear contribution : -0.238375545 -1.679131538 0.265820101 + ----------------------------------------- +Total Dipole Moment : 0.250666389 -0.994056698 0.062768760 + ----------------------------------------- +Magnitude (a.u.) : 1.027094093 +Magnitude (Debye) : 2.610665711 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.258093 0.423923 0.380716 +Rotational constants in MHz : 97675.185487 12708.877626 11413.589786 + +Dipole components along the rotational axes: +x,y,z [a.u.] : -0.813116 0.551937 0.298547 +x,y,z [Debye]: -2.066776 1.402913 0.758846 + + + +Dipole moment calculation done in 0.0 sec + +Maximum memory used throughout the entire PROP-calculation: 4.8 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 6 * + * * + * Dihedral ( 2, 1, 0, 3) : -133.84615385 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2946 0.712086 + 2. B(O 2,O 1) 1.2939 0.721371 + 3. B(H 3,N 0) 1.0365 0.397227 + 4. A(O 1,N 0,H 3) 101.0425 0.359628 + 5. A(N 0,O 1,O 2) 116.9555 0.445371 + 6. D(O 2,O 1,N 0,H 3) -133.8462 0.039774 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.603125 -0.436967 -0.141622 + O 0.437664 0.322762 -0.265969 + O 0.324271 1.544683 0.144245 + H -0.177519 -1.292634 0.259638 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.139741 -0.825749 -0.267626 + 1 O 8.0000 0 15.999 0.827066 0.609932 -0.502609 + 2 O 8.0000 0 15.999 0.612784 2.919028 0.272584 + 3 H 1.0000 0 1.008 -0.335462 -2.442725 0.490644 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.294402113210 0.00000000 0.00000000 + O 2 1 0 1.290875638545 117.08747946 0.00000000 + H 1 2 3 1.033289195035 101.04600779 216.92307700 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.446065501135 0.00000000 0.00000000 + O 2 1 0 2.439401429800 117.08747946 0.00000000 + H 1 2 3 1.952633595756 101.04600779 216.92307700 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1669 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.880536525996 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.848e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22307 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.8805365260 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5402049516051193 0.00e+00 3.95e-04 4.04e-03 3.04e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.066) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5414513629201565 -1.25e-03 4.70e-04 4.62e-03 2.41e-02 0.700 0.1 + ***Turning on AO-DIIS*** + 3 -205.5424794002967701 -1.03e-03 3.58e-04 3.30e-03 1.72e-02 0.700 0.1 + 4 -205.5431972409715513 -7.18e-04 8.93e-04 7.75e-03 1.21e-02 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5448730673487603 -1.68e-03 8.38e-05 1.02e-03 8.86e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -205.5448759634502949 -2.90e-06 3.06e-04 4.18e-03 9.68e-04 0.0 + 7 -205.5447296090814575 1.46e-04 2.25e-04 3.43e-03 4.51e-03 0.0 + 8 -205.5448884446204261 -1.59e-04 2.07e-05 2.01e-04 1.15e-04 0.0 + 9 -205.5448885728610549 -1.28e-07 1.06e-05 1.20e-04 8.67e-05 0.0 + 10 -205.5448886126883394 -3.98e-08 7.93e-06 7.79e-05 8.79e-05 0.0 + 11 -205.5448886715220738 -5.88e-08 4.42e-06 6.15e-05 3.19e-05 0.0 + 12 -205.5448886902732397 -1.88e-08 1.38e-06 1.80e-05 9.25e-06 0.0 + 13 -205.5448886921068947 -1.83e-09 4.20e-07 3.63e-06 4.62e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 13 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.54488869210689 Eh -5593.16077 eV + +Components: +Nuclear Repulsion : 69.88053652599577 Eh 1901.54607 eV +Electronic Energy : -275.42542521810265 Eh -7494.70684 eV +One Electron Energy: -419.46307761518682 Eh -11414.17063 eV +Two Electron Energy: 144.03765239708417 Eh 3919.46378 eV + +Virial components: +Potential Energy : -410.39884577987129 Eh -11167.52034 eV +Kinetic Energy : 204.85395708776443 Eh 5574.35957 eV +Virial Ratio : 2.00337280086831 + +DFT components: +N(Alpha) : 11.999998871205 electrons +N(Beta) : 11.999998871205 electrons +N(Total) : 23.999997742410 electrons +E(X) : -23.343945442945 Eh +E(C) : -0.804563470809 Eh +E(XC) : -24.148508913754 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.8337e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.6263e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.1970e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.8621e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.6250e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 4.0834e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.188461 -522.1446 + 1 2.0000 -19.029835 -517.8281 + 2 2.0000 -14.259849 -388.0302 + 3 2.0000 -1.253629 -34.1130 + 4 2.0000 -0.970911 -26.4198 + 5 2.0000 -0.701087 -19.0775 + 6 2.0000 -0.564843 -15.3701 + 7 2.0000 -0.517291 -14.0762 + 8 2.0000 -0.507585 -13.8121 + 9 2.0000 -0.333604 -9.0778 + 10 2.0000 -0.272361 -7.4113 + 11 2.0000 -0.262748 -7.1497 + 12 0.0000 -0.195776 -5.3273 + 13 0.0000 0.052949 1.4408 + 14 0.0000 0.082000 2.2313 + 15 0.0000 0.144162 3.9229 + 16 0.0000 0.225331 6.1316 + 17 0.0000 0.268108 7.2956 + 18 0.0000 0.311451 8.4750 + 19 0.0000 0.330761 9.0005 + 20 0.0000 0.340425 9.2634 + 21 0.0000 0.382177 10.3996 + 22 0.0000 0.400056 10.8861 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.330165 + 1 O : 0.212119 + 2 O : -0.158488 + 3 H : 0.276534 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.894422 s : 3.894422 + pz : 1.092094 p : 3.380437 + px : 1.200898 + py : 1.087446 + dz2 : 0.005961 d : 0.055306 + dxz : 0.015903 + dyz : 0.005312 + dx2y2 : 0.009181 + dxy : 0.018949 + + 1 O s : 3.751814 s : 3.751814 + pz : 1.383001 p : 3.908197 + px : 1.453644 + py : 1.071552 + dz2 : 0.009399 d : 0.127871 + dxz : 0.018933 + dyz : 0.035260 + dx2y2 : 0.020089 + dxy : 0.044189 + + 2 O s : 3.942426 s : 3.942426 + pz : 1.334708 p : 4.192930 + px : 1.836385 + py : 1.021837 + dz2 : 0.003978 d : 0.023132 + dxz : 0.000046 + dyz : 0.008976 + dx2y2 : 0.006573 + dxy : 0.003559 + + 3 H s : 0.693486 s : 0.693486 + pz : 0.008938 p : 0.029980 + px : 0.007118 + py : 0.013924 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.083591 + 1 O : -0.193200 + 2 O : -0.007284 + 3 H : 0.284075 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.355969 s : 3.355969 + pz : 1.019698 p : 3.412613 + px : 1.291157 + py : 1.101759 + dz2 : 0.032559 d : 0.315009 + dxz : 0.045270 + dyz : 0.036782 + dx2y2 : 0.110371 + dxy : 0.090027 + + 1 O s : 3.365259 s : 3.365259 + pz : 1.291387 p : 4.045315 + px : 1.499489 + py : 1.254439 + dz2 : 0.060453 d : 0.782626 + dxz : 0.059348 + dyz : 0.189011 + dx2y2 : 0.243906 + dxy : 0.229908 + + 2 O s : 3.599212 s : 3.599212 + pz : 1.285115 p : 4.151405 + px : 1.714961 + py : 1.151330 + dz2 : 0.034708 d : 0.256667 + dxz : 0.008782 + dyz : 0.072449 + dx2y2 : 0.066114 + dxy : 0.074614 + + 3 H s : 0.640788 s : 0.640788 + pz : 0.021111 p : 0.075137 + px : 0.019601 + py : 0.034425 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3302 7.0000 -0.3302 2.6607 2.6607 -0.0000 + 1 O 7.7879 8.0000 0.2121 2.6062 2.6062 0.0000 + 2 O 8.1585 8.0000 -0.1585 1.7080 1.7080 -0.0000 + 3 H 0.7235 1.0000 0.2765 0.9085 0.9085 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3599 B( 0-N , 2-O ) : 0.4372 B( 0-N , 3-H ) : 0.8635 +B( 1-O , 2-O ) : 1.2361 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.122 sec +Sum of individual times .... 1.106 sec ( 98.6%) + +SCF preparation .... 0.530 sec ( 47.2%) +Fock matrix formation .... 0.331 sec ( 29.5%) + Startup .... 0.015 sec ( 4.4% of F) + Split-RI-J .... 0.050 sec ( 15.3% of F) + XC integration .... 0.214 sec ( 64.7% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.017 sec ( 7.8% of XC) + Density eval. .... 0.019 sec ( 9.1% of XC) + XC-Functional eval. .... 0.015 sec ( 6.9% of XC) + XC-Potential eval. .... 0.020 sec ( 9.4% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.034 sec ( 3.1%) +Total Energy calculation .... 0.027 sec ( 2.4%) +Population analysis .... 0.047 sec ( 4.2%) +Orbital Transformation .... 0.014 sec ( 1.2%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.077 sec ( 6.8%) +SOSCF solution .... 0.047 sec ( 4.2%) +Finished LeanSCF after 1.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 8.0 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000361042 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007184585 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.538065148477 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000714 -0.000006862 0.000000883 + 2 O : 0.000000633 0.000000220 -0.000000337 + 3 O : 0.000002458 0.000008631 0.000000504 + 4 H : -0.000002377 -0.000001989 -0.000001050 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000118506 +RMS gradient ... 0.0000034210 +MAX gradient ... 0.0000086311 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.011511754 -0.011811402 -0.024371439 + 2 O : -0.017478861 0.009047600 -0.032328721 + 3 O : 0.008827546 -0.007808376 0.026073261 + 4 H : -0.002860439 0.010572178 0.030626899 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000294837 -0.0000352898 0.0000251102 + +Norm of the Cartesian gradient ... 0.0646156626 +RMS gradient ... 0.0186529351 +MAX gradient ... 0.0323287214 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.133 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.8%) +RI-J Coulomb gradient .... 0.059 sec ( 44.6%) +XC gradient .... 0.019 sec ( 14.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.538065148 Eh +Current gradient norm .... 0.064615663 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999928624 +Lowest eigenvalues of augmented Hessian: + -0.000074130 0.358891728 0.392590452 0.444422961 0.711709305 +Length of the computed step .... 0.011948546 +The final length of the internal step .... 0.011948546 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0048779736 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0038382669 RMS(Int)= 0.0048785886 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0026654555 0.0001000000 NO + MAX gradient 0.0056248400 0.0003000000 NO + RMS step 0.0048779736 0.0020000000 NO + MAX step 0.0079029534 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0042 Max(Angles) 0.43 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2946 -0.005625 0.0042 1.2987 + 2. B(O 2,O 1) 1.2939 0.000115 -0.0001 1.2938 + 3. B(H 3,N 0) 1.0365 0.001956 -0.0026 1.0339 + 4. A(O 1,N 0,H 3) 101.04 -0.002672 0.43 101.47 + 5. A(N 0,O 1,O 2) 116.96 -0.000097 0.01 116.97 + 6. D(O 2,O 1,N 0,H 3) -133.85 0.062361 0.00 -133.85 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.671 %) +Internal coordinates : 0.000 s ( 3.963 %) +B/P matrices and projection : 0.000 s (18.293 %) +Hessian update/contruction : 0.000 s (24.390 %) +Making the step : 0.000 s ( 7.774 %) +Converting the step to Cartesian: 0.000 s ( 5.183 %) +Storing new data : 0.000 s ( 4.116 %) +Checking convergence : 0.000 s ( 0.152 %) +Final printing : 0.000 s (25.152 %) +Total time : 0.001 s + +Time for energy+gradient : 4.431 s +Time for complete geometry iter : 5.303 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.601886 -0.439559 -0.139758 + O 0.439705 0.325707 -0.267019 + O 0.324185 1.547066 0.144005 + H -0.180711 -1.295369 0.259064 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.137401 -0.830646 -0.264104 + 1 O 8.0000 0 15.999 0.830922 0.615496 -0.504592 + 2 O 8.0000 0 15.999 0.612620 2.923531 0.272130 + 3 H 1.0000 0 1.008 -0.341494 -2.447893 0.489560 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.298745381020 0.00000000 0.00000000 + O 2 1 0 1.293832906793 116.96804256 0.00000000 + H 1 2 3 1.033856229943 101.46905894 226.15384591 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.454273087823 0.00000000 0.00000000 + O 2 1 0 2.444989856894 116.96804256 0.00000000 + H 1 2 3 1.953705136441 101.46905894 226.15384591 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1668 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.783662923780 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.850e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22307 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5448902788714918 0.00e+00 1.07e-04 9.75e-04 2.17e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5449124682667730 -2.22e-05 9.93e-05 1.06e-03 3.73e-04 0.1 + 3 -205.5449034521640783 9.02e-06 6.99e-05 1.25e-03 1.07e-03 0.0 + 4 -205.5449128134089847 -9.36e-06 1.05e-04 1.65e-03 5.38e-04 0.0 + 5 -205.5448936460796858 1.92e-05 7.66e-05 1.29e-03 1.60e-03 0.0 + 6 -205.5449156173766028 -2.20e-05 1.29e-05 2.07e-04 4.23e-05 0.0 + 7 -205.5449156181761055 -8.00e-10 6.45e-06 1.09e-04 4.64e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.54491561817611 Eh -5593.16150 eV + +Components: +Nuclear Repulsion : 69.78366292378014 Eh 1898.91001 eV +Electronic Energy : -275.32857854195623 Eh -7492.07151 eV +One Electron Energy: -419.27806672032557 Eh -11409.13622 eV +Two Electron Energy: 143.94948817836934 Eh 3917.06471 eV + +Virial components: +Potential Energy : -410.39048329397497 Eh -11167.29278 eV +Kinetic Energy : 204.84556767579886 Eh 5574.13128 eV +Virial Ratio : 2.00341402525967 + +DFT components: +N(Alpha) : 11.999998841060 electrons +N(Beta) : 11.999998841060 electrons +N(Total) : 23.999997682120 electrons +E(X) : -23.342256804300 Eh +E(C) : -0.804390270843 Eh +E(XC) : -24.146647075143 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 7.9950e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.0946e-04 Tolerance : 1.0000e-07 + Last RMS-Density change ... 6.4499e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.6458e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.6380e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 5.0657e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.7 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 8.2 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360938 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007166729 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.538109827486 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000730 -0.000006888 0.000000879 + 2 O : 0.000000639 0.000000236 -0.000000342 + 3 O : 0.000002469 0.000008678 0.000000502 + 4 H : -0.000002378 -0.000002026 -0.000001039 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000119090 +RMS gradient ... 0.0000034378 +MAX gradient ... 0.0000086778 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.011025480 -0.015976639 -0.023267111 + 2 O : -0.015425706 0.011393092 -0.032654504 + 3 O : 0.009109343 -0.006831720 0.026041353 + 4 H : -0.004709117 0.011415267 0.029880262 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000170402 -0.0000348461 0.0000489907 + +Norm of the Cartesian gradient ... 0.0648487699 +RMS gradient ... 0.0187202274 +MAX gradient ... 0.0326545039 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.137 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.9%) +RI-J Coulomb gradient .... 0.063 sec ( 45.9%) +XC gradient .... 0.020 sec ( 14.4%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.538109827 Eh +Current gradient norm .... 0.064848770 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999988254 +Lowest eigenvalues of augmented Hessian: + -0.000010123 0.338035083 0.382301385 0.468978221 0.551537316 +Length of the computed step .... 0.004846947 +The final length of the internal step .... 0.004846947 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0019787579 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0012279555 RMS(Int)= 0.0019785167 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000005062 +Previously predicted energy change .... -0.000037070 +Actually observed energy change .... -0.000044679 +Ratio of predicted to observed change .... 1.205256588 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000446790 0.0000050000 NO + RMS gradient 0.0008775603 0.0001000000 NO + MAX gradient 0.0017252774 0.0003000000 NO + RMS step 0.0019787579 0.0020000000 YES + MAX step 0.0037105854 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0020 Max(Angles) 0.12 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2987 -0.001725 0.0020 1.3007 + 2. B(O 2,O 1) 1.2938 0.001006 -0.0009 1.2929 + 3. B(H 3,N 0) 1.0339 0.000158 -0.0005 1.0334 + 4. A(O 1,N 0,H 3) 101.47 -0.000105 0.06 101.53 + 5. A(N 0,O 1,O 2) 116.97 0.000772 -0.12 116.84 + 6. D(O 2,O 1,N 0,H 3) -133.85 0.061900 0.00 -133.85 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 7.200 %) +Internal coordinates : 0.000 s ( 3.200 %) +B/P matrices and projection : 0.000 s (13.829 %) +Hessian update/contruction : 0.000 s (40.114 %) +Making the step : 0.000 s ( 6.057 %) +Converting the step to Cartesian: 0.000 s ( 3.657 %) +Storing new data : 0.000 s ( 3.086 %) +Checking convergence : 0.000 s ( 1.257 %) +Final printing : 0.000 s (21.486 %) +Total time : 0.001 s + +Time for energy+gradient : 4.063 s +Time for complete geometry iter : 4.860 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.601922 -0.439749 -0.139101 + O 0.441122 0.326655 -0.267666 + O 0.323536 1.546582 0.144047 + H -0.181445 -1.295643 0.259012 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.137467 -0.831006 -0.262864 + 1 O 8.0000 0 15.999 0.833600 0.617288 -0.505816 + 2 O 8.0000 0 15.999 0.611395 2.922615 0.272210 + 3 H 1.0000 0 1.008 -0.342880 -2.448410 0.489462 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.300708938252 0.00000000 0.00000000 + O 2 1 0 1.292886822423 116.84394068 0.00000000 + H 1 2 3 1.033367562696 101.52588953 226.15384591 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.457983673240 0.00000000 0.00000000 + O 2 1 0 2.443202016535 116.84394068 0.00000000 + H 1 2 3 1.952781689174 101.52588953 226.15384591 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1667 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.771234533292 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.844e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22308 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5449162343813896 0.00e+00 5.71e-05 4.15e-04 1.38e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5449229208836073 -6.69e-06 5.53e-05 5.77e-04 1.54e-04 0.0 + 3 -205.5449200116252086 2.91e-06 3.92e-05 6.28e-04 7.04e-04 0.0 + 4 -205.5449234783095562 -3.47e-06 3.01e-05 4.40e-04 1.63e-04 0.0 + 5 -205.5449227550801652 7.23e-07 1.62e-05 2.97e-04 3.47e-04 0.0 + 6 -205.5449237294196223 -9.74e-07 9.59e-06 1.24e-04 3.82e-05 0.0 + 7 -205.5449237339887532 -4.57e-09 4.49e-06 6.76e-05 2.50e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.54492373398875 Eh -5593.16173 eV + +Components: +Nuclear Repulsion : 69.77123453329233 Eh 1898.57181 eV +Electronic Energy : -275.31615826728108 Eh -7491.73354 eV +One Electron Energy: -419.25313468780683 Eh -11408.45779 eV +Two Electron Energy: 143.93697642052575 Eh 3916.72425 eV + +Virial components: +Potential Energy : -410.38910711043025 Eh -11167.25534 eV +Kinetic Energy : 204.84418337644146 Eh 5574.09361 eV +Virial Ratio : 2.00342084576675 + +DFT components: +N(Alpha) : 11.999998811975 electrons +N(Beta) : 11.999998811975 electrons +N(Total) : 23.999997623950 electrons +E(X) : -23.341664348513 Eh +E(C) : -0.804358811978 Eh +E(XC) : -24.146023160492 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 4.5691e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.7555e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.4867e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.7206e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.5036e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 5.6355e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.7 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 8.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360938 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007168458 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.538116214795 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000730 -0.000006888 0.000000880 + 2 O : 0.000000642 0.000000243 -0.000000343 + 3 O : 0.000002466 0.000008671 0.000000500 + 4 H : -0.000002378 -0.000002026 -0.000001037 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000119038 +RMS gradient ... 0.0000034363 +MAX gradient ... 0.0000086712 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.010275091 -0.016731593 -0.022898180 + 2 O : -0.014129372 0.012441776 -0.032691277 + 3 O : 0.008869369 -0.007288476 0.025890721 + 4 H : -0.005015088 0.011578293 0.029698736 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000145360 -0.0000352649 0.0000367890 + +Norm of the Cartesian gradient ... 0.0646246607 +RMS gradient ... 0.0186555326 +MAX gradient ... 0.0326912772 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.127 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.1%) +RI-J Coulomb gradient .... 0.062 sec ( 48.7%) +XC gradient .... 0.019 sec ( 15.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.538116215 Eh +Current gradient norm .... 0.064624661 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999997264 +Lowest eigenvalues of augmented Hessian: + -0.000001931 0.316278464 0.379214638 0.426865240 0.497938193 +Length of the computed step .... 0.002339158 +The final length of the internal step .... 0.002339158 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0009549573 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0004481971 RMS(Int)= 0.0009549432 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000966 +Previously predicted energy change .... -0.000005062 +Actually observed energy change .... -0.000006387 +Ratio of predicted to observed change .... 1.261931843 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000063873 0.0000050000 NO + RMS gradient 0.0003466093 0.0001000000 NO + MAX gradient 0.0005573564 0.0003000000 NO + RMS step 0.0009549573 0.0020000000 YES + MAX step 0.0017144274 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0009 Max(Angles) 0.05 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3007 -0.000506 0.0009 1.3016 + 2. B(O 2,O 1) 1.2929 0.000557 -0.0007 1.2922 + 3. B(H 3,N 0) 1.0334 -0.000189 0.0002 1.0335 + 4. A(O 1,N 0,H 3) 101.53 0.000342 -0.05 101.48 + 5. A(N 0,O 1,O 2) 116.84 0.000041 -0.02 116.82 + 6. D(O 2,O 1,N 0,H 3) -133.85 0.061734 -0.00 -133.85 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.699 %) +Internal coordinates : 0.000 s ( 3.005 %) +B/P matrices and projection : 0.000 s (12.022 %) +Hessian update/contruction : 0.000 s (32.787 %) +Making the step : 0.000 s ( 7.514 %) +Converting the step to Cartesian: 0.000 s ( 3.962 %) +Storing new data : 0.000 s ( 3.552 %) +Checking convergence : 0.000 s ( 1.366 %) +Final printing : 0.000 s (25.820 %) +Total time : 0.001 s + +Time for energy+gradient : 3.901 s +Time for complete geometry iter : 4.664 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 4 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.602423 -0.439831 -0.139156 + O 0.441453 0.326998 -0.267623 + O 0.323520 1.546215 0.144002 + H -0.181258 -1.295538 0.259070 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.138414 -0.831159 -0.262967 + 1 O 8.0000 0 15.999 0.834225 0.617936 -0.505734 + 2 O 8.0000 0 15.999 0.611365 2.921923 0.272124 + 3 H 1.0000 0 1.008 -0.342529 -2.448212 0.489570 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.301616174143 0.00000000 0.00000000 + O 2 1 0 1.292220557057 116.82208131 0.00000000 + H 1 2 3 1.033536803660 101.47797540 226.15384591 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.459698100612 0.00000000 0.00000000 + O 2 1 0 2.441942957462 116.82208131 0.00000000 + H 1 2 3 1.953101508245 101.47797540 226.15384591 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1667 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.768499084138 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.838e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22308 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5449254772220797 0.00e+00 2.63e-05 2.74e-04 5.13e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5449266779612572 -1.20e-06 3.31e-05 4.76e-04 1.16e-04 0.0 + 3 -205.5449246425096703 2.04e-06 2.65e-05 3.98e-04 5.43e-04 0.0 + 4 -205.5449268171788617 -2.17e-06 8.95e-06 1.59e-04 5.22e-05 0.0 + 5 -205.5449266752540325 1.42e-07 6.35e-06 1.14e-04 1.39e-04 0.0 + 6 -205.5449268399827361 -1.65e-07 7.41e-07 1.13e-05 2.89e-06 0.0 + 7 -205.5449268396897082 2.93e-10 3.50e-07 5.98e-06 2.67e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.54492683968971 Eh -5593.16181 eV + +Components: +Nuclear Repulsion : 69.76849908413766 Eh 1898.49738 eV +Electronic Energy : -275.31342592382737 Eh -7491.65919 eV +One Electron Energy: -419.24661886882114 Eh -11408.28049 eV +Two Electron Energy: 143.93319294499378 Eh 3916.62130 eV + +Virial components: +Potential Energy : -410.38874252653159 Eh -11167.24542 eV +Kinetic Energy : 204.84381568684191 Eh 5574.08361 eV +Virial Ratio : 2.00342266204375 + +DFT components: +N(Alpha) : 11.999998796153 electrons +N(Beta) : 11.999998796153 electrons +N(Total) : 23.999997592305 electrons +E(X) : -23.341336768184 Eh +E(C) : -0.804352248764 Eh +E(XC) : -24.145689016948 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -2.9303e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.9771e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.5019e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 4.1724e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.6719e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.1023e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 8.5 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360944 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007170301 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.538117481981 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000729 -0.000006887 0.000000880 + 2 O : 0.000000643 0.000000245 -0.000000343 + 3 O : 0.000002467 0.000008666 0.000000499 + 4 H : -0.000002380 -0.000002024 -0.000001037 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000118999 +RMS gradient ... 0.0000034352 +MAX gradient ... 0.0000086663 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.009763299 -0.016793741 -0.022853383 + 2 O : -0.013676181 0.012954558 -0.032648858 + 3 O : 0.008834745 -0.007639941 0.025787764 + 4 H : -0.004921863 0.011479124 0.029714476 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000169423 -0.0000241496 0.0000241687 + +Norm of the Cartesian gradient ... 0.0645043452 +RMS gradient ... 0.0186208005 +MAX gradient ... 0.0326488578 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.134 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.8%) +RI-J Coulomb gradient .... 0.063 sec ( 47.1%) +XC gradient .... 0.018 sec ( 13.1%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.538117482 Eh +Current gradient norm .... 0.064504345 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999085 +Lowest eigenvalues of augmented Hessian: + -0.000000461 0.226367369 0.400156569 0.420576530 0.488473759 +Length of the computed step .... 0.001352872 +The final length of the internal step .... 0.001352872 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0005523075 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0003882865 RMS(Int)= 0.0005523403 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000230 +Previously predicted energy change .... -0.000000966 +Actually observed energy change .... -0.000001267 +Ratio of predicted to observed change .... 1.312389202 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000012672 0.0000050000 YES + RMS gradient 0.0001462662 0.0001000000 NO + MAX gradient 0.0002564244 0.0003000000 YES + RMS step 0.0005523075 0.0020000000 YES + MAX step 0.0009843690 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0003 Max(Angles) 0.06 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3016 -0.000072 0.0003 1.3019 + 2. B(O 2,O 1) 1.2922 0.000197 -0.0003 1.2919 + 3. B(H 3,N 0) 1.0335 -0.000060 0.0001 1.0336 + 4. A(O 1,N 0,H 3) 101.48 0.000256 -0.06 101.42 + 5. A(N 0,O 1,O 2) 116.82 -0.000122 0.01 116.84 + 6. D(O 2,O 1,N 0,H 3) -133.85 0.061693 -0.00 -133.85 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (11.307 %) +Internal coordinates : 0.000 s ( 3.141 %) +B/P matrices and projection : 0.000 s (11.683 %) +Hessian update/contruction : 0.000 s (31.658 %) +Making the step : 0.000 s ( 5.528 %) +Converting the step to Cartesian: 0.000 s ( 3.894 %) +Storing new data : 0.000 s ( 3.141 %) +Checking convergence : 0.000 s ( 1.508 %) +Final printing : 0.000 s (28.015 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 4 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.602837 -0.439929 -0.139337 + O 0.441389 0.327039 -0.267412 + O 0.323669 1.546012 0.143950 + H -0.180929 -1.295278 0.259091 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.139197 -0.831345 -0.263309 + 1 O 8.0000 0 15.999 0.834105 0.618015 -0.505335 + 2 O 8.0000 0 15.999 0.611646 2.921539 0.272026 + 3 H 1.0000 0 1.008 -0.341907 -2.447721 0.489611 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.301941744331 0.00000000 0.00000000 + O 2 1 0 1.291886586790 116.83599701 0.00000000 + H 1 2 3 1.033621256512 101.42157521 226.15384591 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.460313339105 0.00000000 0.00000000 + O 2 1 0 2.441311845120 116.83599701 0.00000000 + H 1 2 3 1.953261101008 101.42157521 226.15384591 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1667 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.769064986751 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.835e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22308 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.7690649868 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5449275602119883 0.00e+00 1.54e-05 1.47e-04 3.35e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5449279242700982 -3.64e-07 1.58e-05 2.51e-04 6.03e-05 0.1 + 3 -205.5449275546523040 3.70e-07 1.25e-05 1.79e-04 2.41e-04 0.1 + 4 -205.5449279712515249 -4.17e-07 7.44e-06 1.17e-04 3.84e-05 0.1 + 5 -205.5449278856436308 8.56e-08 5.01e-06 8.66e-05 1.08e-04 0.1 + 6 -205.5449279871361341 -1.01e-07 5.98e-07 4.84e-06 2.50e-06 0.1 + 7 -205.5449279870640567 7.21e-11 1.73e-07 1.94e-06 1.19e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.54492798706406 Eh -5593.16184 eV + +Components: +Nuclear Repulsion : 69.76906498675079 Eh 1898.51278 eV +Electronic Energy : -275.31399297381483 Eh -7491.67462 eV +One Electron Energy: -419.24728584708697 Eh -11408.29863 eV +Two Electron Energy: 143.93329287327211 Eh 3916.62402 eV + +Virial components: +Potential Energy : -410.38883373515739 Eh -11167.24790 eV +Kinetic Energy : 204.84390574809331 Eh 5574.08606 eV +Virial Ratio : 2.00342222648221 + +DFT components: +N(Alpha) : 11.999998791083 electrons +N(Beta) : 11.999998791083 electrons +N(Total) : 23.999997582167 electrons +E(X) : -23.341307801294 Eh +E(C) : -0.804355824370 Eh +E(XC) : -24.145663625664 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -7.2077e-11 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.9388e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.7338e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.0221e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.1873e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.6941e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.188435 -522.1439 + 1 2.0000 -19.031034 -517.8608 + 2 2.0000 -14.259174 -388.0119 + 3 2.0000 -1.252308 -34.0770 + 4 2.0000 -0.968972 -26.3671 + 5 2.0000 -0.702382 -19.1128 + 6 2.0000 -0.563921 -15.3451 + 7 2.0000 -0.516355 -14.0507 + 8 2.0000 -0.507564 -13.8115 + 9 2.0000 -0.333822 -9.0838 + 10 2.0000 -0.272456 -7.4139 + 11 2.0000 -0.263081 -7.1588 + 12 0.0000 -0.196551 -5.3484 + 13 0.0000 0.052434 1.4268 + 14 0.0000 0.083897 2.2830 + 15 0.0000 0.140968 3.8359 + 16 0.0000 0.224452 6.1076 + 17 0.0000 0.268748 7.3130 + 18 0.0000 0.311687 8.4814 + 19 0.0000 0.330097 8.9824 + 20 0.0000 0.340962 9.2780 + 21 0.0000 0.381559 10.3827 + 22 0.0000 0.400151 10.8887 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.331350 + 1 O : 0.211359 + 2 O : -0.155265 + 3 H : 0.275256 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.894193 s : 3.894193 + pz : 1.095279 p : 3.382738 + px : 1.200976 + py : 1.086483 + dz2 : 0.005911 d : 0.054419 + dxz : 0.015635 + dyz : 0.005160 + dx2y2 : 0.009007 + dxy : 0.018706 + + 1 O s : 3.753923 s : 3.753923 + pz : 1.384828 p : 3.907252 + px : 1.453612 + py : 1.068812 + dz2 : 0.009478 d : 0.127465 + dxz : 0.018847 + dyz : 0.034965 + dx2y2 : 0.020117 + dxy : 0.044058 + + 2 O s : 3.942676 s : 3.942676 + pz : 1.334484 p : 4.189293 + px : 1.832088 + py : 1.022721 + dz2 : 0.004050 d : 0.023296 + dxz : 0.000056 + dyz : 0.008980 + dx2y2 : 0.006613 + dxy : 0.003597 + + 3 H s : 0.694557 s : 0.694557 + pz : 0.009012 p : 0.030187 + px : 0.007136 + py : 0.014039 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.084485 + 1 O : -0.191074 + 2 O : -0.006232 + 3 H : 0.281790 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.358357 s : 3.358357 + pz : 1.023061 p : 3.414495 + px : 1.289495 + py : 1.101940 + dz2 : 0.032399 d : 0.311633 + dxz : 0.044667 + dyz : 0.036440 + dx2y2 : 0.108641 + dxy : 0.089486 + + 1 O s : 3.367787 s : 3.367787 + pz : 1.293381 p : 4.043937 + px : 1.497570 + py : 1.252986 + dz2 : 0.060283 d : 0.779350 + dxz : 0.058951 + dyz : 0.188676 + dx2y2 : 0.241738 + dxy : 0.229702 + + 2 O s : 3.598254 s : 3.598254 + pz : 1.285474 p : 4.149757 + px : 1.711132 + py : 1.153151 + dz2 : 0.034906 d : 0.258221 + dxz : 0.008955 + dyz : 0.073020 + dx2y2 : 0.066254 + dxy : 0.075085 + + 3 H s : 0.642282 s : 0.642282 + pz : 0.021348 p : 0.075927 + px : 0.019720 + py : 0.034859 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3313 7.0000 -0.3313 2.6614 2.6614 0.0000 + 1 O 7.7886 8.0000 0.2114 2.6053 2.6053 0.0000 + 2 O 8.1553 8.0000 -0.1553 1.7111 1.7111 -0.0000 + 3 H 0.7247 1.0000 0.2753 0.9092 0.9092 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3571 B( 0-N , 2-O ) : 0.4398 B( 0-N , 3-H ) : 0.8645 +B( 1-O , 2-O ) : 1.2374 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.894 sec +Sum of individual times .... 0.872 sec ( 97.5%) + +SCF preparation .... 0.414 sec ( 46.3%) +Fock matrix formation .... 0.284 sec ( 31.7%) + Startup .... 0.014 sec ( 4.8% of F) + Split-RI-J .... 0.055 sec ( 19.5% of F) + XC integration .... 0.171 sec ( 60.4% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.011 sec ( 6.5% of XC) + Density eval. .... 0.016 sec ( 9.5% of XC) + XC-Functional eval. .... 0.007 sec ( 4.2% of XC) + XC-Potential eval. .... 0.013 sec ( 7.4% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.016 sec ( 1.7%) +Total Energy calculation .... 0.021 sec ( 2.3%) +Population analysis .... 0.065 sec ( 7.3%) +Orbital Transformation .... 0.008 sec ( 0.8%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.011 sec ( 1.2%) +SOSCF solution .... 0.054 sec ( 6.0%) +Finished LeanSCF after 1.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 8.8 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360948 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007171184 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.538117750593 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.006.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.006.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.145262 0.904375 -0.147350 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5449279870640567 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.507036231 0.719164329 -0.238649791 +Nuclear contribution : -0.236562284 -1.655698995 0.316368868 + ----------------------------------------- +Total Dipole Moment : 0.270473947 -0.936534665 0.077719077 + ----------------------------------------- +Magnitude (a.u.) : 0.977902649 +Magnitude (Debye) : 2.485630997 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.155317 0.422564 0.380783 +Rotational constants in MHz : 94594.030293 12668.140691 11415.580014 + +Dipole components along the rotational axes: +x,y,z [a.u.] : -0.744463 0.512517 0.373357 +x,y,z [Debye]: -1.892274 1.302714 0.948997 + + + +Dipole moment calculation done in 0.0 sec + +Maximum memory used throughout the entire PROP-calculation: 5.4 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 7 * + * * + * Dihedral ( 2, 1, 0, 3) : -124.61538462 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.3021 0.692634 + 2. B(O 2,O 1) 1.2948 0.718697 + 3. B(H 3,N 0) 1.0369 0.396742 + 4. A(O 1,N 0,H 3) 101.3997 0.357862 + 5. A(N 0,O 1,O 2) 116.7071 0.442846 + 6. D(O 2,O 1,N 0,H 3) -124.6154 0.037407 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.601538 -0.449818 -0.172491 + O 0.430488 0.331793 -0.312349 + O 0.328209 1.524601 0.180963 + H -0.175867 -1.268732 0.300170 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.136743 -0.850033 -0.325962 + 1 O 8.0000 0 15.999 0.813505 0.626998 -0.590255 + 2 O 8.0000 0 15.999 0.620226 2.881079 0.341970 + 3 H 1.0000 0 1.008 -0.332341 -2.397557 0.567239 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.301941744331 0.00000000 0.00000000 + O 2 1 0 1.291886586790 116.83599701 0.00000000 + H 1 2 3 1.033621256512 101.42157521 226.15384591 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.460313339105 0.00000000 0.00000000 + O 2 1 0 2.441311845120 116.83599701 0.00000000 + H 1 2 3 1.953261101008 101.42157521 226.15384591 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1674 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.708943639269 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.860e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22309 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.7089436393 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5295258714255624 0.00e+00 4.00e-04 3.58e-03 2.92e-02 0.700 0.1 +Warning: op=0 Small HOMO/LUMO gap ( 0.055) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5307550751244889 -1.23e-03 4.78e-04 4.11e-03 2.32e-02 0.700 0.1 + ***Turning on AO-DIIS*** + 3 -205.5317728818716887 -1.02e-03 3.67e-04 2.93e-03 1.65e-02 0.700 0.0 + 4 -205.5324834151585378 -7.11e-04 9.20e-04 6.86e-03 1.16e-02 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5341447114578273 -1.66e-03 8.84e-05 9.31e-04 7.74e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -205.5341494256827559 -4.71e-06 2.94e-04 3.88e-03 1.04e-03 0.0 + 7 -205.5340365180411482 1.13e-04 2.01e-04 2.95e-03 4.32e-03 0.0 + 8 -205.5341627790381267 -1.26e-04 3.94e-05 5.57e-04 1.90e-04 0.0 + 9 -205.5341615385265754 1.24e-06 2.25e-05 3.38e-04 4.97e-04 0.0 + 10 -205.5341633930605667 -1.85e-06 8.19e-06 1.05e-04 3.64e-05 0.0 + 11 -205.5341634015589420 -8.50e-09 4.01e-06 6.32e-05 2.93e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.53416340155894 Eh -5592.86892 eV + +Components: +Nuclear Repulsion : 69.70894363926931 Eh 1896.87679 eV +Electronic Energy : -275.24310704082825 Eh -7489.74571 eV +One Electron Energy: -419.12405639267706 Eh -11404.94539 eV +Two Electron Energy: 143.88094935184884 Eh 3915.19968 eV + +Virial components: +Potential Energy : -410.37979003417001 Eh -11167.00181 eV +Kinetic Energy : 204.84562663261110 Eh 5574.13288 eV +Virial Ratio : 2.00336124710235 + +DFT components: +N(Alpha) : 11.999997837790 electrons +N(Beta) : 11.999997837790 electrons +N(Total) : 23.999995675580 electrons +E(X) : -23.337691540824 Eh +E(C) : -0.804264781029 Eh +E(XC) : -24.141956321854 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 8.4984e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.3223e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.0133e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.7359e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.9319e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.2625e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.187043 -522.1060 + 1 2.0000 -19.035867 -517.9923 + 2 2.0000 -14.254913 -387.8959 + 3 2.0000 -1.251199 -34.0469 + 4 2.0000 -0.967926 -26.3386 + 5 2.0000 -0.703243 -19.1362 + 6 2.0000 -0.562795 -15.3144 + 7 2.0000 -0.515769 -14.0348 + 8 2.0000 -0.506642 -13.7864 + 9 2.0000 -0.335072 -9.1178 + 10 2.0000 -0.271526 -7.3886 + 11 2.0000 -0.259458 -7.0602 + 12 0.0000 -0.203956 -5.5499 + 13 0.0000 0.051242 1.3944 + 14 0.0000 0.083640 2.2760 + 15 0.0000 0.140095 3.8122 + 16 0.0000 0.226412 6.1610 + 17 0.0000 0.266620 7.2551 + 18 0.0000 0.315076 8.5736 + 19 0.0000 0.332168 9.0387 + 20 0.0000 0.338144 9.2014 + 21 0.0000 0.382869 10.4184 + 22 0.0000 0.397840 10.8258 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.346762 + 1 O : 0.204611 + 2 O : -0.137428 + 3 H : 0.279578 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.893898 s : 3.893898 + pz : 1.094082 p : 3.400191 + px : 1.209637 + py : 1.096472 + dz2 : 0.005224 d : 0.052672 + dxz : 0.014827 + dyz : 0.005457 + dx2y2 : 0.008851 + dxy : 0.018313 + + 1 O s : 3.757062 s : 3.757062 + pz : 1.384788 p : 3.914634 + px : 1.452678 + py : 1.077169 + dz2 : 0.011300 d : 0.123692 + dxz : 0.021411 + dyz : 0.031248 + dx2y2 : 0.018172 + dxy : 0.041561 + + 2 O s : 3.941354 s : 3.941354 + pz : 1.303894 p : 4.174249 + px : 1.799505 + py : 1.070850 + dz2 : 0.004373 d : 0.021825 + dxz : 0.000230 + dyz : 0.007869 + dx2y2 : 0.005580 + dxy : 0.003774 + + 3 H s : 0.690158 s : 0.690158 + pz : 0.009901 p : 0.030264 + px : 0.007186 + py : 0.013177 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.096653 + 1 O : -0.190457 + 2 O : 0.002008 + 3 H : 0.285102 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.356276 s : 3.356276 + pz : 1.025979 p : 3.429078 + px : 1.296160 + py : 1.106938 + dz2 : 0.030499 d : 0.311300 + dxz : 0.045341 + dyz : 0.039916 + dx2y2 : 0.105467 + dxy : 0.090077 + + 1 O s : 3.369734 s : 3.369734 + pz : 1.299545 p : 4.045417 + px : 1.494386 + py : 1.251485 + dz2 : 0.061533 d : 0.775307 + dxz : 0.067001 + dyz : 0.188386 + dx2y2 : 0.236076 + dxy : 0.222311 + + 2 O s : 3.600749 s : 3.600749 + pz : 1.267649 p : 4.139892 + px : 1.682089 + py : 1.190155 + dz2 : 0.037366 d : 0.257350 + dxz : 0.012295 + dyz : 0.075147 + dx2y2 : 0.062544 + dxy : 0.069997 + + 3 H s : 0.638952 s : 0.638952 + pz : 0.023747 p : 0.075946 + px : 0.019804 + py : 0.032395 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3468 7.0000 -0.3468 2.6353 2.6353 -0.0000 + 1 O 7.7954 8.0000 0.2046 2.5899 2.5899 -0.0000 + 2 O 8.1374 8.0000 -0.1374 1.6977 1.6977 0.0000 + 3 H 0.7204 1.0000 0.2796 0.9063 0.9063 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3491 B( 0-N , 2-O ) : 0.4292 B( 0-N , 3-H ) : 0.8571 +B( 1-O , 2-O ) : 1.2301 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.953 sec +Sum of individual times .... 0.939 sec ( 98.6%) + +SCF preparation .... 0.413 sec ( 43.4%) +Fock matrix formation .... 0.282 sec ( 29.6%) + Startup .... 0.013 sec ( 4.5% of F) + Split-RI-J .... 0.040 sec ( 14.3% of F) + XC integration .... 0.185 sec ( 65.4% of F) + Basis function eval. .... 0.013 sec ( 6.8% of XC) + Density eval. .... 0.017 sec ( 9.0% of XC) + XC-Functional eval. .... 0.010 sec ( 5.6% of XC) + XC-Potential eval. .... 0.017 sec ( 8.9% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.034 sec ( 3.5%) +Total Energy calculation .... 0.024 sec ( 2.5%) +Population analysis .... 0.065 sec ( 6.8%) +Orbital Transformation .... 0.014 sec ( 1.5%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.070 sec ( 7.3%) +SOSCF solution .... 0.038 sec ( 4.0%) +Finished LeanSCF after 1.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 9.2 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000361353 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007186881 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.527337874323 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000709 -0.000006771 0.000001013 + 2 O : 0.000000626 0.000000252 -0.000000405 + 3 O : 0.000002450 0.000008392 0.000000667 + 4 H : -0.000002367 -0.000001874 -0.000001275 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000116450 +RMS gradient ... 0.0000033616 +MAX gradient ... 0.0000083920 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.015804526 -0.017018301 -0.028034165 + 2 O : -0.023142242 0.013126571 -0.034776046 + 3 O : 0.012127806 -0.010736199 0.028606710 + 4 H : -0.004790090 0.014627929 0.034203502 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000134555 -0.0000141858 0.0000224470 + +Norm of the Cartesian gradient ... 0.0756971458 +RMS gradient ... 0.0218518838 +MAX gradient ... 0.0347760458 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.135 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 4.0%) +RI-J Coulomb gradient .... 0.064 sec ( 47.7%) +XC gradient .... 0.020 sec ( 15.1%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.527337874 Eh +Current gradient norm .... 0.075697146 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999893777 +Lowest eigenvalues of augmented Hessian: + -0.000107624 0.357113457 0.391959238 0.441922078 0.692206928 +Length of the computed step .... 0.014576711 +The final length of the internal step .... 0.014576711 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0059509172 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0048703878 RMS(Int)= 0.0059516491 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000003 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0031651573 0.0001000000 NO + MAX gradient 0.0066299347 0.0003000000 NO + RMS step 0.0059509172 0.0020000000 NO + MAX step 0.0096223928 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0051 Max(Angles) 0.55 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3021 -0.006630 0.0051 1.3072 + 2. B(O 2,O 1) 1.2948 0.000048 -0.0000 1.2948 + 3. B(H 3,N 0) 1.0369 0.002072 -0.0028 1.0341 + 4. A(O 1,N 0,H 3) 101.40 -0.003437 0.55 101.95 + 5. A(N 0,O 1,O 2) 116.71 0.000212 -0.03 116.68 + 6. D(O 2,O 1,N 0,H 3) -124.62 0.071859 0.00 -124.62 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.160 %) +Internal coordinates : 0.000 s ( 6.016 %) +B/P matrices and projection : 0.000 s (22.594 %) +Hessian update/contruction : 0.000 s (25.936 %) +Making the step : 0.000 s ( 5.615 %) +Converting the step to Cartesian: 0.000 s ( 4.545 %) +Storing new data : 0.000 s ( 3.476 %) +Checking convergence : 0.000 s ( 0.134 %) +Final printing : 0.000 s (21.257 %) +Total time : 0.001 s + +Time for energy+gradient : 4.292 s +Time for complete geometry iter : 5.079 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.599971 -0.452589 -0.169912 + O 0.432932 0.335539 -0.313945 + O 0.328119 1.527560 0.180642 + H -0.179788 -1.272665 0.299507 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.133780 -0.855270 -0.321088 + 1 O 8.0000 0 15.999 0.818122 0.634076 -0.593270 + 2 O 8.0000 0 15.999 0.620055 2.886670 0.341365 + 3 H 1.0000 0 1.008 -0.339750 -2.404989 0.565987 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.307202669949 0.00000000 0.00000000 + O 2 1 0 1.294803690497 116.67964957 0.00000000 + H 1 2 3 1.034134055991 101.95100534 235.38461539 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.470255047735 0.00000000 0.00000000 + O 2 1 0 2.446824372230 116.67964957 0.00000000 + H 1 2 3 1.954230151583 101.95100534 235.38461539 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1667 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.591492030535 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.864e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22311 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5341701165942254 0.00e+00 1.32e-04 1.15e-03 2.86e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5342039636485083 -3.38e-05 1.20e-04 1.24e-03 4.54e-04 0.0 + 3 -205.5341942697767195 9.69e-06 8.20e-05 1.44e-03 1.29e-03 0.0 + 4 -205.5342053969878293 -1.11e-05 1.17e-04 1.77e-03 5.59e-04 0.0 + 5 -205.5341837090438162 2.17e-05 8.37e-05 1.36e-03 1.66e-03 0.0 + 6 -205.5342093179575613 -2.56e-05 1.84e-05 2.89e-04 5.70e-05 0.0 + 7 -205.5342093277087656 -9.75e-09 8.99e-06 1.53e-04 6.07e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.53420932770877 Eh -5592.87017 eV + +Components: +Nuclear Repulsion : 69.59149203053488 Eh 1893.68077 eV +Electronic Energy : -275.12570135824365 Eh -7486.55094 eV +One Electron Energy: -418.89927230417163 Eh -11398.82870 eV +Two Electron Energy: 143.77357094592799 Eh 3912.27776 eV + +Virial components: +Potential Energy : -410.36955309510631 Eh -11166.72324 eV +Kinetic Energy : 204.83534376739757 Eh 5573.85307 eV +Virial Ratio : 2.00341184068851 + +DFT components: +N(Alpha) : 11.999997715272 electrons +N(Beta) : 11.999997715272 electrons +N(Total) : 23.999995430544 electrons +E(X) : -23.335463559224 Eh +E(C) : -0.804046460979 Eh +E(XC) : -24.139510020203 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 9.7512e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.5325e-04 Tolerance : 1.0000e-07 + Last RMS-Density change ... 8.9941e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.9674e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 6.0718e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 6.4204e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.7 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 9.4 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361230 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007166012 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.527404545631 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000728 -0.000006804 0.000001009 + 2 O : 0.000000633 0.000000274 -0.000000413 + 3 O : 0.000002463 0.000008452 0.000000664 + 4 H : -0.000002369 -0.000001921 -0.000001259 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000117179 +RMS gradient ... 0.0000033827 +MAX gradient ... 0.0000084515 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.015200020 -0.021468510 -0.026625746 + 2 O : -0.020741930 0.015721143 -0.035221180 + 3 O : 0.012388291 -0.009522698 0.028585934 + 4 H : -0.006846381 0.015270066 0.033260992 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000067670 -0.0000179497 0.0000355028 + +Norm of the Cartesian gradient ... 0.0759370134 +RMS gradient ... 0.0219211276 +MAX gradient ... 0.0352211800 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.131 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.9%) +RI-J Coulomb gradient .... 0.059 sec ( 45.0%) +XC gradient .... 0.022 sec ( 17.2%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.527404546 Eh +Current gradient norm .... 0.075937013 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999978037 +Lowest eigenvalues of augmented Hessian: + -0.000017119 0.317748420 0.384206498 0.461476474 0.549861958 +Length of the computed step .... 0.006627737 +The final length of the internal step .... 0.006627737 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0027057623 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0018009244 RMS(Int)= 0.0027054658 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000008560 +Previously predicted energy change .... -0.000053824 +Actually observed energy change .... -0.000066671 +Ratio of predicted to observed change .... 1.238699455 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000666713 0.0000050000 NO + RMS gradient 0.0010911717 0.0001000000 NO + MAX gradient 0.0021291298 0.0003000000 NO + RMS step 0.0027057623 0.0020000000 NO + MAX step 0.0048509561 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0026 Max(Angles) 0.18 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3072 -0.002129 0.0026 1.3098 + 2. B(O 2,O 1) 1.2948 0.001147 -0.0011 1.2937 + 3. B(H 3,N 0) 1.0341 0.000206 -0.0006 1.0335 + 4. A(O 1,N 0,H 3) 101.95 -0.000347 0.12 102.07 + 5. A(N 0,O 1,O 2) 116.68 0.001064 -0.18 116.50 + 6. D(O 2,O 1,N 0,H 3) -124.62 0.071182 0.00 -124.62 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 7.862 %) +Internal coordinates : 0.000 s ( 2.948 %) +B/P matrices and projection : 0.000 s (11.794 %) +Hessian update/contruction : 0.000 s (42.138 %) +Making the step : 0.000 s ( 4.668 %) +Converting the step to Cartesian: 0.000 s ( 4.300 %) +Storing new data : 0.000 s ( 3.194 %) +Checking convergence : 0.000 s ( 1.229 %) +Final printing : 0.000 s (21.622 %) +Total time : 0.001 s + +Time for energy+gradient : 3.917 s +Time for complete geometry iter : 4.717 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.599831 -0.452749 -0.168819 + O 0.434814 0.336946 -0.315071 + O 0.327228 1.527006 0.180710 + H -0.180919 -1.273359 0.299471 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.133516 -0.855571 -0.319022 + 1 O 8.0000 0 15.999 0.821679 0.636735 -0.595397 + 2 O 8.0000 0 15.999 0.618372 2.885622 0.341493 + 3 H 1.0000 0 1.008 -0.341888 -2.406299 0.565918 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.309769685355 0.00000000 0.00000000 + O 2 1 0 1.293683088742 116.49669020 0.00000000 + H 1 2 3 1.033529396919 102.07130376 235.38461539 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.475106003833 0.00000000 0.00000000 + O 2 1 0 2.444706741808 116.49669020 0.00000000 + H 1 2 3 1.953087511533 102.07130376 235.38461539 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1667 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.573361064213 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.858e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22312 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5342071167133895 0.00e+00 7.84e-05 5.57e-04 2.04e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5342197686497911 -1.27e-05 7.29e-05 6.89e-04 2.23e-04 0.0 + 3 -205.5342164277648180 3.34e-06 5.50e-05 8.26e-04 8.99e-04 0.0 + 4 -205.5342208975744711 -4.47e-06 4.43e-05 5.58e-04 2.00e-04 0.0 + 5 -205.5342202134320928 6.84e-07 2.02e-05 3.58e-04 4.40e-04 0.0 + 6 -205.5342214821172888 -1.27e-06 2.13e-05 2.40e-04 1.17e-04 0.0 + 7 -205.5342215371545649 -5.50e-08 9.64e-06 1.34e-04 4.30e-05 0.0 + 8 -205.5342216137033802 -7.65e-08 1.62e-06 1.42e-05 8.20e-06 0.0 + 9 -205.5342216146714236 -9.68e-10 7.09e-07 6.51e-06 4.65e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.53422161467142 Eh -5592.87051 eV + +Components: +Nuclear Repulsion : 69.57336106421276 Eh 1893.18740 eV +Electronic Energy : -275.10758267888417 Eh -7486.05791 eV +One Electron Energy: -418.86154049605238 Eh -11397.80197 eV +Two Electron Energy: 143.75395781716821 Eh 3911.74406 eV + +Virial components: +Potential Energy : -410.36771531326360 Eh -11166.67324 eV +Kinetic Energy : 204.83349369859218 Eh 5573.80273 eV +Virial Ratio : 2.00342096355155 + +DFT components: +N(Alpha) : 11.999997605929 electrons +N(Beta) : 11.999997605929 electrons +N(Total) : 23.999995211858 electrons +E(X) : -23.334451392647 Eh +E(C) : -0.803993502492 Eh +E(XC) : -24.138444895139 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 9.6804e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.5143e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 7.0909e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.9906e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.6529e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.5376e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 9.5 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361227 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007167744 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.527415097707 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000729 -0.000006805 0.000001009 + 2 O : 0.000000638 0.000000283 -0.000000415 + 3 O : 0.000002459 0.000008445 0.000000660 + 4 H : -0.000002368 -0.000001924 -0.000001255 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000117130 +RMS gradient ... 0.0000033813 +MAX gradient ... 0.0000084448 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.014347933 -0.022343126 -0.026082130 + 2 O : -0.019146812 0.016988515 -0.035282241 + 3 O : 0.012065131 -0.010024482 0.028367949 + 4 H : -0.007266252 0.015379093 0.032996422 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000165537 -0.0000039748 -0.0000044474 + +Norm of the Cartesian gradient ... 0.0755928534 +RMS gradient ... 0.0218217771 +MAX gradient ... 0.0352822411 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.140 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.8%) +RI-J Coulomb gradient .... 0.062 sec ( 44.2%) +XC gradient .... 0.021 sec ( 15.1%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.527415098 Eh +Current gradient norm .... 0.075592853 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999996433 +Lowest eigenvalues of augmented Hessian: + -0.000002586 0.304143622 0.377841610 0.424000084 0.504755117 +Length of the computed step .... 0.002670967 +The final length of the internal step .... 0.002670967 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0010904176 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0005089305 RMS(Int)= 0.0010903683 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000001293 +Previously predicted energy change .... -0.000008560 +Actually observed energy change .... -0.000010552 +Ratio of predicted to observed change .... 1.232731395 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000105521 0.0000050000 NO + RMS gradient 0.0004093662 0.0001000000 NO + MAX gradient 0.0006460598 0.0003000000 NO + RMS step 0.0010904176 0.0020000000 YES + MAX step 0.0020240420 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0011 Max(Angles) 0.05 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3098 -0.000623 0.0011 1.3108 + 2. B(O 2,O 1) 1.2937 0.000646 -0.0007 1.2929 + 3. B(H 3,N 0) 1.0335 -0.000204 0.0002 1.0337 + 4. A(O 1,N 0,H 3) 102.07 0.000388 -0.05 102.03 + 5. A(N 0,O 1,O 2) 116.50 0.000084 -0.03 116.46 + 6. D(O 2,O 1,N 0,H 3) -124.62 0.070903 -0.00 -124.62 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.830 %) +Internal coordinates : 0.000 s ( 3.516 %) +B/P matrices and projection : 0.000 s (14.205 %) +Hessian update/contruction : 0.000 s (29.114 %) +Making the step : 0.000 s ( 5.485 %) +Converting the step to Cartesian: 0.000 s ( 5.626 %) +Storing new data : 0.000 s ( 3.516 %) +Checking convergence : 0.000 s ( 1.688 %) +Final printing : 0.000 s (25.879 %) +Total time : 0.001 s + +Time for energy+gradient : 4.065 s +Time for complete geometry iter : 4.864 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 4 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.600343 -0.452829 -0.168830 + O 0.435273 0.337367 -0.315094 + O 0.327144 1.526590 0.180666 + H -0.180782 -1.273284 0.299550 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.134483 -0.855724 -0.319043 + 1 O 8.0000 0 15.999 0.822546 0.637532 -0.595441 + 2 O 8.0000 0 15.999 0.618212 2.884836 0.341409 + 3 H 1.0000 0 1.008 -0.341628 -2.406157 0.566068 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.310840762260 0.00000000 0.00000000 + O 2 1 0 1.292949798878 116.46181975 0.00000000 + H 1 2 3 1.033710274173 102.02583123 235.38461539 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.477130045851 0.00000000 0.00000000 + O 2 1 0 2.443321024788 116.46181975 0.00000000 + H 1 2 3 1.953429320007 102.02583123 235.38461539 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1667 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.569559947138 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.852e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22313 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5342236335183657 0.00e+00 3.03e-05 3.01e-04 5.41e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5342252699980463 -1.64e-06 3.68e-05 4.66e-04 1.44e-04 0.0 + 3 -205.5342228966450193 2.37e-06 2.90e-05 4.17e-04 6.42e-04 0.0 + 4 -205.5342254657893477 -2.57e-06 9.95e-06 1.72e-04 5.55e-05 0.0 + 5 -205.5342252965755847 1.69e-07 7.06e-06 1.23e-04 1.64e-04 0.0 + 6 -205.5342254938643691 -1.97e-07 1.04e-06 1.67e-05 3.74e-06 0.0 + 7 -205.5342254933593154 5.05e-10 4.88e-07 8.27e-06 3.54e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.53422549335932 Eh -5592.87061 eV + +Components: +Nuclear Repulsion : 69.56955994713752 Eh 1893.08397 eV +Electronic Energy : -275.10378544049684 Eh -7485.95458 eV +One Electron Energy: -418.85414300572535 Eh -11397.60067 eV +Two Electron Energy: 143.75035756522851 Eh 3911.64609 eV + +Virial components: +Potential Energy : -410.36718031149462 Eh -11166.65868 eV +Kinetic Energy : 204.83295481813533 Eh 5573.78807 eV +Virial Ratio : 2.00342362231628 + +DFT components: +N(Alpha) : 11.999997575849 electrons +N(Beta) : 11.999997575849 electrons +N(Total) : 23.999995151697 electrons +E(X) : -23.334215988742 Eh +E(C) : -0.803985615568 Eh +E(XC) : -24.138201604310 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -5.0505e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.2679e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.8772e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 4.4299e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.5434e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.9489e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 9.7 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361233 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007169898 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.527416828434 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000728 -0.000006804 0.000001010 + 2 O : 0.000000639 0.000000286 -0.000000415 + 3 O : 0.000002459 0.000008439 0.000000660 + 4 H : -0.000002370 -0.000001922 -0.000001255 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000117086 +RMS gradient ... 0.0000033800 +MAX gradient ... 0.0000084393 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.013807065 -0.022417869 -0.026016811 + 2 O : -0.018618046 0.017529396 -0.035232209 + 3 O : 0.011997422 -0.010381924 0.028237545 + 4 H : -0.007186440 0.015270398 0.033011475 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000172800 -0.0000057275 -0.0000012672 + +Norm of the Cartesian gradient ... 0.0754251893 +RMS gradient ... 0.0217733767 +MAX gradient ... 0.0352322089 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.126 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.9%) +RI-J Coulomb gradient .... 0.059 sec ( 47.0%) +XC gradient .... 0.019 sec ( 15.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.527416828 Eh +Current gradient norm .... 0.075425189 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.675 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999998042 +Lowest eigenvalues of augmented Hessian: + -0.000000923 0.215211124 0.393247509 0.404795398 0.488963755 +Length of the computed step .... 0.001978779 +The final length of the internal step .... 0.001978779 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0008078332 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0005184071 RMS(Int)= 0.0008078972 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000462 +Previously predicted energy change .... -0.000001293 +Actually observed energy change .... -0.000001731 +Ratio of predicted to observed change .... 1.338361855 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000017307 0.0000050000 YES + RMS gradient 0.0001996159 0.0001000000 NO + MAX gradient 0.0003428165 0.0003000000 NO + RMS step 0.0008078332 0.0020000000 YES + MAX step 0.0013775012 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0005 Max(Angles) 0.08 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3108 -0.000141 0.0005 1.3114 + 2. B(O 2,O 1) 1.2929 0.000274 -0.0005 1.2925 + 3. B(H 3,N 0) 1.0337 -0.000078 0.0001 1.0338 + 4. A(O 1,N 0,H 3) 102.03 0.000343 -0.08 101.95 + 5. A(N 0,O 1,O 2) 116.46 -0.000143 0.01 116.48 + 6. D(O 2,O 1,N 0,H 3) -124.62 0.070838 -0.00 -124.62 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.112 %) +Internal coordinates : 0.000 s ( 2.996 %) +B/P matrices and projection : 0.000 s (11.610 %) +Hessian update/contruction : 0.000 s (33.833 %) +Making the step : 0.000 s ( 5.243 %) +Converting the step to Cartesian: 0.000 s ( 3.870 %) +Storing new data : 0.000 s ( 2.996 %) +Checking convergence : 0.000 s ( 1.373 %) +Final printing : 0.000 s (27.591 %) +Total time : 0.001 s + +Time for energy+gradient : 4.041 s +Time for complete geometry iter : 4.818 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 5 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.600913 -0.452977 -0.169078 + O 0.435284 0.337451 -0.314810 + O 0.327292 1.526299 0.180594 + H -0.180371 -1.272929 0.299586 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.135561 -0.856002 -0.319512 + 1 O 8.0000 0 15.999 0.822568 0.637690 -0.594904 + 2 O 8.0000 0 15.999 0.618493 2.884287 0.341273 + 3 H 1.0000 0 1.008 -0.340853 -2.405488 0.566136 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.311380344729 0.00000000 0.00000000 + O 2 1 0 1.292457547485 116.47507582 0.00000000 + H 1 2 3 1.033839360726 101.94690622 235.38461539 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.478149708944 0.00000000 0.00000000 + O 2 1 0 2.442390804466 116.47507582 0.00000000 + H 1 2 3 1.953673258240 101.94690622 235.38461539 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1668 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.569499490676 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.847e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22313 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5342265553496190 0.00e+00 2.20e-05 2.10e-04 4.71e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5342273128811712 -7.58e-07 2.30e-05 3.41e-04 9.86e-05 0.0 + 3 -205.5342264893602078 8.24e-07 1.84e-05 2.58e-04 3.90e-04 0.0 + 4 -205.5342274211423614 -9.32e-07 9.91e-06 1.63e-04 4.99e-05 0.0 + 5 -205.5342272583603744 1.63e-07 6.96e-06 1.16e-04 1.59e-04 0.0 + 6 -205.5342274494680055 -1.91e-07 6.61e-07 5.09e-06 2.09e-06 0.0 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 6 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.53422744946801 Eh -5592.87066 eV + +Components: +Nuclear Repulsion : 69.56949949067649 Eh 1893.08232 eV +Electronic Energy : -275.10372694014450 Eh -7485.95299 eV +One Electron Energy: -418.85338453467710 Eh -11397.58003 eV +Two Electron Energy: 143.74965759453261 Eh 3911.62705 eV + +Virial components: +Potential Energy : -410.36726958787324 Eh -11166.66111 eV +Kinetic Energy : 204.83304213840523 Eh 5573.79044 eV +Virial Ratio : 2.00342320410683 + +DFT components: +N(Alpha) : 11.999997573527 electrons +N(Beta) : 11.999997573527 electrons +N(Total) : 23.999995147054 electrons +E(X) : -23.334142430757 Eh +E(C) : -0.803987650558 Eh +E(XC) : -24.138130081315 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.9111e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.0913e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 6.6065e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.8885e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.0888e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.5646e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 9.9 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361238 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007171312 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.527417374842 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000727 -0.000006803 0.000001010 + 2 O : 0.000000639 0.000000287 -0.000000414 + 3 O : 0.000002460 0.000008435 0.000000659 + 4 H : -0.000002372 -0.000001919 -0.000001256 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000117052 +RMS gradient ... 0.0000033790 +MAX gradient ... 0.0000084351 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.013493124 -0.022427414 -0.026020895 + 2 O : -0.018456232 0.017793853 -0.035162139 + 3 O : 0.012023523 -0.010616522 0.028154898 + 4 H : -0.007060416 0.015250083 0.033028136 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000187509 -0.0000063281 -0.0000034652 + +Norm of the Cartesian gradient ... 0.0753592480 +RMS gradient ... 0.0217543411 +MAX gradient ... 0.0351621391 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.141 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.8%) +RI-J Coulomb gradient .... 0.064 sec ( 45.6%) +XC gradient .... 0.022 sec ( 16.0%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.527417375 Eh +Current gradient norm .... 0.075359248 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.675 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999838 +Lowest eigenvalues of augmented Hessian: + -0.000000080 0.186212848 0.377802414 0.407287382 0.477055152 +Length of the computed step .... 0.000569333 +The final length of the internal step .... 0.000569333 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0002324293 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0002018621 RMS(Int)= 0.0002324333 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000040 +Previously predicted energy change .... -0.000000462 +Actually observed energy change .... -0.000000546 +Ratio of predicted to observed change .... 1.183456330 +New trust radius .... 0.700000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000005464 0.0000050000 YES + RMS gradient 0.0000618871 0.0001000000 YES + MAX gradient 0.0001103792 0.0003000000 YES + RMS step 0.0002324293 0.0020000000 YES + MAX step 0.0004815505 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.03 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3114 0.000022 0.0000 1.3114 + 2. B(O 2,O 1) 1.2925 0.000021 -0.0001 1.2924 + 3. B(H 3,N 0) 1.0338 0.000007 0.0000 1.0338 + 4. A(O 1,N 0,H 3) 101.95 0.000110 -0.03 101.92 + 5. A(N 0,O 1,O 2) 116.48 -0.000099 0.01 116.49 + 6. D(O 2,O 1,N 0,H 3) -124.62 0.070835 -0.00 -124.62 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.993 %) +Internal coordinates : 0.000 s ( 3.073 %) +B/P matrices and projection : 0.000 s (13.357 %) +Hessian update/contruction : 0.000 s (31.797 %) +Making the step : 0.000 s ( 4.728 %) +Converting the step to Cartesian: 0.000 s ( 3.783 %) +Storing new data : 0.000 s ( 4.019 %) +Checking convergence : 0.000 s ( 1.418 %) +Final printing : 0.000 s (26.596 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 5 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.601077 -0.453048 -0.169191 + O 0.435191 0.337405 -0.314666 + O 0.327388 1.526264 0.180568 + H -0.180210 -1.272776 0.299581 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.135871 -0.856137 -0.319725 + 1 O 8.0000 0 15.999 0.822391 0.637602 -0.594632 + 2 O 8.0000 0 15.999 0.618674 2.884221 0.341223 + 3 H 1.0000 0 1.008 -0.340547 -2.405199 0.566127 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.311422470461 0.00000000 0.00000000 + O 2 1 0 1.292386812099 116.49001605 0.00000000 + H 1 2 3 1.033843120315 101.91931541 235.38461539 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.478229315041 0.00000000 0.00000000 + O 2 1 0 2.442257133959 116.49001605 0.00000000 + H 1 2 3 1.953680362834 101.91931541 235.38461539 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1668 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.569755734286 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.846e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22313 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.5697557343 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5342275284617699 0.00e+00 6.72e-06 5.02e-05 1.69e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5342276033592270 -7.49e-08 5.48e-06 6.62e-05 2.06e-05 0.1 + 3 -205.5342276031592519 2.00e-10 7.00e-06 6.47e-05 4.71e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 3 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.53422760315925 Eh -5592.87067 eV + +Components: +Nuclear Repulsion : 69.56975573428569 Eh 1893.08930 eV +Electronic Energy : -275.10398333744496 Eh -7485.95997 eV +One Electron Energy: -418.85366270027447 Eh -11397.58760 eV +Two Electron Energy: 143.74967936282951 Eh 3911.62764 eV + +Virial components: +Potential Energy : -410.36750100499899 Eh -11166.66740 eV +Kinetic Energy : 204.83327340183970 Eh 5573.79674 eV +Virial Ratio : 2.00342207195969 + +DFT components: +N(Alpha) : 11.999997579157 electrons +N(Beta) : 11.999997579157 electrons +N(Total) : 23.999995158315 electrons +E(X) : -23.334149860679 Eh +E(C) : -0.803989767230 Eh +E(XC) : -24.138139627909 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.9998e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.4697e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 6.9989e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.4593e-05 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.7059e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.2953e-04 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.187001 -522.1049 + 1 2.0000 -19.037523 -518.0373 + 2 2.0000 -14.254223 -387.8771 + 3 2.0000 -1.249778 -34.0082 + 4 2.0000 -0.965289 -26.2668 + 5 2.0000 -0.704824 -19.1792 + 6 2.0000 -0.561729 -15.2854 + 7 2.0000 -0.514859 -14.0100 + 8 2.0000 -0.506558 -13.7841 + 9 2.0000 -0.335267 -9.1231 + 10 2.0000 -0.271863 -7.3978 + 11 2.0000 -0.259730 -7.0676 + 12 0.0000 -0.204848 -5.5742 + 13 0.0000 0.050372 1.3707 + 14 0.0000 0.085948 2.3388 + 15 0.0000 0.135855 3.6968 + 16 0.0000 0.225332 6.1316 + 17 0.0000 0.267440 7.2774 + 18 0.0000 0.314991 8.5713 + 19 0.0000 0.332018 9.0347 + 20 0.0000 0.338567 9.2129 + 21 0.0000 0.381966 10.3938 + 22 0.0000 0.397960 10.8290 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.347598 + 1 O : 0.203465 + 2 O : -0.133746 + 3 H : 0.277880 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.893485 s : 3.893485 + pz : 1.097846 p : 3.402516 + px : 1.209250 + py : 1.095421 + dz2 : 0.005174 d : 0.051597 + dxz : 0.014472 + dyz : 0.005262 + dx2y2 : 0.008686 + dxy : 0.018004 + + 1 O s : 3.760030 s : 3.760030 + pz : 1.387298 p : 3.913347 + px : 1.452016 + py : 1.074033 + dz2 : 0.011440 d : 0.123158 + dxz : 0.021335 + dyz : 0.030856 + dx2y2 : 0.018167 + dxy : 0.041360 + + 2 O s : 3.941672 s : 3.941672 + pz : 1.305680 p : 4.170016 + px : 1.792501 + py : 1.071836 + dz2 : 0.004479 d : 0.022058 + dxz : 0.000246 + dyz : 0.007860 + dx2y2 : 0.005615 + dxy : 0.003858 + + 3 H s : 0.691642 s : 0.691642 + pz : 0.009975 p : 0.030478 + px : 0.007197 + py : 0.013307 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.097587 + 1 O : -0.187684 + 2 O : 0.002968 + 3 H : 0.282304 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.359457 s : 3.359457 + pz : 1.030100 p : 3.430916 + px : 1.293741 + py : 1.107075 + dz2 : 0.030274 d : 0.307214 + dxz : 0.044622 + dyz : 0.039493 + dx2y2 : 0.103477 + dxy : 0.089348 + + 1 O s : 3.373035 s : 3.373035 + pz : 1.302532 p : 4.043713 + px : 1.491434 + py : 1.249747 + dz2 : 0.061421 d : 0.770937 + dxz : 0.066612 + dyz : 0.187780 + dx2y2 : 0.233276 + dxy : 0.221847 + + 2 O s : 3.599571 s : 3.599571 + pz : 1.270118 p : 4.138120 + px : 1.675754 + py : 1.192249 + dz2 : 0.037739 d : 0.259341 + dxz : 0.012590 + dyz : 0.075881 + dx2y2 : 0.062687 + dxy : 0.070443 + + 3 H s : 0.640870 s : 0.640870 + pz : 0.023995 p : 0.076826 + px : 0.019914 + py : 0.032917 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3476 7.0000 -0.3476 2.6367 2.6367 -0.0000 + 1 O 7.7965 8.0000 0.2035 2.5889 2.5889 -0.0000 + 2 O 8.1337 8.0000 -0.1337 1.7014 1.7014 -0.0000 + 3 H 0.7221 1.0000 0.2779 0.9073 0.9073 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3459 B( 0-N , 2-O ) : 0.4323 B( 0-N , 3-H ) : 0.8585 +B( 1-O , 2-O ) : 1.2317 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.666 sec +Sum of individual times .... 0.653 sec ( 98.0%) + +SCF preparation .... 0.431 sec ( 64.7%) +Fock matrix formation .... 0.099 sec ( 14.9%) + Startup .... 0.006 sec ( 5.8% of F) + Split-RI-J .... 0.014 sec ( 13.8% of F) + XC integration .... 0.069 sec ( 69.3% of F) + Basis function eval. .... 0.004 sec ( 5.6% of XC) + Density eval. .... 0.005 sec ( 7.3% of XC) + XC-Functional eval. .... 0.003 sec ( 4.4% of XC) + XC-Potential eval. .... 0.005 sec ( 7.1% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.005 sec ( 0.8%) +Total Energy calculation .... 0.007 sec ( 1.0%) +Population analysis .... 0.075 sec ( 11.3%) +Orbital Transformation .... 0.007 sec ( 1.0%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.010 sec ( 1.5%) +SOSCF solution .... 0.018 sec ( 2.8%) +Finished LeanSCF after 0.7 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 10.2 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000361239 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007171439 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.527417403177 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.007.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.007.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.144687 0.891866 -0.169358 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5342276031592519 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.530057881 0.761635820 -0.269177917 +Nuclear contribution : -0.235618539 -1.628357114 0.365369436 + ----------------------------------------- +Total Dipole Moment : 0.294439342 -0.866721294 0.096191518 + ----------------------------------------- +Magnitude (a.u.) : 0.920409222 +Magnitude (Debye) : 2.339494319 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.042310 0.421412 0.380753 +Rotational constants in MHz : 91206.163321 12633.621884 11414.699607 + +Dipole components along the rotational axes: +x,y,z [a.u.] : -0.661379 0.460016 0.445102 +x,y,z [Debye]: -1.681092 1.169269 1.131359 + + + +Dipole moment calculation done in 0.0 sec + +Maximum memory used throughout the entire PROP-calculation: 6.1 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 8 * + * * + * Dihedral ( 2, 1, 0, 3) : -115.38461538 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.3117 0.668926 + 2. B(O 2,O 1) 1.2952 0.717378 + 3. B(H 3,N 0) 1.0372 0.396419 + 4. A(O 1,N 0,H 3) 101.8765 0.355702 + 5. A(N 0,O 1,O 2) 116.3626 0.439922 + 6. D(O 2,O 1,N 0,H 3) -115.3846 0.034643 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.598491 -0.464837 -0.201998 + O 0.422815 0.343444 -0.357183 + O 0.332316 1.501257 0.216346 + H -0.175347 -1.242020 0.339127 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.130984 -0.878414 -0.381721 + 1 O 8.0000 0 15.999 0.799004 0.649015 -0.674978 + 2 O 8.0000 0 15.999 0.627986 2.836965 0.408835 + 3 H 1.0000 0 1.008 -0.331358 -2.347078 0.640857 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.311422470461 0.00000000 0.00000000 + O 2 1 0 1.292386812099 116.49001605 0.00000000 + H 1 2 3 1.033843120315 101.91931541 235.38461539 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.478229315041 0.00000000 0.00000000 + O 2 1 0 2.442257133959 116.49001605 0.00000000 + H 1 2 3 1.953680362834 101.91931541 235.38461539 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1674 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.515799244081 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.867e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22309 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.5157992441 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5174717357348300 0.00e+00 4.01e-04 3.54e-03 2.80e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.040) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5186921718085955 -1.22e-03 4.84e-04 3.96e-03 2.22e-02 0.700 0.1 + ***Turning on AO-DIIS*** + 3 -205.5197094255266848 -1.02e-03 3.75e-04 3.26e-03 1.59e-02 0.700 0.0 + 4 -205.5204194593714533 -7.10e-04 9.52e-04 7.79e-03 1.11e-02 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5220845245611940 -1.67e-03 1.02e-04 9.03e-04 7.88e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -205.5220918367933791 -7.31e-06 3.04e-04 3.85e-03 1.06e-03 0.1 + 7 -205.5219962339231756 9.56e-05 1.91e-04 2.68e-03 4.22e-03 0.0 + 8 -205.5221085951527584 -1.12e-04 7.12e-05 1.11e-03 4.19e-04 0.0 + 9 -205.5221025676551108 6.03e-06 4.54e-05 6.69e-04 1.14e-03 0.0 + 10 -205.5221105838808171 -8.02e-06 1.06e-05 9.23e-05 3.04e-05 0.0 + 11 -205.5221106088901024 -2.50e-08 4.05e-06 6.23e-05 2.44e-05 0.0 + 12 -205.5221106270118412 -1.81e-08 4.87e-07 3.67e-06 3.27e-06 0.0 + 13 -205.5221106273503437 -3.39e-10 1.60e-07 1.57e-06 1.78e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 13 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.52211062735034 Eh -5592.54095 eV + +Components: +Nuclear Repulsion : 69.51579924408124 Eh 1891.62107 eV +Electronic Energy : -275.03790987143157 Eh -7484.16202 eV +One Electron Energy: -418.73647370818446 Eh -11394.39873 eV +Two Electron Energy: 143.69856383675292 Eh 3910.23671 eV + +Virial components: +Potential Energy : -410.35645804613370 Eh -11166.36691 eV +Kinetic Energy : 204.83434741878335 Eh 5573.82596 eV +Virial Ratio : 2.00335765567266 + +DFT components: +N(Alpha) : 11.999998655640 electrons +N(Beta) : 11.999998655640 electrons +N(Total) : 23.999997311281 electrons +E(X) : -23.330002109369 Eh +E(C) : -0.803911460137 Eh +E(XC) : -24.133913569507 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.3850e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.5750e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.6049e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.8785e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.7822e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.8910e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.186295 -522.0856 + 1 2.0000 -19.043310 -518.1948 + 2 2.0000 -14.249024 -387.7357 + 3 2.0000 -1.249169 -33.9916 + 4 2.0000 -0.964424 -26.2433 + 5 2.0000 -0.705654 -19.2018 + 6 2.0000 -0.560888 -15.2625 + 7 2.0000 -0.515318 -14.0225 + 8 2.0000 -0.505117 -13.7449 + 9 2.0000 -0.336591 -9.1591 + 10 2.0000 -0.274461 -7.4685 + 11 2.0000 -0.252317 -6.8659 + 12 0.0000 -0.213100 -5.7987 + 13 0.0000 0.049025 1.3340 + 14 0.0000 0.086096 2.3428 + 15 0.0000 0.134655 3.6642 + 16 0.0000 0.227051 6.1784 + 17 0.0000 0.265357 7.2207 + 18 0.0000 0.317370 8.6361 + 19 0.0000 0.330269 8.9871 + 20 0.0000 0.342737 9.3264 + 21 0.0000 0.382983 10.4215 + 22 0.0000 0.394640 10.7387 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.367096 + 1 O : 0.197042 + 2 O : -0.113095 + 3 H : 0.283150 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.890952 s : 3.890952 + pz : 1.099258 p : 3.426121 + px : 1.220861 + py : 1.106001 + dz2 : 0.004576 d : 0.050024 + dxz : 0.013538 + dyz : 0.005625 + dx2y2 : 0.008604 + dxy : 0.017681 + + 1 O s : 3.763746 s : 3.763746 + pz : 1.387329 p : 3.918774 + px : 1.449341 + py : 1.082104 + dz2 : 0.013358 d : 0.120438 + dxz : 0.024111 + dyz : 0.027305 + dx2y2 : 0.016876 + dxy : 0.038788 + + 2 O s : 3.939837 s : 3.939837 + pz : 1.278412 p : 4.152592 + px : 1.750974 + py : 1.123206 + dz2 : 0.004645 d : 0.020666 + dxz : 0.000598 + dyz : 0.006996 + dx2y2 : 0.004455 + dxy : 0.003972 + + 3 H s : 0.686222 s : 0.686222 + pz : 0.010936 p : 0.030628 + px : 0.007272 + py : 0.012420 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.112787 + 1 O : -0.186409 + 2 O : 0.012872 + 3 H : 0.286324 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.356085 s : 3.356085 + pz : 1.035912 p : 3.450339 + px : 1.301867 + py : 1.112560 + dz2 : 0.028752 d : 0.306363 + dxz : 0.045144 + dyz : 0.042604 + dx2y2 : 0.099932 + dxy : 0.089932 + + 1 O s : 3.375328 s : 3.375328 + pz : 1.309601 p : 4.043827 + px : 1.485848 + py : 1.248378 + dz2 : 0.064028 d : 0.767254 + dxz : 0.074895 + dyz : 0.186988 + dx2y2 : 0.227662 + dxy : 0.213680 + + 2 O s : 3.602216 s : 3.602216 + pz : 1.255917 p : 4.126502 + px : 1.639153 + py : 1.231431 + dz2 : 0.040814 d : 0.258410 + dxz : 0.016208 + dyz : 0.077835 + dx2y2 : 0.058646 + dxy : 0.064907 + + 3 H s : 0.636777 s : 0.636777 + pz : 0.026550 p : 0.076899 + px : 0.020014 + py : 0.030335 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3671 7.0000 -0.3671 2.6063 2.6063 0.0000 + 1 O 7.8030 8.0000 0.1970 2.5761 2.5761 0.0000 + 2 O 8.1131 8.0000 -0.1131 1.6880 1.6880 0.0000 + 3 H 0.7169 1.0000 0.2831 0.9042 0.9042 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3383 B( 0-N , 2-O ) : 0.4188 B( 0-N , 3-H ) : 0.8492 +B( 1-O , 2-O ) : 1.2260 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.045 sec +Sum of individual times .... 1.030 sec ( 98.6%) + +SCF preparation .... 0.409 sec ( 39.1%) +Fock matrix formation .... 0.355 sec ( 34.0%) + Startup .... 0.015 sec ( 4.1% of F) + Split-RI-J .... 0.050 sec ( 14.0% of F) + XC integration .... 0.237 sec ( 66.6% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.015 sec ( 6.3% of XC) + Density eval. .... 0.019 sec ( 7.9% of XC) + XC-Functional eval. .... 0.013 sec ( 5.4% of XC) + XC-Potential eval. .... 0.019 sec ( 7.9% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.027 sec ( 2.6%) +Total Energy calculation .... 0.027 sec ( 2.6%) +Population analysis .... 0.079 sec ( 7.6%) +Orbital Transformation .... 0.014 sec ( 1.4%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.069 sec ( 6.6%) +SOSCF solution .... 0.049 sec ( 4.7%) +Finished LeanSCF after 1.1 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 10.6 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000361683 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007190178 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.515282132861 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000708 -0.000006664 0.000001141 + 2 O : 0.000000620 0.000000295 -0.000000476 + 3 O : 0.000002437 0.000008115 0.000000828 + 4 H : -0.000002348 -0.000001747 -0.000001493 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000114095 +RMS gradient ... 0.0000032937 +MAX gradient ... 0.0000081152 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.019934207 -0.022173564 -0.031025217 + 2 O : -0.028497423 0.016873192 -0.035376539 + 3 O : 0.015459621 -0.013307549 0.029930057 + 4 H : -0.006896406 0.018607921 0.036471699 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000421470 -0.0000068390 -0.0000022192 + +Norm of the Cartesian gradient ... 0.0850635636 +RMS gradient ... 0.0245557357 +MAX gradient ... 0.0364716989 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.127 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.7%) +RI-J Coulomb gradient .... 0.061 sec ( 48.1%) +XC gradient .... 0.020 sec ( 16.0%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.515282133 Eh +Current gradient norm .... 0.085063564 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999842213 +Lowest eigenvalues of augmented Hessian: + -0.000150931 0.354951609 0.391506031 0.439019171 0.668409987 +Length of the computed step .... 0.017766478 +The final length of the internal step .... 0.017766478 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0072531344 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0061168949 RMS(Int)= 0.0072536169 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0036332645 0.0001000000 NO + MAX gradient 0.0073095845 0.0003000000 NO + RMS step 0.0072531344 0.0020000000 NO + MAX step 0.0126911866 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0058 Max(Angles) 0.73 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3117 -0.007310 0.0058 1.3175 + 2. B(O 2,O 1) 1.2952 0.000275 -0.0002 1.2950 + 3. B(H 3,N 0) 1.0372 0.002273 -0.0031 1.0342 + 4. A(O 1,N 0,H 3) 101.88 -0.004506 0.73 102.60 + 5. A(N 0,O 1,O 2) 116.36 0.000477 -0.06 116.30 + 6. D(O 2,O 1,N 0,H 3) -115.38 0.079415 0.00 -115.38 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.191 %) +Internal coordinates : 0.000 s ( 4.140 %) +B/P matrices and projection : 0.000 s (17.357 %) +Hessian update/contruction : 0.000 s (25.955 %) +Making the step : 0.000 s ( 6.688 %) +Converting the step to Cartesian: 0.000 s ( 5.573 %) +Storing new data : 0.000 s ( 4.299 %) +Checking convergence : 0.000 s ( 0.159 %) +Final printing : 0.000 s (25.478 %) +Total time : 0.001 s + +Time for energy+gradient : 4.192 s +Time for complete geometry iter : 5.004 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.596332 -0.467698 -0.198552 + O 0.425481 0.348220 -0.359348 + O 0.332297 1.504779 0.215816 + H -0.180154 -1.247456 0.338376 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.126904 -0.883821 -0.375209 + 1 O 8.0000 0 15.999 0.804042 0.658040 -0.679070 + 2 O 8.0000 0 15.999 0.627951 2.843620 0.407833 + 3 H 1.0000 0 1.008 -0.340442 -2.357351 0.639439 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.317451282400 0.00000000 0.00000000 + O 2 1 0 1.295038983629 116.30038281 0.00000000 + H 1 2 3 1.034175786420 102.60361027 244.61538488 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.489622118520 0.00000000 0.00000000 + O 2 1 0 2.447269011810 116.30038281 0.00000000 + H 1 2 3 1.954309010667 102.60361027 244.61538488 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1674 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.387107525903 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.870e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22310 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5221224877907957 0.00e+00 1.59e-04 1.43e-03 3.93e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5221714692215187 -4.90e-05 1.38e-04 1.45e-03 5.70e-04 0.0 + 3 -205.5221638476821795 7.62e-06 9.64e-05 1.65e-03 1.40e-03 0.0 + 4 -205.5221753996040661 -1.16e-05 1.19e-04 1.66e-03 6.78e-04 0.0 + 5 -205.5221562874206143 1.91e-05 8.36e-05 1.24e-03 1.78e-03 0.0 + 6 -205.5221803150473647 -2.40e-05 2.55e-05 3.71e-04 8.51e-05 0.0 + 7 -205.5221803633332911 -4.83e-08 1.18e-05 1.98e-04 7.57e-05 0.0 + 8 -205.5221805343466031 -1.71e-07 9.84e-07 9.28e-06 5.93e-06 0.0 + 9 -205.5221805348967337 -5.50e-10 4.62e-07 4.44e-06 1.62e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.52218053489673 Eh -5592.54285 eV + +Components: +Nuclear Repulsion : 69.38710752590349 Eh 1888.11919 eV +Electronic Energy : -274.90928806080024 Eh -7480.66204 eV +One Electron Energy: -418.48790878928105 Eh -11387.63493 eV +Two Electron Energy: 143.57862072848081 Eh 3906.97290 eV + +Virial components: +Potential Energy : -410.34519898934514 Eh -11166.06054 eV +Kinetic Energy : 204.82301845444837 Eh 5573.51768 eV +Virial Ratio : 2.00341349368701 + +DFT components: +N(Alpha) : 11.999998486027 electrons +N(Beta) : 11.999998486027 electrons +N(Total) : 23.999996972055 electrons +E(X) : -23.327313881040 Eh +E(C) : -0.803661491610 Eh +E(XC) : -24.130975372651 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 5.5013e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.4417e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.6242e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.2937e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.6238e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.3935e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 10.7 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361540 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007164422 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.515377653076 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000732 -0.000006704 0.000001136 + 2 O : 0.000000629 0.000000323 -0.000000486 + 3 O : 0.000002452 0.000008188 0.000000821 + 4 H : -0.000002349 -0.000001806 -0.000001471 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000114966 +RMS gradient ... 0.0000033188 +MAX gradient ... 0.0000081876 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.019457714 -0.026811290 -0.029290009 + 2 O : -0.026003779 0.019766285 -0.035852973 + 3 O : 0.015738188 -0.011993683 0.029846464 + 4 H : -0.009192123 0.019038688 0.035296517 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000403511 -0.0000070079 -0.0000201687 + +Norm of the Cartesian gradient ... 0.0853396275 +RMS gradient ... 0.0246354284 +MAX gradient ... 0.0358529726 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.135 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.006 sec ( 4.3%) +RI-J Coulomb gradient .... 0.061 sec ( 45.6%) +XC gradient .... 0.022 sec ( 16.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.515377653 Eh +Current gradient norm .... 0.085339627 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999958435 +Lowest eigenvalues of augmented Hessian: + -0.000028351 0.289299913 0.386231950 0.457627364 0.554278311 +Length of the computed step .... 0.009117880 +The final length of the internal step .... 0.009117880 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0037223590 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0026701157 RMS(Int)= 0.0037217945 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000002 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000014177 +Previously predicted energy change .... -0.000075489 +Actually observed energy change .... -0.000095520 +Ratio of predicted to observed change .... 1.265348951 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000955202 0.0000050000 NO + RMS gradient 0.0013249087 0.0001000000 NO + MAX gradient 0.0024165201 0.0003000000 NO + RMS step 0.0037223590 0.0020000000 NO + MAX step 0.0059163933 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0031 Max(Angles) 0.25 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3175 -0.002417 0.0031 1.3206 + 2. B(O 2,O 1) 1.2950 0.001411 -0.0015 1.2936 + 3. B(H 3,N 0) 1.0342 0.000274 -0.0008 1.0334 + 4. A(O 1,N 0,H 3) 102.60 -0.000831 0.25 102.85 + 5. A(N 0,O 1,O 2) 116.30 0.001391 -0.25 116.05 + 6. D(O 2,O 1,N 0,H 3) -115.38 0.078475 0.00 -115.38 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 8.216 %) +Internal coordinates : 0.000 s ( 3.135 %) +B/P matrices and projection : 0.000 s (11.027 %) +Hessian update/contruction : 0.000 s (43.243 %) +Making the step : 0.000 s ( 5.514 %) +Converting the step to Cartesian: 0.000 s ( 3.784 %) +Storing new data : 0.000 s ( 3.135 %) +Checking convergence : 0.000 s ( 1.189 %) +Final printing : 0.000 s (20.324 %) +Total time : 0.001 s + +Time for energy+gradient : 4.193 s +Time for complete geometry iter : 5.024 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.595722 -0.467727 -0.196785 + O 0.427808 0.350386 -0.361141 + O 0.331134 1.504120 0.215840 + H -0.181928 -1.248934 0.338377 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.125751 -0.883877 -0.371869 + 1 O 8.0000 0 15.999 0.808440 0.662134 -0.682457 + 2 O 8.0000 0 15.999 0.625752 2.842374 0.407879 + 3 H 1.0000 0 1.008 -0.343794 -2.360144 0.639440 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.320582102760 0.00000000 0.00000000 + O 2 1 0 1.293581785642 116.04645020 0.00000000 + H 1 2 3 1.033396248160 102.85162098 244.61538488 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.495538511575 0.00000000 0.00000000 + O 2 1 0 2.444515306691 116.04645020 0.00000000 + H 1 2 3 1.952835896845 102.85162098 244.61538488 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1674 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.368806767280 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.861e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22313 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5221700066725816 0.00e+00 1.06e-04 7.64e-04 2.71e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5221932679212387 -2.33e-05 9.50e-05 9.81e-04 3.15e-04 0.0 + 3 -205.5221901545458536 3.11e-06 8.32e-05 1.13e-03 1.11e-03 0.0 + 4 -205.5221957128135841 -5.56e-06 5.90e-05 5.74e-04 2.32e-04 0.0 + 5 -205.5221962397859556 -5.27e-07 2.50e-05 3.79e-04 4.27e-04 0.0 + 6 -205.5221967538298600 -5.14e-07 3.16e-05 2.92e-04 2.91e-04 0.0 + 7 -205.5221972832621304 -5.29e-07 1.15e-05 1.67e-04 4.85e-05 0.0 + 8 -205.5221973601464356 -7.69e-08 3.12e-06 3.85e-05 2.25e-05 0.0 + 9 -205.5221973698527904 -9.71e-09 1.31e-06 1.26e-05 5.63e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.52219736985279 Eh -5592.54331 eV + +Components: +Nuclear Repulsion : 69.36880676728022 Eh 1887.62120 eV +Electronic Energy : -274.89100413713300 Eh -7480.16451 eV +One Electron Energy: -418.45362764644682 Eh -11386.70210 eV +Two Electron Energy: 143.56262350931382 Eh 3906.53759 eV + +Virial components: +Potential Energy : -410.34324374877667 Eh -11166.00733 eV +Kinetic Energy : 204.82104637892388 Eh 5573.46402 eV +Virial Ratio : 2.00342323703215 + +DFT components: +N(Alpha) : 11.999998372998 electrons +N(Beta) : 11.999998372998 electrons +N(Total) : 23.999996745996 electrons +E(X) : -23.326663663963 Eh +E(C) : -0.803608069677 Eh +E(XC) : -24.130271733640 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 9.7064e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.2611e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.3134e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.2387e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 5.6284e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.5661e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 10.9 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361533 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007164798 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.515394104940 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000734 -0.000006706 0.000001137 + 2 O : 0.000000635 0.000000337 -0.000000490 + 3 O : 0.000002447 0.000008181 0.000000816 + 4 H : -0.000002347 -0.000001813 -0.000001463 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000114922 +RMS gradient ... 0.0000033175 +MAX gradient ... 0.0000081809 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.018679795 -0.027822934 -0.028528134 + 2 O : -0.024185075 0.021343717 -0.035910764 + 3 O : 0.015318660 -0.012584987 0.029508955 + 4 H : -0.009813380 0.019064204 0.034929943 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000358377 -0.0000085325 -0.0000303671 + +Norm of the Cartesian gradient ... 0.0849154207 +RMS gradient ... 0.0245129705 +MAX gradient ... 0.0359107636 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.129 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.0%) +RI-J Coulomb gradient .... 0.060 sec ( 46.0%) +XC gradient .... 0.019 sec ( 14.9%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.515394105 Eh +Current gradient norm .... 0.084915421 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999996161 +Lowest eigenvalues of augmented Hessian: + -0.000003002 0.283337680 0.383050206 0.427934563 0.514487153 +Length of the computed step .... 0.002770964 +The final length of the internal step .... 0.002770964 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0011312413 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0005513020 RMS(Int)= 0.0011311518 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000001501 +Previously predicted energy change .... -0.000014177 +Actually observed energy change .... -0.000016452 +Ratio of predicted to observed change .... 1.160491839 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000164519 0.0000050000 NO + RMS gradient 0.0004633442 0.0001000000 NO + MAX gradient 0.0007922127 0.0003000000 NO + RMS step 0.0011312413 0.0020000000 YES + MAX step 0.0020126412 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0011 Max(Angles) 0.05 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3206 -0.000652 0.0011 1.3216 + 2. B(O 2,O 1) 1.2936 0.000792 -0.0008 1.2927 + 3. B(H 3,N 0) 1.0334 -0.000248 0.0002 1.0336 + 4. A(O 1,N 0,H 3) 102.85 0.000391 -0.03 102.82 + 5. A(N 0,O 1,O 2) 116.05 0.000147 -0.05 116.00 + 6. D(O 2,O 1,N 0,H 3) -115.38 0.078040 -0.00 -115.38 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.058 %) +Internal coordinates : 0.000 s ( 3.456 %) +B/P matrices and projection : 0.000 s (13.349 %) +Hessian update/contruction : 0.000 s (34.446 %) +Making the step : 0.000 s ( 5.840 %) +Converting the step to Cartesian: 0.000 s ( 4.291 %) +Storing new data : 0.000 s ( 3.337 %) +Checking convergence : 0.000 s ( 1.430 %) +Final printing : 0.000 s (24.672 %) +Total time : 0.001 s + +Time for energy+gradient : 4.022 s +Time for complete geometry iter : 4.809 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 4 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.596149 -0.467730 -0.196739 + O 0.428323 0.350895 -0.361244 + O 0.330975 1.503615 0.215781 + H -0.181857 -1.248936 0.338494 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.126559 -0.883881 -0.371783 + 1 O 8.0000 0 15.999 0.809413 0.663096 -0.682652 + 2 O 8.0000 0 15.999 0.625452 2.841420 0.407767 + 3 H 1.0000 0 1.008 -0.343659 -2.360148 0.639661 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.321647146588 0.00000000 0.00000000 + O 2 1 0 1.292747788205 116.00036373 0.00000000 + H 1 2 3 1.033633164234 102.82043713 244.61538488 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.497551152730 0.00000000 0.00000000 + O 2 1 0 2.442939279940 116.00036373 0.00000000 + H 1 2 3 1.953283603341 102.82043713 244.61538488 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1673 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.368380994578 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.854e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22313 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5221995505133918 0.00e+00 3.21e-05 3.14e-04 6.65e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5222014223603537 -1.87e-06 3.84e-05 4.80e-04 1.63e-04 0.1 + 3 -205.5221989965693297 2.43e-06 2.96e-05 4.15e-04 6.93e-04 0.0 + 4 -205.5222016808976377 -2.68e-06 7.20e-06 1.19e-04 4.84e-05 0.0 + 5 -205.5222015968291771 8.41e-08 5.08e-06 8.59e-05 1.29e-04 0.0 + 6 -205.5222016975342285 -1.01e-07 9.67e-07 1.32e-05 3.33e-06 0.0 + 7 -205.5222016977202202 -1.86e-10 4.05e-07 6.51e-06 3.07e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.52220169772022 Eh -5592.54343 eV + +Components: +Nuclear Repulsion : 69.36838099457761 Eh 1887.60961 eV +Electronic Energy : -274.89058269229781 Eh -7480.15304 eV +One Electron Energy: -418.45268295231000 Eh -11386.67639 eV +Two Electron Energy: 143.56210026001222 Eh 3906.52335 eV + +Virial components: +Potential Energy : -410.34301125954886 Eh -11166.00100 eV +Kinetic Energy : 204.82080956182864 Eh 5573.45758 eV +Virial Ratio : 2.00342441833616 + +DFT components: +N(Alpha) : 11.999998348293 electrons +N(Beta) : 11.999998348293 electrons +N(Total) : 23.999996696587 electrons +E(X) : -23.326495858059 Eh +E(C) : -0.803603775139 Eh +E(XC) : -24.130099633198 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.8599e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.5108e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.0478e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 4.6923e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.0669e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.2253e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 11.1 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361541 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007167032 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.515396206611 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000733 -0.000006704 0.000001138 + 2 O : 0.000000636 0.000000341 -0.000000490 + 3 O : 0.000002446 0.000008174 0.000000814 + 4 H : -0.000002349 -0.000001811 -0.000001462 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000114862 +RMS gradient ... 0.0000033158 +MAX gradient ... 0.0000081741 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.018215883 -0.027806011 -0.028476687 + 2 O : -0.023714566 0.021902354 -0.035824270 + 3 O : 0.015236095 -0.013005512 0.029329226 + 4 H : -0.009737412 0.018909169 0.034971730 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000348988 -0.0000091552 -0.0000276664 + +Norm of the Cartesian gradient ... 0.0847246572 +RMS gradient ... 0.0244579018 +MAX gradient ... 0.0358242695 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.134 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.006 sec ( 4.2%) +RI-J Coulomb gradient .... 0.062 sec ( 46.2%) +XC gradient .... 0.020 sec ( 15.2%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.515396207 Eh +Current gradient norm .... 0.084724657 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999996352 +Lowest eigenvalues of augmented Hessian: + -0.000001605 0.206146281 0.363551282 0.399585436 0.490650931 +Length of the computed step .... 0.002701045 +The final length of the internal step .... 0.002701045 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0011026969 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0006392891 RMS(Int)= 0.0011027774 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000803 +Previously predicted energy change .... -0.000001501 +Actually observed energy change .... -0.000002102 +Ratio of predicted to observed change .... 1.400219793 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000021017 0.0000050000 YES + RMS gradient 0.0002505431 0.0001000000 NO + MAX gradient 0.0004083420 0.0003000000 NO + RMS step 0.0011026969 0.0020000000 YES + MAX step 0.0017145398 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0008 Max(Angles) 0.10 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3216 -0.000255 0.0008 1.3225 + 2. B(O 2,O 1) 1.2927 0.000347 -0.0007 1.2920 + 3. B(H 3,N 0) 1.0336 -0.000082 0.0002 1.0338 + 4. A(O 1,N 0,H 3) 102.82 0.000408 -0.10 102.72 + 5. A(N 0,O 1,O 2) 116.00 -0.000134 0.01 116.01 + 6. D(O 2,O 1,N 0,H 3) -115.38 0.077965 -0.00 -115.38 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.801 %) +Internal coordinates : 0.000 s ( 2.978 %) +B/P matrices and projection : 0.000 s (13.772 %) +Hessian update/contruction : 0.000 s (34.864 %) +Making the step : 0.000 s ( 5.335 %) +Converting the step to Cartesian: 0.000 s ( 3.970 %) +Storing new data : 0.000 s ( 3.350 %) +Checking convergence : 0.000 s ( 1.365 %) +Final printing : 0.000 s (24.442 %) +Total time : 0.001 s + +Time for energy+gradient : 3.943 s +Time for complete geometry iter : 4.707 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 5 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.596862 -0.467923 -0.197020 + O 0.428474 0.351073 -0.360924 + O 0.331080 1.503198 0.215686 + H -0.181400 -1.248504 0.338551 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.127906 -0.884246 -0.372315 + 1 O 8.0000 0 15.999 0.809699 0.663431 -0.682047 + 2 O 8.0000 0 15.999 0.625651 2.840633 0.407587 + 3 H 1.0000 0 1.008 -0.342796 -2.359330 0.639768 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.322472073517 0.00000000 0.00000000 + O 2 1 0 1.292036069494 116.00668278 0.00000000 + H 1 2 3 1.033804480003 102.72220124 244.61538488 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.499110038707 0.00000000 0.00000000 + O 2 1 0 2.441594326492 116.00668278 0.00000000 + H 1 2 3 1.953607343227 102.72220124 244.61538488 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1673 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.368160241138 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.848e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22313 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5222030027318851 0.00e+00 2.96e-05 2.85e-04 5.26e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5222044191097552 -1.42e-06 3.09e-05 4.04e-04 1.48e-04 0.0 + 3 -205.5222028929535441 1.53e-06 2.47e-05 3.37e-04 5.60e-04 0.0 + 4 -205.5222046338443533 -1.74e-06 1.12e-05 1.91e-04 6.56e-05 0.0 + 5 -205.5222044217263146 2.12e-07 8.10e-06 1.29e-04 2.01e-04 0.0 + 6 -205.5222046737462165 -2.52e-07 1.17e-06 8.58e-06 3.26e-06 0.0 + 7 -205.5222046742444491 -4.98e-10 6.32e-07 5.52e-06 1.60e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.52220467424445 Eh -5592.54351 eV + +Components: +Nuclear Repulsion : 69.36816024113824 Eh 1887.60360 eV +Electronic Energy : -274.89036491538269 Eh -7480.14711 eV +One Electron Energy: -418.45156903400817 Eh -11386.64608 eV +Two Electron Energy: 143.56120411862548 Eh 3906.49897 eV + +Virial components: +Potential Energy : -410.34310884899224 Eh -11166.00366 eV +Kinetic Energy : 204.82090417474780 Eh 5573.46015 eV +Virial Ratio : 2.00342396935665 + +DFT components: +N(Alpha) : 11.999998341011 electrons +N(Beta) : 11.999998341011 electrons +N(Total) : 23.999996682022 electrons +E(X) : -23.326415562631 Eh +E(C) : -0.803603956656 Eh +E(XC) : -24.130019519287 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 4.9823e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.5222e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 6.3181e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 4.0070e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.5953e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.6567e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 11.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361548 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007169051 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.515397171363 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000732 -0.000006703 0.000001138 + 2 O : 0.000000637 0.000000342 -0.000000489 + 3 O : 0.000002447 0.000008168 0.000000814 + 4 H : -0.000002351 -0.000001807 -0.000001464 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000114813 +RMS gradient ... 0.0000033144 +MAX gradient ... 0.0000081680 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.017824663 -0.027819111 -0.028467954 + 2 O : -0.023472513 0.022282162 -0.035718768 + 3 O : 0.015248923 -0.013335629 0.029191586 + 4 H : -0.009601072 0.018872577 0.034995136 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000346081 -0.0000094999 -0.0000286231 + +Norm of the Cartesian gradient ... 0.0846218742 +RMS gradient ... 0.0244282309 +MAX gradient ... 0.0357187676 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.143 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.5%) +RI-J Coulomb gradient .... 0.064 sec ( 44.4%) +XC gradient .... 0.020 sec ( 13.7%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.515397171 Eh +Current gradient norm .... 0.084621874 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999563 +Lowest eigenvalues of augmented Hessian: + -0.000000187 0.167443222 0.352315476 0.406197787 0.479572159 +Length of the computed step .... 0.000934489 +The final length of the internal step .... 0.000934489 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0003815037 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0003020693 RMS(Int)= 0.0003815172 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000093 +Previously predicted energy change .... -0.000000803 +Actually observed energy change .... -0.000000965 +Ratio of predicted to observed change .... 1.202053958 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000009648 0.0000050000 YES + RMS gradient 0.0000899812 0.0001000000 YES + MAX gradient 0.0001702424 0.0003000000 YES + RMS step 0.0003815037 0.0020000000 YES + MAX step 0.0008016448 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0002 Max(Angles) 0.05 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3225 -0.000029 0.0002 1.3226 + 2. B(O 2,O 1) 1.2920 -0.000014 -0.0001 1.2919 + 3. B(H 3,N 0) 1.0338 0.000025 -0.0000 1.0338 + 4. A(O 1,N 0,H 3) 102.72 0.000170 -0.05 102.68 + 5. A(N 0,O 1,O 2) 116.01 -0.000134 0.02 116.03 + 6. D(O 2,O 1,N 0,H 3) -115.38 0.077953 0.00 -115.38 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (11.704 %) +Internal coordinates : 0.000 s ( 3.121 %) +B/P matrices and projection : 0.000 s (16.255 %) +Hessian update/contruction : 0.000 s (26.528 %) +Making the step : 0.000 s ( 6.112 %) +Converting the step to Cartesian: 0.000 s ( 4.031 %) +Storing new data : 0.000 s ( 3.251 %) +Checking convergence : 0.000 s ( 1.300 %) +Final printing : 0.000 s (27.308 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 5 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.597137 -0.468059 -0.197190 + O 0.428400 0.351007 -0.360712 + O 0.331200 1.503156 0.215656 + H -0.181171 -1.248260 0.338538 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.128426 -0.884504 -0.372636 + 1 O 8.0000 0 15.999 0.809559 0.663307 -0.681647 + 2 O 8.0000 0 15.999 0.625877 2.840554 0.407530 + 3 H 1.0000 0 1.008 -0.342363 -2.358870 0.639745 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.322624587145 0.00000000 0.00000000 + O 2 1 0 1.291935066319 116.02578216 0.00000000 + H 1 2 3 1.033802075423 102.67627037 244.61538488 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.499398247695 0.00000000 0.00000000 + O 2 1 0 2.441403458153 116.02578216 0.00000000 + H 1 2 3 1.953602799230 102.67627037 244.61538488 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1673 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.366695016430 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.847e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22313 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.3666950164 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5222049195697309 0.00e+00 1.03e-05 9.64e-05 2.88e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5222050906128288 -1.71e-07 8.39e-06 1.04e-04 3.12e-05 0.0 + 3 -205.5222050758488308 1.48e-08 9.00e-06 9.47e-05 8.65e-05 0.0 + 4 -205.5222051070022076 -3.12e-08 7.06e-06 8.89e-05 4.80e-05 0.0 + 5 -205.5222050661181470 4.09e-08 4.81e-06 7.75e-05 1.03e-04 0.0 + 6 -205.5222051329797068 -6.69e-08 2.13e-06 1.84e-05 1.04e-05 0.0 + 7 -205.5222051343708927 -1.39e-09 5.55e-07 4.76e-06 3.66e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.52220513437089 Eh -5592.54352 eV + +Components: +Nuclear Repulsion : 69.36669501643001 Eh 1887.56373 eV +Electronic Energy : -274.88890015080096 Eh -7480.10725 eV +One Electron Energy: -418.44837900468150 Eh -11386.55927 eV +Two Electron Energy: 143.55947885388056 Eh 3906.45202 eV + +Virial components: +Potential Energy : -410.34316500424518 Eh -11166.00519 eV +Kinetic Energy : 204.82095986987426 Eh 5573.46167 eV +Virial Ratio : 2.00342369875106 + +DFT components: +N(Alpha) : 11.999998345108 electrons +N(Beta) : 11.999998345108 electrons +N(Total) : 23.999996690216 electrons +E(X) : -23.326393550715 Eh +E(C) : -0.803602493210 Eh +E(XC) : -24.129996043925 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.3912e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.7596e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 5.5522e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.0938e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.6561e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.1319e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.186262 -522.0847 + 1 2.0000 -19.044839 -518.2364 + 2 2.0000 -14.248185 -387.7128 + 3 2.0000 -1.247982 -33.9593 + 4 2.0000 -0.960967 -26.1492 + 5 2.0000 -0.707433 -19.2502 + 6 2.0000 -0.559864 -15.2347 + 7 2.0000 -0.514498 -14.0002 + 8 2.0000 -0.505060 -13.7434 + 9 2.0000 -0.336507 -9.1568 + 10 2.0000 -0.274720 -7.4755 + 11 2.0000 -0.252434 -6.8691 + 12 0.0000 -0.213849 -5.8191 + 13 0.0000 0.048171 1.3108 + 14 0.0000 0.088992 2.4216 + 15 0.0000 0.129602 3.5267 + 16 0.0000 0.225896 6.1470 + 17 0.0000 0.266346 7.2476 + 18 0.0000 0.316967 8.6251 + 19 0.0000 0.331000 9.0070 + 20 0.0000 0.342777 9.3274 + 21 0.0000 0.381810 10.3896 + 22 0.0000 0.394840 10.7441 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.367842 + 1 O : 0.195950 + 2 O : -0.108904 + 3 H : 0.280796 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.889792 s : 3.889792 + pz : 1.104104 p : 3.429311 + px : 1.220154 + py : 1.105053 + dz2 : 0.004534 d : 0.048739 + dxz : 0.013063 + dyz : 0.005391 + dx2y2 : 0.008467 + dxy : 0.017285 + + 1 O s : 3.767435 s : 3.767435 + pz : 1.390622 p : 3.916756 + px : 1.447522 + py : 1.078612 + dz2 : 0.013605 d : 0.119859 + dxz : 0.024076 + dyz : 0.026844 + dx2y2 : 0.016802 + dxy : 0.038531 + + 2 O s : 3.940160 s : 3.940160 + pz : 1.283611 p : 4.147709 + px : 1.739290 + py : 1.124808 + dz2 : 0.004796 d : 0.021036 + dxz : 0.000635 + dyz : 0.006982 + dx2y2 : 0.004496 + dxy : 0.004127 + + 3 H s : 0.688344 s : 0.688344 + pz : 0.011010 p : 0.030861 + px : 0.007267 + py : 0.012584 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.114036 + 1 O : -0.182792 + 2 O : 0.013983 + 3 H : 0.282845 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.359559 s : 3.359559 + pz : 1.041250 p : 3.452788 + px : 1.298724 + py : 1.112814 + dz2 : 0.028427 d : 0.301689 + dxz : 0.044292 + dyz : 0.042183 + dx2y2 : 0.097810 + dxy : 0.088978 + + 1 O s : 3.379099 s : 3.379099 + pz : 1.313966 p : 4.041664 + px : 1.481242 + py : 1.246456 + dz2 : 0.064167 d : 0.762029 + dxz : 0.074585 + dyz : 0.186114 + dx2y2 : 0.224226 + dxy : 0.212937 + + 2 O s : 3.600514 s : 3.600514 + pz : 1.261805 p : 4.124491 + px : 1.628433 + py : 1.234253 + dz2 : 0.041502 d : 0.261011 + dxz : 0.016678 + dyz : 0.078755 + dx2y2 : 0.058802 + dxy : 0.065273 + + 3 H s : 0.639241 s : 0.639241 + pz : 0.026811 p : 0.077915 + px : 0.020094 + py : 0.031009 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3678 7.0000 -0.3678 2.6085 2.6085 -0.0000 + 1 O 7.8040 8.0000 0.1960 2.5756 2.5756 0.0000 + 2 O 8.1089 8.0000 -0.1089 1.6925 1.6925 -0.0000 + 3 H 0.7192 1.0000 0.2808 0.9055 0.9055 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3349 B( 0-N , 2-O ) : 0.4224 B( 0-N , 3-H ) : 0.8512 +B( 1-O , 2-O ) : 1.2283 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.812 sec +Sum of individual times .... 0.794 sec ( 97.8%) + +SCF preparation .... 0.410 sec ( 50.5%) +Fock matrix formation .... 0.202 sec ( 24.8%) + Startup .... 0.010 sec ( 4.8% of F) + Split-RI-J .... 0.029 sec ( 14.5% of F) + XC integration .... 0.134 sec ( 66.3% of F) + Basis function eval. .... 0.009 sec ( 7.0% of XC) + Density eval. .... 0.012 sec ( 9.1% of XC) + XC-Functional eval. .... 0.008 sec ( 5.9% of XC) + XC-Potential eval. .... 0.012 sec ( 8.9% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.012 sec ( 1.5%) +Total Energy calculation .... 0.016 sec ( 1.9%) +Population analysis .... 0.096 sec ( 11.9%) +Orbital Transformation .... 0.007 sec ( 0.9%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.010 sec ( 1.3%) +SOSCF solution .... 0.041 sec ( 5.0%) +Finished LeanSCF after 0.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 11.6 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000361548 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007169403 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.515397279925 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.008.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.008.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.144951 0.878295 -0.190591 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5222051343708927 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.559932440 0.815256568 -0.294386271 +Nuclear contribution : -0.236677861 -1.598590382 0.412537095 + ----------------------------------------- +Total Dipole Moment : 0.323254579 -0.783333814 0.118150824 + ----------------------------------------- +Magnitude (a.u.) : 0.855607973 +Magnitude (Debye) : 2.174782635 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.924605 0.420846 0.380638 +Rotational constants in MHz : 87677.446718 12616.632429 11411.235337 + +Dipole components along the rotational axes: +x,y,z [a.u.] : -0.562993 0.393782 0.509940 +x,y,z [Debye]: -1.431014 1.000915 1.296166 + + + +Dipole moment calculation done in 0.0 sec + +Maximum memory used throughout the entire PROP-calculation: 6.8 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 9 * + * * + * Dihedral ( 2, 1, 0, 3) : -106.15384615 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.3229 0.641956 + 2. B(O 2,O 1) 1.2947 0.718569 + 3. B(H 3,N 0) 1.0373 0.396479 + 4. A(O 1,N 0,H 3) 102.6095 0.353238 + 5. A(N 0,O 1,O 2) 115.8983 0.436799 + 6. D(O 2,O 1,N 0,H 3) -106.1538 0.031659 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.592908 -0.481727 -0.229425 + O 0.414613 0.358384 -0.400527 + O 0.336481 1.475053 0.249981 + H -0.176895 -1.213865 0.376264 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.120433 -0.910333 -0.433551 + 1 O 8.0000 0 15.999 0.783505 0.677247 -0.756887 + 2 O 8.0000 0 15.999 0.635857 2.787446 0.472396 + 3 H 1.0000 0 1.008 -0.334282 -2.293873 0.711035 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.322624587145 0.00000000 0.00000000 + O 2 1 0 1.291935066319 116.02578216 0.00000000 + H 1 2 3 1.033802075423 102.67627037 244.61538488 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.499398247695 0.00000000 0.00000000 + O 2 1 0 2.441403458153 116.02578216 0.00000000 + H 1 2 3 1.953602799230 102.67627037 244.61538488 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1673 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.318652569885 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.863e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22312 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.3186525699 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5044258186065349 0.00e+00 3.98e-04 3.95e-03 2.70e-02 0.700 0.1 +Warning: op=0 Small HOMO/LUMO gap ( 0.022) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5056446583107004 -1.22e-03 4.89e-04 4.46e-03 2.12e-02 0.700 0.1 + ***Turning on AO-DIIS*** + 3 -205.5066723103812478 -1.03e-03 3.84e-04 3.65e-03 1.51e-02 0.700 0.0 + 4 -205.5073911253828669 -7.19e-04 1.00e-03 8.83e-03 1.05e-02 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5090845771635486 -1.69e-03 1.23e-04 8.90e-04 9.55e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -205.5090988373441405 -1.43e-05 2.98e-04 3.19e-03 1.03e-03 0.0 + 7 -205.5090623050111844 3.65e-05 1.80e-04 2.17e-03 2.90e-03 0.0 + 8 -205.5091233816652334 -6.11e-05 1.34e-04 2.11e-03 8.71e-04 0.0 + 9 -205.5090950635869831 2.83e-05 9.01e-05 1.41e-03 2.40e-03 0.0 + 10 -205.5091298902873973 -3.48e-05 1.64e-05 1.10e-04 4.22e-05 0.0 + 11 -205.5091299436429608 -5.34e-08 6.14e-06 8.55e-05 3.48e-05 0.0 + 12 -205.5091299764432051 -3.28e-08 9.83e-07 7.98e-06 3.07e-06 0.0 + 13 -205.5091299772679463 -8.25e-10 5.05e-07 3.18e-06 1.78e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 13 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50912997726795 Eh -5592.18773 eV + +Components: +Nuclear Repulsion : 69.31865256988543 Eh 1886.25643 eV +Electronic Energy : -274.82778254715345 Eh -7478.44416 eV +One Electron Energy: -418.33615691938917 Eh -11383.50556 eV +Two Electron Energy: 143.50837437223575 Eh 3905.06140 eV + +Virial components: +Potential Energy : -410.32736537705881 Eh -11165.57526 eV +Kinetic Energy : 204.81823539979086 Eh 5573.38753 eV +Virial Ratio : 2.00337320832849 + +DFT components: +N(Alpha) : 11.999999322146 electrons +N(Beta) : 11.999999322146 electrons +N(Total) : 23.999998644292 electrons +E(X) : -23.321419008069 Eh +E(C) : -0.803547695266 Eh +E(XC) : -24.124966703335 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 8.2474e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.1768e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 5.0500e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.5511e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.7810e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.2458e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.186794 -522.0992 + 1 2.0000 -19.051989 -518.4310 + 2 2.0000 -14.241302 -387.5255 + 3 2.0000 -1.248088 -33.9622 + 4 2.0000 -0.960238 -26.1294 + 5 2.0000 -0.708101 -19.2684 + 6 2.0000 -0.559467 -15.2239 + 7 2.0000 -0.515841 -14.0368 + 8 2.0000 -0.503609 -13.7039 + 9 2.0000 -0.337806 -9.1922 + 10 2.0000 -0.278752 -7.5852 + 11 2.0000 -0.243428 -6.6240 + 12 0.0000 -0.222721 -6.0605 + 13 0.0000 0.046509 1.2656 + 14 0.0000 0.089840 2.4447 + 15 0.0000 0.128007 3.4832 + 16 0.0000 0.227195 6.1823 + 17 0.0000 0.264335 7.1929 + 18 0.0000 0.318830 8.6758 + 19 0.0000 0.328378 8.9356 + 20 0.0000 0.350464 9.5366 + 21 0.0000 0.382340 10.4040 + 22 0.0000 0.390602 10.6288 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.393570 + 1 O : 0.191287 + 2 O : -0.085622 + 3 H : 0.287905 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.883618 s : 3.883618 + pz : 1.112114 p : 3.462523 + px : 1.233626 + py : 1.116783 + dz2 : 0.004128 d : 0.047429 + dxz : 0.012033 + dyz : 0.005837 + dx2y2 : 0.008422 + dxy : 0.017009 + + 1 O s : 3.772208 s : 3.772208 + pz : 1.390967 p : 3.918294 + px : 1.440566 + py : 1.086762 + dz2 : 0.015600 d : 0.118211 + dxz : 0.026828 + dyz : 0.023624 + dx2y2 : 0.016478 + dxy : 0.035680 + + 2 O s : 3.937859 s : 3.937859 + pz : 1.264154 p : 4.127999 + px : 1.687315 + py : 1.176530 + dz2 : 0.004842 d : 0.019765 + dxz : 0.001206 + dyz : 0.006223 + dx2y2 : 0.003337 + dxy : 0.004157 + + 3 H s : 0.680974 s : 0.680974 + pz : 0.012027 p : 0.031121 + px : 0.007390 + py : 0.011704 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.133208 + 1 O : -0.180198 + 2 O : 0.025533 + 3 H : 0.287872 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.353824 s : 3.353824 + pz : 1.053052 p : 3.479510 + px : 1.306827 + py : 1.119631 + dz2 : 0.027489 d : 0.299874 + dxz : 0.044548 + dyz : 0.044570 + dx2y2 : 0.093760 + dxy : 0.089507 + + 1 O s : 3.381979 s : 3.381979 + pz : 1.322495 p : 4.038865 + px : 1.470654 + py : 1.245716 + dz2 : 0.068351 d : 0.759354 + dxz : 0.082589 + dyz : 0.184844 + dx2y2 : 0.219439 + dxy : 0.204132 + + 2 O s : 3.603437 s : 3.603437 + pz : 1.254601 p : 4.111090 + px : 1.582977 + py : 1.273512 + dz2 : 0.045144 d : 0.259939 + dxz : 0.020363 + dyz : 0.080363 + dx2y2 : 0.054596 + dxy : 0.059474 + + 3 H s : 0.634070 s : 0.634070 + pz : 0.029460 p : 0.078058 + px : 0.020214 + py : 0.028383 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3936 7.0000 -0.3936 2.5700 2.5700 -0.0000 + 1 O 7.8087 8.0000 0.1913 2.5681 2.5681 0.0000 + 2 O 8.0856 8.0000 -0.0856 1.6792 1.6792 -0.0000 + 3 H 0.7121 1.0000 0.2879 0.9020 0.9020 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3278 B( 0-N , 2-O ) : 0.4035 B( 0-N , 3-H ) : 0.8387 +B( 1-O , 2-O ) : 1.2263 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.121 sec +Sum of individual times .... 1.105 sec ( 98.6%) + +SCF preparation .... 0.439 sec ( 39.1%) +Fock matrix formation .... 0.355 sec ( 31.6%) + Startup .... 0.015 sec ( 4.4% of F) + Split-RI-J .... 0.051 sec ( 14.5% of F) + XC integration .... 0.232 sec ( 65.3% of F) + Basis function eval. .... 0.016 sec ( 6.8% of XC) + Density eval. .... 0.020 sec ( 8.7% of XC) + XC-Functional eval. .... 0.014 sec ( 6.0% of XC) + XC-Potential eval. .... 0.020 sec ( 8.8% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.034 sec ( 3.0%) +Total Energy calculation .... 0.029 sec ( 2.6%) +Population analysis .... 0.108 sec ( 9.7%) +Orbital Transformation .... 0.016 sec ( 1.4%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.074 sec ( 6.6%) +SOSCF solution .... 0.051 sec ( 4.5%) +Finished LeanSCF after 1.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 12.0 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000362013 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007191918 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502300073054 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000717 -0.000006542 0.000001266 + 2 O : 0.000000614 0.000000352 -0.000000549 + 3 O : 0.000002417 0.000007809 0.000000981 + 4 H : -0.000002314 -0.000001620 -0.000001698 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000111514 +RMS gradient ... 0.0000032191 +MAX gradient ... 0.0000078088 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.022780536 -0.026741090 -0.033016688 + 2 O : -0.032242837 0.019729090 -0.034079808 + 3 O : 0.018276459 -0.014950912 0.029943786 + 4 H : -0.008814158 0.021962912 0.037152709 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000042425 -0.0000175508 -0.0000179682 + +Norm of the Cartesian gradient ... 0.0911536231 +RMS gradient ... 0.0263137844 +MAX gradient ... 0.0371527094 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.143 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.6%) +RI-J Coulomb gradient .... 0.064 sec ( 44.6%) +XC gradient .... 0.024 sec ( 16.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.502300073 Eh +Current gradient norm .... 0.091153623 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999767614 +Lowest eigenvalues of augmented Hessian: + -0.000201628 0.352510677 0.391462728 0.435914290 0.641299424 +Length of the computed step .... 0.021562331 +The final length of the internal step .... 0.021562331 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0088027847 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0076758765 RMS(Int)= 0.0088019543 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000002 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0039763515 0.0001000000 NO + MAX gradient 0.0070692287 0.0003000000 NO + RMS step 0.0088027847 0.0020000000 NO + MAX step 0.0171704785 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0058 Max(Angles) 0.98 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3229 -0.007069 0.0058 1.3288 + 2. B(O 2,O 1) 1.2947 0.001047 -0.0008 1.2939 + 3. B(H 3,N 0) 1.0373 0.002660 -0.0036 1.0337 + 4. A(O 1,N 0,H 3) 102.61 -0.006054 0.98 103.59 + 5. A(N 0,O 1,O 2) 115.90 0.000258 -0.03 115.86 + 6. D(O 2,O 1,N 0,H 3) -106.15 0.083896 0.00 -106.15 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.871 %) +Internal coordinates : 0.000 s ( 3.720 %) +B/P matrices and projection : 0.000 s (16.881 %) +Hessian update/contruction : 0.000 s (27.039 %) +Making the step : 0.000 s ( 6.009 %) +Converting the step to Cartesian: 0.000 s ( 4.864 %) +Storing new data : 0.000 s ( 3.720 %) +Checking convergence : 0.000 s ( 1.001 %) +Final printing : 0.000 s (26.609 %) +Total time : 0.001 s + +Time for energy+gradient : 4.451 s +Time for complete geometry iter : 5.249 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.589617 -0.484620 -0.224993 + O 0.416909 0.364426 -0.402905 + O 0.336833 1.479314 0.248871 + H -0.182833 -1.221275 0.375319 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.114215 -0.915800 -0.425174 + 1 O 8.0000 0 15.999 0.787843 0.688664 -0.761380 + 2 O 8.0000 0 15.999 0.636523 2.795499 0.470297 + 3 H 1.0000 0 1.008 -0.345504 -2.307876 0.709251 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.328768555556 0.00000000 0.00000000 + O 2 1 0 1.293908918208 115.86440432 0.00000000 + H 1 2 3 1.033686617460 103.59327306 253.84615379 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.511008665367 0.00000000 0.00000000 + O 2 1 0 2.445133497652 115.86440432 0.00000000 + H 1 2 3 1.953384615299 103.59327306 253.84615379 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1670 + la=0 lb=0: 144 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.199982102081 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.859e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22312 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5091482950672344 0.00e+00 1.86e-04 1.96e-03 5.25e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5092114089550819 -6.31e-05 1.49e-04 1.71e-03 6.42e-04 0.1 + 3 -205.5092085249955858 2.88e-06 1.18e-04 1.88e-03 1.38e-03 0.0 + 4 -205.5092191471865704 -1.06e-05 1.14e-04 1.37e-03 7.83e-04 0.0 + 5 -205.5092061535549988 1.30e-05 8.16e-05 1.09e-03 1.53e-03 0.0 + 6 -205.5092247944319865 -1.86e-05 3.26e-05 3.90e-04 1.04e-04 0.0 + 7 -205.5092249698329852 -1.75e-07 1.37e-05 2.12e-04 8.54e-05 0.0 + 8 -205.5092251862595276 -2.16e-07 2.50e-06 1.97e-05 1.02e-05 0.0 + 9 -205.5092251899379789 -3.68e-09 1.68e-06 1.22e-05 3.88e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50922518993798 Eh -5592.19032 eV + +Components: +Nuclear Repulsion : 69.19998210208134 Eh 1883.02724 eV +Electronic Energy : -274.70920729201930 Eh -7475.21756 eV +One Electron Energy: -418.10615368366979 Eh -11377.24685 eV +Two Electron Energy: 143.39694639165049 Eh 3902.02929 eV + +Virial components: +Potential Energy : -410.31705818053013 Eh -11165.29479 eV +Kinetic Energy : 204.80783299059212 Eh 5573.10447 eV +Virial Ratio : 2.00342463561625 + +DFT components: +N(Alpha) : 11.999999179145 electrons +N(Beta) : 11.999999179145 electrons +N(Total) : 23.999998358290 electrons +E(X) : -23.319195454481 Eh +E(C) : -0.803319192287 Eh +E(XC) : -24.122514646769 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.6785e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.2164e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.6757e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.5222e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.8837e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 4.1250e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 12.1 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361847 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007156523 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502430513733 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000746 -0.000006591 0.000001260 + 2 O : 0.000000624 0.000000387 -0.000000562 + 3 O : 0.000002435 0.000007896 0.000000970 + 4 H : -0.000002313 -0.000001693 -0.000001668 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000112546 +RMS gradient ... 0.0000032489 +MAX gradient ... 0.0000078963 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.022851485 -0.031519322 -0.030929613 + 2 O : -0.030125936 0.023042947 -0.034361081 + 3 O : 0.018680314 -0.013748378 0.029622884 + 4 H : -0.011405863 0.022224754 0.035667810 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000020829 -0.0000062424 -0.0000264304 + +Norm of the Cartesian gradient ... 0.0916692183 +RMS gradient ... 0.0264626239 +MAX gradient ... 0.0356678103 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.136 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 4.0%) +RI-J Coulomb gradient .... 0.064 sec ( 47.4%) +XC gradient .... 0.022 sec ( 16.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.502430514 Eh +Current gradient norm .... 0.091669218 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999924218 +Lowest eigenvalues of augmented Hessian: + -0.000043159 0.253496367 0.389195990 0.457409365 0.574378390 +Length of the computed step .... 0.012311865 +The final length of the internal step .... 0.012311865 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0050262980 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0038977468 RMS(Int)= 0.0050244669 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000009 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000021583 +Previously predicted energy change .... -0.000100861 +Actually observed energy change .... -0.000130441 +Ratio of predicted to observed change .... 1.293275592 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0001304407 0.0000050000 NO + RMS gradient 0.0015102593 0.0001000000 NO + MAX gradient 0.0020991300 0.0003000000 NO + RMS step 0.0050262980 0.0020000000 NO + MAX step 0.0086569167 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0030 Max(Angles) 0.50 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3288 -0.002099 0.0030 1.3317 + 2. B(O 2,O 1) 1.2939 0.001920 -0.0021 1.2918 + 3. B(H 3,N 0) 1.0337 0.000389 -0.0011 1.0326 + 4. A(O 1,N 0,H 3) 103.59 -0.001769 0.50 104.09 + 5. A(N 0,O 1,O 2) 115.86 0.001520 -0.29 115.58 + 6. D(O 2,O 1,N 0,H 3) -106.15 0.082654 0.00 -106.15 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 7.843 %) +Internal coordinates : 0.000 s ( 2.819 %) +B/P matrices and projection : 0.000 s (14.216 %) +Hessian update/contruction : 0.000 s (40.074 %) +Making the step : 0.000 s ( 5.025 %) +Converting the step to Cartesian: 0.000 s ( 4.289 %) +Storing new data : 0.000 s ( 3.064 %) +Checking convergence : 0.000 s ( 1.348 %) +Final printing : 0.000 s (21.078 %) +Total time : 0.001 s + +Time for energy+gradient : 4.172 s +Time for complete geometry iter : 5.019 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.587825 -0.484334 -0.222289 + O 0.419195 0.367708 -0.405289 + O 0.335567 1.478684 0.248553 + H -0.185644 -1.224214 0.375317 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.110828 -0.915259 -0.420065 + 1 O 8.0000 0 15.999 0.792163 0.694868 -0.765885 + 2 O 8.0000 0 15.999 0.634129 2.794307 0.469696 + 3 H 1.0000 0 1.008 -0.350817 -2.313429 0.709247 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.331748463860 0.00000000 0.00000000 + O 2 1 0 1.291808183746 115.57730266 0.00000000 + H 1 2 3 1.032620215491 104.08927786 253.84615379 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.516639875965 0.00000000 0.00000000 + O 2 1 0 2.441163684839 115.57730266 0.00000000 + H 1 2 3 1.951369407629 104.08927786 253.84615379 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1670 + la=0 lb=0: 144 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.201689895871 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.843e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22313 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5092006231657251 0.00e+00 1.32e-04 9.44e-04 4.15e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5092360578448165 -3.54e-05 1.16e-04 1.25e-03 3.99e-04 0.0 + 3 -205.5092350205649154 1.04e-06 1.24e-04 1.50e-03 1.22e-03 0.0 + 4 -205.5092407162231325 -5.70e-06 7.24e-05 5.25e-04 3.86e-04 0.0 + 5 -205.5092437869064383 -3.07e-06 1.63e-05 1.92e-04 8.22e-05 0.0 + 6 -205.5092438280932470 -4.12e-08 1.16e-05 1.45e-04 1.36e-04 0.0 + 7 -205.5092439220991878 -9.40e-08 8.22e-06 1.24e-04 5.55e-05 0.0 + 8 -205.5092439612007524 -3.91e-08 3.41e-06 5.02e-05 2.37e-05 0.0 + 9 -205.5092439753589133 -1.42e-08 1.16e-06 1.12e-05 4.37e-06 0.0 + 10 -205.5092439758706746 -5.12e-10 3.25e-07 2.73e-06 2.14e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 10 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50924397587067 Eh -5592.19083 eV + +Components: +Nuclear Repulsion : 69.20168989587074 Eh 1883.07372 eV +Electronic Energy : -274.71093387174142 Eh -7475.26455 eV +One Electron Energy: -418.11023162987283 Eh -11377.35782 eV +Two Electron Energy: 143.39929775813141 Eh 3902.09327 eV + +Virial components: +Potential Energy : -410.31657603681668 Eh -11165.28167 eV +Kinetic Energy : 204.80733206094601 Eh 5573.09084 eV +Virial Ratio : 2.00342718157530 + +DFT components: +N(Alpha) : 11.999999147338 electrons +N(Beta) : 11.999999147338 electrons +N(Total) : 23.999998294675 electrons +E(X) : -23.319080018565 Eh +E(C) : -0.803300437695 Eh +E(XC) : -24.122380456260 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 5.1176e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.7321e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.2468e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.5147e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.1393e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 5.6883e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 12.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361833 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007151221 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502454587679 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000750 -0.000006595 0.000001263 + 2 O : 0.000000631 0.000000409 -0.000000568 + 3 O : 0.000002429 0.000007892 0.000000959 + 4 H : -0.000002309 -0.000001706 -0.000001653 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000112529 +RMS gradient ... 0.0000032484 +MAX gradient ... 0.0000078923 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.022622969 -0.032521754 -0.029975966 + 2 O : -0.028580718 0.025098753 -0.034181082 + 3 O : 0.018273774 -0.014668479 0.028966670 + 4 H : -0.012316025 0.022091481 0.035190379 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000013264 -0.0000099242 -0.0000324751 + +Norm of the Cartesian gradient ... 0.0913751434 +RMS gradient ... 0.0263777318 +MAX gradient ... 0.0351903787 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.135 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.5%) +RI-J Coulomb gradient .... 0.060 sec ( 44.8%) +XC gradient .... 0.023 sec ( 17.0%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.502454588 Eh +Current gradient norm .... 0.091375143 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999997549 +Lowest eigenvalues of augmented Hessian: + -0.000002105 0.246186682 0.392126797 0.444492803 0.543389091 +Length of the computed step .... 0.002214259 +The final length of the internal step .... 0.002214259 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0009039675 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0005241692 RMS(Int)= 0.0009038721 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000001052 +Previously predicted energy change .... -0.000021583 +Actually observed energy change .... -0.000024074 +Ratio of predicted to observed change .... 1.115412606 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000240739 0.0000050000 NO + RMS gradient 0.0004171798 0.0001000000 NO + MAX gradient 0.0008642704 0.0003000000 NO + RMS step 0.0009039675 0.0020000000 YES + MAX step 0.0015779175 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0008 Max(Angles) 0.04 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3317 -0.000407 0.0006 1.3324 + 2. B(O 2,O 1) 1.2918 0.000864 -0.0008 1.2910 + 3. B(H 3,N 0) 1.0326 -0.000257 0.0003 1.0329 + 4. A(O 1,N 0,H 3) 104.09 0.000146 0.02 104.11 + 5. A(N 0,O 1,O 2) 115.58 0.000210 -0.04 115.53 + 6. D(O 2,O 1,N 0,H 3) -106.15 0.082014 -0.00 -106.15 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.795 %) +Internal coordinates : 0.000 s ( 3.295 %) +B/P matrices and projection : 0.000 s (16.818 %) +Hessian update/contruction : 0.000 s (28.182 %) +Making the step : 0.000 s ( 5.455 %) +Converting the step to Cartesian: 0.000 s ( 4.318 %) +Storing new data : 0.000 s ( 3.409 %) +Checking convergence : 0.000 s ( 1.591 %) +Final printing : 0.000 s (25.909 %) +Total time : 0.001 s + +Time for energy+gradient : 4.121 s +Time for complete geometry iter : 4.884 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 4 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.587905 -0.484167 -0.222138 + O 0.419577 0.368264 -0.405466 + O 0.335367 1.478185 0.248442 + H -0.185747 -1.224437 0.375454 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.110980 -0.914943 -0.419780 + 1 O 8.0000 0 15.999 0.792886 0.695917 -0.766220 + 2 O 8.0000 0 15.999 0.633751 2.793364 0.469487 + 3 H 1.0000 0 1.008 -0.351010 -2.313851 0.709506 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.332392021163 0.00000000 0.00000000 + O 2 1 0 1.290973185761 115.53307577 0.00000000 + H 1 2 3 1.032883522158 104.10653194 253.84615379 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.517856023020 0.00000000 0.00000000 + O 2 1 0 2.439585767324 115.53307577 0.00000000 + H 1 2 3 1.951866985118 104.10653194 253.84615379 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 146 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.210169661687 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.836e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.003 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22313 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5092450558105668 0.00e+00 2.69e-05 2.58e-04 6.98e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5092463642698419 -1.31e-06 3.25e-05 4.12e-04 1.32e-04 0.0 + 3 -205.5092448454691691 1.52e-06 2.38e-05 3.27e-04 5.73e-04 0.0 + 4 -205.5092465819851384 -1.74e-06 2.95e-06 2.74e-05 1.08e-05 0.0 + 5 -205.5092465848915992 -2.91e-09 2.86e-06 3.45e-05 1.38e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50924658489160 Eh -5592.19090 eV + +Components: +Nuclear Repulsion : 69.21016966168705 Eh 1883.30446 eV +Electronic Energy : -274.71941624657865 Eh -7475.49536 eV +One Electron Energy: -418.12657027339208 Eh -11377.80241 eV +Two Electron Energy: 143.40715402681343 Eh 3902.30705 eV + +Virial components: +Potential Energy : -410.31700613113333 Eh -11165.29337 eV +Kinetic Energy : 204.80775954624175 Eh 5573.10247 eV +Virial Ratio : 2.00342509990932 + +DFT components: +N(Alpha) : 11.999999145881 electrons +N(Beta) : 11.999999145881 electrons +N(Total) : 23.999998291761 electrons +E(X) : -23.319153367324 Eh +E(C) : -0.803312044313 Eh +E(XC) : -24.122465411636 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.9065e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.4539e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.8551e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 4.1750e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.3818e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 8.0629e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 12.5 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361841 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007152404 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502456022746 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000750 -0.000006593 0.000001264 + 2 O : 0.000000632 0.000000413 -0.000000568 + 3 O : 0.000002427 0.000007886 0.000000957 + 4 H : -0.000002309 -0.000001705 -0.000001652 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000112463 +RMS gradient ... 0.0000032465 +MAX gradient ... 0.0000078855 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.022417861 -0.032368011 -0.029987537 + 2 O : -0.028358028 0.025607210 -0.034026902 + 3 O : 0.018213575 -0.015129469 0.028736709 + 4 H : -0.012273407 0.021890269 0.035277730 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000067686 -0.0000042816 -0.0000382784 + +Norm of the Cartesian gradient ... 0.0912579327 +RMS gradient ... 0.0263438960 +MAX gradient ... 0.0352777304 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.138 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.9%) +RI-J Coulomb gradient .... 0.059 sec ( 42.5%) +XC gradient .... 0.019 sec ( 13.7%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.502456023 Eh +Current gradient norm .... 0.091257933 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999998152 +Lowest eigenvalues of augmented Hessian: + -0.000000989 0.246839808 0.311640668 0.402006246 0.488997930 +Length of the computed step .... 0.001922495 +The final length of the internal step .... 0.001922495 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0007848553 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0004127538 RMS(Int)= 0.0007848676 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000494 +Previously predicted energy change .... -0.000001052 +Actually observed energy change .... -0.000001435 +Ratio of predicted to observed change .... 1.363682286 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000014351 0.0000050000 YES + RMS gradient 0.0002135323 0.0001000000 NO + MAX gradient 0.0003612549 0.0003000000 NO + RMS step 0.0007848553 0.0020000000 YES + MAX step 0.0012719816 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0007 Max(Angles) 0.05 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3324 -0.000243 0.0006 1.3330 + 2. B(O 2,O 1) 1.2910 0.000361 -0.0007 1.2903 + 3. B(H 3,N 0) 1.0329 -0.000054 0.0001 1.0330 + 4. A(O 1,N 0,H 3) 104.11 0.000279 -0.05 104.05 + 5. A(N 0,O 1,O 2) 115.53 -0.000055 -0.00 115.53 + 6. D(O 2,O 1,N 0,H 3) -106.15 0.081952 0.00 -106.15 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.907 %) +Internal coordinates : 0.000 s ( 3.154 %) +B/P matrices and projection : 0.000 s (12.615 %) +Hessian update/contruction : 0.000 s (31.537 %) +Making the step : 0.000 s ( 5.650 %) +Converting the step to Cartesian: 0.000 s ( 4.205 %) +Storing new data : 0.000 s ( 3.285 %) +Checking convergence : 0.000 s ( 1.314 %) +Final printing : 0.000 s (26.675 %) +Total time : 0.001 s + +Time for energy+gradient : 4.292 s +Time for complete geometry iter : 5.129 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 5 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.588299 -0.484229 -0.222270 + O 0.419743 0.368493 -0.405288 + O 0.335360 1.477783 0.248339 + H -0.185512 -1.224203 0.375511 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.111724 -0.915060 -0.420029 + 1 O 8.0000 0 15.999 0.793199 0.696351 -0.765884 + 2 O 8.0000 0 15.999 0.633739 2.792606 0.469293 + 3 H 1.0000 0 1.008 -0.350566 -2.313409 0.709612 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.332958747944 0.00000000 0.00000000 + O 2 1 0 1.290300082103 115.52902665 0.00000000 + H 1 2 3 1.033025078446 104.05356676 253.84615379 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.518926981428 0.00000000 0.00000000 + O 2 1 0 2.438313785751 115.52902665 0.00000000 + H 1 2 3 1.952134487735 104.05356676 253.84615379 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 146 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.215167998511 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.830e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22313 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5092476188625596 0.00e+00 2.25e-05 2.51e-04 3.68e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5092484391269068 -8.20e-07 2.25e-05 2.79e-04 1.10e-04 0.0 + 3 -205.5092476348509081 8.04e-07 1.77e-05 2.42e-04 4.17e-04 0.0 + 4 -205.5092485627605470 -9.28e-07 3.06e-06 2.51e-05 6.44e-06 0.0 + 5 -205.5092485661567707 -3.40e-09 3.57e-06 2.35e-05 4.14e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50924856615677 Eh -5592.19095 eV + +Components: +Nuclear Repulsion : 69.21516799851095 Eh 1883.44047 eV +Electronic Energy : -274.72441656466771 Eh -7475.63143 eV +One Electron Energy: -418.13571567216155 Eh -11378.05127 eV +Two Electron Energy: 143.41129910749385 Eh 3902.41984 eV + +Virial components: +Potential Energy : -410.31765242546180 Eh -11165.31096 eV +Kinetic Energy : 204.80840385930506 Eh 5573.12000 eV +Virial Ratio : 2.00342195287715 + +DFT components: +N(Alpha) : 11.999999142086 electrons +N(Beta) : 11.999999142086 electrons +N(Total) : 23.999998284172 electrons +E(X) : -23.319232679262 Eh +E(C) : -0.803320372288 Eh +E(XC) : -24.122553051550 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.3962e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.3461e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.5661e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.4207e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.1372e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 9.3932e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 12.7 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361848 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007153738 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502456677058 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000749 -0.000006592 0.000001264 + 2 O : 0.000000632 0.000000415 -0.000000567 + 3 O : 0.000002427 0.000007880 0.000000956 + 4 H : -0.000002310 -0.000001703 -0.000001653 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000112410 +RMS gradient ... 0.0000032450 +MAX gradient ... 0.0000078796 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.022252516 -0.032308173 -0.029997501 + 2 O : -0.028257156 0.025952523 -0.033881449 + 3 O : 0.018212452 -0.015481993 0.028562828 + 4 H : -0.012207812 0.021837643 0.035316122 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000041812 -0.0000158078 -0.0000263679 + +Norm of the Cartesian gradient ... 0.0912094176 +RMS gradient ... 0.0263298909 +MAX gradient ... 0.0353161220 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.152 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.006 sec ( 3.6%) +RI-J Coulomb gradient .... 0.067 sec ( 44.0%) +XC gradient .... 0.023 sec ( 15.0%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.502456677 Eh +Current gradient norm .... 0.091209418 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999052 +Lowest eigenvalues of augmented Hessian: + -0.000000341 0.157466860 0.304886308 0.406911486 0.476042465 +Length of the computed step .... 0.001376629 +The final length of the internal step .... 0.001376629 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0005620066 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0003611860 RMS(Int)= 0.0005620294 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000171 +Previously predicted energy change .... -0.000000494 +Actually observed energy change .... -0.000000654 +Ratio of predicted to observed change .... 1.323689560 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000006543 0.0000050000 YES + RMS gradient 0.0001166511 0.0001000000 NO + MAX gradient 0.0001959318 0.0003000000 YES + RMS step 0.0005620066 0.0020000000 YES + MAX step 0.0010436917 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0004 Max(Angles) 0.06 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3330 -0.000171 0.0004 1.3334 + 2. B(O 2,O 1) 1.2903 -0.000031 -0.0002 1.2901 + 3. B(H 3,N 0) 1.0330 0.000037 0.0000 1.0330 + 4. A(O 1,N 0,H 3) 104.05 0.000196 -0.06 103.99 + 5. A(N 0,O 1,O 2) 115.53 -0.000109 0.01 115.54 + 6. D(O 2,O 1,N 0,H 3) -106.15 0.081950 0.00 -106.15 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.674 %) +Internal coordinates : 0.000 s ( 3.258 %) +B/P matrices and projection : 0.000 s (10.787 %) +Hessian update/contruction : 0.000 s (30.562 %) +Making the step : 0.000 s ( 6.067 %) +Converting the step to Cartesian: 0.000 s ( 3.596 %) +Storing new data : 0.000 s ( 3.034 %) +Checking convergence : 0.000 s ( 1.124 %) +Final printing : 0.000 s (30.674 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 5 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.588688 -0.484415 -0.222454 + O 0.419783 0.368502 -0.405067 + O 0.335452 1.477675 0.248303 + H -0.185255 -1.223918 0.375510 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.112458 -0.915412 -0.420377 + 1 O 8.0000 0 15.999 0.793275 0.696368 -0.765465 + 2 O 8.0000 0 15.999 0.633912 2.792402 0.469224 + 3 H 1.0000 0 1.008 -0.350081 -2.312871 0.709611 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.333352345367 0.00000000 0.00000000 + O 2 1 0 1.290065085759 115.54232441 0.00000000 + H 1 2 3 1.033045700965 103.99376763 253.84615379 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.519670772766 0.00000000 0.00000000 + O 2 1 0 2.437869707018 115.54232441 0.00000000 + H 1 2 3 1.952173458648 103.99376763 253.84615379 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 146 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.212219929596 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.828e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22314 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.2122199296 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5092491095709306 0.00e+00 1.46e-05 1.42e-04 3.21e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5092494407425647 -3.31e-07 1.37e-05 1.71e-04 6.89e-05 0.0 + 3 -205.5092492279128464 2.13e-07 1.07e-05 1.25e-04 2.09e-04 0.0 + 4 -205.5092494976904050 -2.70e-07 1.11e-05 1.66e-04 4.61e-05 0.0 + 5 -205.5092492879749670 2.10e-07 8.47e-06 1.17e-04 1.82e-04 0.0 + 6 -205.5092495325887398 -2.45e-07 1.33e-06 9.54e-06 3.43e-06 0.0 + 7 -205.5092495330732163 -4.84e-10 1.27e-06 8.86e-06 1.48e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50924953307322 Eh -5592.19098 eV + +Components: +Nuclear Repulsion : 69.21221992959632 Eh 1883.36025 eV +Electronic Energy : -274.72146946266952 Eh -7475.55123 eV +One Electron Energy: -418.12963102576498 Eh -11377.88570 eV +Two Electron Energy: 143.40816156309546 Eh 3902.33447 eV + +Virial components: +Potential Energy : -410.31756076573106 Eh -11165.30846 eV +Kinetic Energy : 204.80831123265781 Eh 5573.11748 eV +Virial Ratio : 2.00342241140604 + +DFT components: +N(Alpha) : 11.999999139805 electrons +N(Beta) : 11.999999139805 electrons +N(Total) : 23.999998279610 electrons +E(X) : -23.319175740738 Eh +E(C) : -0.803314277362 Eh +E(XC) : -24.122490018100 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 4.8448e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.8612e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.2677e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.5146e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.4804e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.1599e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.186976 -522.1042 + 1 2.0000 -19.053414 -518.4698 + 2 2.0000 -14.240109 -387.4931 + 3 2.0000 -1.248078 -33.9619 + 4 2.0000 -0.956684 -26.0327 + 5 2.0000 -0.709851 -19.3160 + 6 2.0000 -0.559132 -15.2148 + 7 2.0000 -0.515433 -14.0256 + 8 2.0000 -0.504198 -13.7199 + 9 2.0000 -0.337128 -9.1737 + 10 2.0000 -0.278866 -7.5883 + 11 2.0000 -0.243224 -6.6185 + 12 0.0000 -0.222999 -6.0681 + 13 0.0000 0.046267 1.2590 + 14 0.0000 0.093752 2.5511 + 15 0.0000 0.123459 3.3595 + 16 0.0000 0.226210 6.1555 + 17 0.0000 0.265301 7.2192 + 18 0.0000 0.318360 8.6630 + 19 0.0000 0.329423 8.9641 + 20 0.0000 0.350232 9.5303 + 21 0.0000 0.381068 10.3694 + 22 0.0000 0.390802 10.6343 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.394421 + 1 O : 0.191163 + 2 O : -0.081642 + 3 H : 0.284899 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.880019 s : 3.880019 + pz : 1.118798 p : 3.468466 + px : 1.233661 + py : 1.116007 + dz2 : 0.004114 d : 0.045936 + dxz : 0.011395 + dyz : 0.005588 + dx2y2 : 0.008295 + dxy : 0.016544 + + 1 O s : 3.775493 s : 3.775493 + pz : 1.395042 p : 3.915491 + px : 1.437173 + py : 1.083275 + dz2 : 0.016017 d : 0.117853 + dxz : 0.026856 + dyz : 0.023264 + dx2y2 : 0.016269 + dxy : 0.035447 + + 2 O s : 3.938012 s : 3.938012 + pz : 1.274643 p : 4.123278 + px : 1.669654 + py : 1.178982 + dz2 : 0.005036 d : 0.020351 + dxz : 0.001292 + dyz : 0.006229 + dx2y2 : 0.003411 + dxy : 0.004384 + + 3 H s : 0.683678 s : 0.683678 + pz : 0.012116 p : 0.031423 + px : 0.007361 + py : 0.011947 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.134652 + 1 O : -0.176043 + 2 O : 0.026925 + 3 H : 0.283770 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.355138 s : 3.355138 + pz : 1.060158 p : 3.484212 + px : 1.303750 + py : 1.120304 + dz2 : 0.027064 d : 0.295302 + dxz : 0.043546 + dyz : 0.044373 + dx2y2 : 0.091889 + dxy : 0.088429 + + 1 O s : 3.384916 s : 3.384916 + pz : 1.328473 p : 4.036371 + px : 1.463847 + py : 1.244050 + dz2 : 0.069003 d : 0.754756 + dxz : 0.082381 + dyz : 0.184005 + dx2y2 : 0.215997 + dxy : 0.203370 + + 2 O s : 3.600871 s : 3.600871 + pz : 1.265356 p : 4.109150 + px : 1.566651 + py : 1.277143 + dz2 : 0.046190 d : 0.263054 + dxz : 0.020964 + dyz : 0.081384 + dx2y2 : 0.054828 + dxy : 0.059687 + + 3 H s : 0.636914 s : 0.636914 + pz : 0.029761 p : 0.079315 + px : 0.020234 + py : 0.029320 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3944 7.0000 -0.3944 2.5724 2.5724 0.0000 + 1 O 7.8088 8.0000 0.1912 2.5693 2.5693 -0.0000 + 2 O 8.0816 8.0000 -0.0816 1.6834 1.6834 0.0000 + 3 H 0.7151 1.0000 0.2849 0.9036 0.9036 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3253 B( 0-N , 2-O ) : 0.4063 B( 0-N , 3-H ) : 0.8408 +B( 1-O , 2-O ) : 1.2291 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.895 sec +Sum of individual times .... 0.875 sec ( 97.8%) + +SCF preparation .... 0.461 sec ( 51.5%) +Fock matrix formation .... 0.206 sec ( 23.0%) + Startup .... 0.010 sec ( 4.9% of F) + Split-RI-J .... 0.031 sec ( 15.0% of F) + XC integration .... 0.134 sec ( 65.1% of F) + Basis function eval. .... 0.009 sec ( 6.8% of XC) + Density eval. .... 0.015 sec ( 11.2% of XC) + XC-Functional eval. .... 0.011 sec ( 8.5% of XC) + XC-Potential eval. .... 0.020 sec ( 14.8% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.013 sec ( 1.4%) +Total Energy calculation .... 0.016 sec ( 1.7%) +Population analysis .... 0.117 sec ( 13.1%) +Orbital Transformation .... 0.007 sec ( 0.8%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.011 sec ( 1.2%) +SOSCF solution .... 0.044 sec ( 4.9%) +Finished LeanSCF after 1.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 13.0 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000361849 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007154492 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502456890020 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.009.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.009.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.146735 0.864937 -0.210846 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5092495330732163 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.596272685 0.881352942 -0.314815520 +Nuclear contribution : -0.241447108 -1.569081924 0.457342436 + ----------------------------------------- +Total Dipole Moment : 0.354825577 -0.687728982 0.142526916 + ----------------------------------------- +Magnitude (a.u.) : 0.786883896 +Magnitude (Debye) : 2.000099913 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.818782 0.421274 0.380655 +Rotational constants in MHz : 84504.957664 12629.478709 11411.743238 + +Dipole components along the rotational axes: +x,y,z [a.u.] : 0.452594 0.314280 -0.561759 +x,y,z [Debye]: 1.150401 0.798837 -1.427878 + + + +Dipole moment calculation done in 0.0 sec + +Maximum memory used throughout the entire PROP-calculation: 7.5 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 10 * + * * + * Dihedral ( 2, 1, 0, 3) : -96.92307692 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.3338 0.617149 + 2. B(O 2,O 1) 1.2927 0.723523 + 3. B(H 3,N 0) 1.0366 0.397582 + 4. A(O 1,N 0,H 3) 103.8993 0.351057 + 5. A(N 0,O 1,O 2) 115.4135 0.434247 + 6. D(O 2,O 1,N 0,H 3) -96.9231 0.029061 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.582457 -0.499846 -0.253887 + O 0.404595 0.377257 -0.441820 + O 0.341084 1.447166 0.280893 + H -0.181929 -1.186733 0.411106 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.100685 -0.944571 -0.479776 + 1 O 8.0000 0 15.999 0.764573 0.712913 -0.834919 + 2 O 8.0000 0 15.999 0.644554 2.734747 0.530811 + 3 H 1.0000 0 1.008 -0.343796 -2.242601 0.776878 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.333352345367 0.00000000 0.00000000 + O 2 1 0 1.290065085759 115.54232441 0.00000000 + H 1 2 3 1.033045700965 103.99376763 253.84615379 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.519670772766 0.00000000 0.00000000 + O 2 1 0 2.437869707018 115.54232441 0.00000000 + H 1 2 3 1.952173458648 103.99376763 253.84615379 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1670 + la=0 lb=0: 144 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.169723171246 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.834e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22306 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.1697231712 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.4909624870395533 0.00e+00 4.03e-04 4.28e-03 2.69e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.003) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.4921914261708480 -1.23e-03 5.13e-04 4.93e-03 2.09e-02 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.4932566418115130 -1.07e-03 4.15e-04 4.04e-03 1.48e-02 0.700 0.0 + 4 -205.4940080894484140 -7.51e-04 1.13e-03 9.87e-03 1.04e-02 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.4958025376358250 -1.79e-03 1.85e-04 1.33e-03 1.39e-03 0.0 + *** Restarting incremental Fock matrix formation *** + 6 -205.4958384841874022 -3.59e-05 3.93e-04 3.19e-03 1.36e-03 0.0 + 7 -205.4958564424663905 -1.80e-05 5.03e-04 3.27e-03 1.90e-03 0.0 + 8 -205.4959263993293348 -7.00e-05 5.18e-04 4.54e-03 1.41e-03 0.0 + 9 -205.4958417323445587 8.47e-05 2.92e-04 3.02e-03 3.68e-03 0.0 + 10 -205.4959487611168356 -1.07e-04 3.43e-05 3.32e-04 1.09e-04 0.0 + 11 -205.4959492217912498 -4.61e-07 2.18e-05 1.46e-04 9.18e-05 0.0 + 12 -205.4959495186771505 -2.97e-07 1.60e-05 1.25e-04 3.46e-05 0.0 + 13 -205.4959495755315402 -5.69e-08 2.90e-06 3.19e-05 7.32e-06 0.0 + 14 -205.4959495779571057 -2.43e-09 4.96e-07 5.67e-06 2.21e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 14 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49594957795711 Eh -5591.82907 eV + +Components: +Nuclear Repulsion : 69.16972317124629 Eh 1882.20386 eV +Electronic Energy : -274.66567274920340 Eh -7474.03293 eV +One Electron Energy: -418.01649977990525 Eh -11374.80724 eV +Two Electron Energy: 143.35082703070188 Eh 3900.77432 eV + +Virial components: +Potential Energy : -410.28685226386568 Eh -11164.47284 eV +Kinetic Energy : 204.79090268590858 Eh 5572.64377 eV +Virial Ratio : 2.00344276470684 + +DFT components: +N(Alpha) : 11.999997918893 electrons +N(Beta) : 11.999997918893 electrons +N(Total) : 23.999995837786 electrons +E(X) : -23.311971517322 Eh +E(C) : -0.803329215587 Eh +E(XC) : -24.115300732909 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.4256e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.6746e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.9598e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.3876e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.2089e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.0801e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.191551 -522.2287 + 1 2.0000 -19.062221 -518.7094 + 2 2.0000 -14.229823 -387.2132 + 3 2.0000 -1.249748 -34.0074 + 4 2.0000 -0.956019 -26.0146 + 5 2.0000 -0.710181 -19.3250 + 6 2.0000 -0.559662 -15.2292 + 7 2.0000 -0.518277 -14.1030 + 8 2.0000 -0.503663 -13.7054 + 9 2.0000 -0.338414 -9.2087 + 10 2.0000 -0.284111 -7.7310 + 11 2.0000 -0.232601 -6.3294 + 12 0.0000 -0.232408 -6.3241 + 13 0.0000 0.043987 1.1969 + 14 0.0000 0.095906 2.6097 + 15 0.0000 0.121263 3.2997 + 16 0.0000 0.226916 6.1747 + 17 0.0000 0.263509 7.1704 + 18 0.0000 0.320367 8.7176 + 19 0.0000 0.327446 8.9102 + 20 0.0000 0.359176 9.7737 + 21 0.0000 0.380854 10.3636 + 22 0.0000 0.385829 10.4990 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.432502 + 1 O : 0.189325 + 2 O : -0.053056 + 3 H : 0.296233 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.864021 s : 3.864021 + pz : 1.151526 p : 3.523684 + px : 1.238518 + py : 1.133639 + dz2 : 0.004069 d : 0.044797 + dxz : 0.010194 + dyz : 0.006133 + dx2y2 : 0.008291 + dxy : 0.016111 + + 1 O s : 3.782500 s : 3.782500 + pz : 1.397384 p : 3.910437 + px : 1.417681 + py : 1.095372 + dz2 : 0.018233 d : 0.117739 + dxz : 0.029456 + dyz : 0.020376 + dx2y2 : 0.017576 + dxy : 0.032098 + + 2 O s : 3.934518 s : 3.934518 + pz : 1.268666 p : 4.099589 + px : 1.604749 + py : 1.226174 + dz2 : 0.004945 d : 0.018949 + dxz : 0.002080 + dyz : 0.005375 + dx2y2 : 0.002406 + dxy : 0.004143 + + 3 H s : 0.671773 s : 0.671773 + pz : 0.013261 p : 0.031994 + px : 0.007578 + py : 0.011155 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.162660 + 1 O : -0.169312 + 2 O : 0.041031 + 3 H : 0.290942 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.342747 s : 3.342747 + pz : 1.093769 p : 3.528925 + px : 1.301603 + py : 1.133552 + dz2 : 0.026914 d : 0.290989 + dxz : 0.043384 + dyz : 0.045571 + dx2y2 : 0.086366 + dxy : 0.088754 + + 1 O s : 3.389089 s : 3.389089 + pz : 1.340669 p : 4.025304 + px : 1.439201 + py : 1.245435 + dz2 : 0.074599 d : 0.754919 + dxz : 0.089583 + dyz : 0.183018 + dx2y2 : 0.213691 + dxy : 0.194028 + + 2 O s : 3.604446 s : 3.604446 + pz : 1.269276 p : 4.092965 + px : 1.510922 + py : 1.312767 + dz2 : 0.050003 d : 0.261558 + dxz : 0.024306 + dyz : 0.082536 + dx2y2 : 0.050648 + dxy : 0.054064 + + 3 H s : 0.629339 s : 0.629339 + pz : 0.032602 p : 0.079719 + px : 0.020361 + py : 0.026756 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.4325 7.0000 -0.4325 2.5143 2.5143 -0.0000 + 1 O 7.8107 8.0000 0.1893 2.5801 2.5801 -0.0000 + 2 O 8.0531 8.0000 -0.0531 1.6701 1.6701 -0.0000 + 3 H 0.7038 1.0000 0.2962 0.8993 0.8993 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3219 B( 0-N , 2-O ) : 0.3725 B( 0-N , 3-H ) : 0.8199 +B( 1-O , 2-O ) : 1.2383 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.064 sec +Sum of individual times .... 1.049 sec ( 98.6%) + +SCF preparation .... 0.423 sec ( 39.7%) +Fock matrix formation .... 0.322 sec ( 30.2%) + Startup .... 0.015 sec ( 4.5% of F) + Split-RI-J .... 0.046 sec ( 14.2% of F) + XC integration .... 0.210 sec ( 65.2% of F) + Basis function eval. .... 0.013 sec ( 6.1% of XC) + Density eval. .... 0.016 sec ( 7.8% of XC) + XC-Functional eval. .... 0.012 sec ( 5.5% of XC) + XC-Potential eval. .... 0.016 sec ( 7.9% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.030 sec ( 2.8%) +Total Energy calculation .... 0.027 sec ( 2.6%) +Population analysis .... 0.120 sec ( 11.3%) +Orbital Transformation .... 0.013 sec ( 1.3%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.063 sec ( 5.9%) +SOSCF solution .... 0.051 sec ( 4.8%) +Finished LeanSCF after 1.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 13.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000362316 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007181300 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.489130594465 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000740 -0.000006411 0.000001387 + 2 O : 0.000000607 0.000000427 -0.000000626 + 3 O : 0.000002390 0.000007493 0.000001120 + 4 H : -0.000002257 -0.000001509 -0.000001881 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000108872 +RMS gradient ... 0.0000031429 +MAX gradient ... 0.0000074926 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.019777323 -0.029648527 -0.032510770 + 2 O : -0.029630987 0.020880215 -0.030878873 + 3 O : 0.018692780 -0.014634428 0.028257580 + 4 H : -0.008839116 0.023402740 0.035132062 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000194075 -0.0000040647 -0.0000175258 + +Norm of the Cartesian gradient ... 0.0884124920 +RMS gradient ... 0.0255224880 +MAX gradient ... 0.0351320619 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.136 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.8%) +RI-J Coulomb gradient .... 0.062 sec ( 45.3%) +XC gradient .... 0.020 sec ( 14.6%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.489130594 Eh +Current gradient norm .... 0.088412492 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999538385 +Lowest eigenvalues of augmented Hessian: + -0.000345073 0.350468914 0.392518264 0.433394355 0.616259787 +Length of the computed step .... 0.030395216 +The final length of the internal step .... 0.030395216 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0124087950 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0114114438 RMS(Int)= 0.0124032659 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000002 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0047124542 0.0001000000 NO + MAX gradient 0.0096244334 0.0003000000 NO + RMS step 0.0124087950 0.0020000000 NO + MAX step 0.0274552345 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0049 Max(Angles) 1.57 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3338 -0.003620 0.0031 1.3369 + 2. B(O 2,O 1) 1.2927 0.002769 -0.0020 1.2906 + 3. B(H 3,N 0) 1.0366 0.003616 -0.0049 1.0317 + 4. A(O 1,N 0,H 3) 103.90 -0.009624 1.57 105.47 + 5. A(N 0,O 1,O 2) 115.41 -0.002601 0.34 115.76 + 6. D(O 2,O 1,N 0,H 3) -96.92 0.081173 0.00 -96.92 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (11.523 %) +Internal coordinates : 0.000 s ( 4.115 %) +B/P matrices and projection : 0.000 s (15.226 %) +Hessian update/contruction : 0.000 s (27.160 %) +Making the step : 0.000 s ( 6.310 %) +Converting the step to Cartesian: 0.000 s ( 5.350 %) +Storing new data : 0.000 s ( 3.841 %) +Checking convergence : 0.000 s ( 0.000 %) +Final printing : 0.000 s (25.926 %) +Total time : 0.001 s + +Time for energy+gradient : 4.585 s +Time for complete geometry iter : 5.364 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.575781 -0.503064 -0.248099 + O 0.404240 0.385154 -0.442585 + O 0.343227 1.454351 0.277738 + H -0.190395 -1.198597 0.409238 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.088068 -0.950654 -0.468839 + 1 O 8.0000 0 15.999 0.763904 0.727835 -0.836365 + 2 O 8.0000 0 15.999 0.648606 2.748325 0.524849 + 3 H 1.0000 0 1.008 -0.359794 -2.265019 0.773348 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.336861359001 0.00000000 0.00000000 + O 2 1 0 1.290647718395 115.75715841 0.00000000 + H 1 2 3 1.031687646261 105.47240468 263.07692328 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.526301847533 0.00000000 0.00000000 + O 2 1 0 2.438970723137 115.75715841 0.00000000 + H 1 2 3 1.949607107182 105.47240468 263.07692328 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 146 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.111520480028 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.807e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22307 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.4960020403714225 0.00e+00 2.66e-04 3.47e-03 6.12e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.4960963865506756 -9.43e-05 1.73e-04 1.64e-03 7.46e-04 0.0 + 3 -205.4961076428588740 -1.13e-05 2.50e-04 2.63e-03 1.01e-03 0.0 + 4 -205.4961151772905055 -7.53e-06 1.23e-04 1.44e-03 1.15e-03 0.0 + 5 -205.4961133085499796 1.87e-06 1.26e-04 1.26e-03 9.63e-04 0.0 + 6 -205.4961247584662374 -1.14e-05 7.97e-05 6.00e-04 2.68e-04 0.0 + 7 -205.4961272129913823 -2.45e-06 2.99e-05 2.21e-04 1.06e-04 0.0 + 8 -205.4961275847363709 -3.72e-07 2.30e-05 1.50e-04 4.09e-05 0.0 + 9 -205.4961277018318242 -1.17e-07 1.62e-05 1.08e-04 4.58e-05 0.0 + 10 -205.4961277359180940 -3.41e-08 2.34e-06 2.83e-05 8.25e-06 0.0 + 11 -205.4961277384625760 -2.54e-09 1.29e-06 1.31e-05 3.27e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49612773846258 Eh -5591.83392 eV + +Components: +Nuclear Repulsion : 69.11152048002772 Eh 1880.62008 eV +Electronic Energy : -274.60764821849034 Eh -7472.45400 eV +One Electron Energy: -417.89866625488298 Eh -11371.60083 eV +Two Electron Energy: 143.29101803639267 Eh 3899.14683 eV + +Virial components: +Potential Energy : -410.27867903469246 Eh -11164.25044 eV +Kinetic Energy : 204.78255129622988 Eh 5572.41652 eV +Virial Ratio : 2.00348455685172 + +DFT components: +N(Alpha) : 11.999997820820 electrons +N(Beta) : 11.999997820820 electrons +N(Total) : 23.999995641640 electrons +E(X) : -23.311584632854 Eh +E(C) : -0.803285925569 Eh +E(XC) : -24.114870558422 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.5445e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.3055e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.2865e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.5395e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.2732e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 4.0957e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 13.5 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000362081 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007114444 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.489375374837 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000783 -0.000006485 0.000001379 + 2 O : 0.000000613 0.000000473 -0.000000638 + 3 O : 0.000002422 0.000007630 0.000001096 + 4 H : -0.000002252 -0.000001617 -0.000001838 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000110420 +RMS gradient ... 0.0000031875 +MAX gradient ... 0.0000076297 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.020201062 -0.034738189 -0.029817901 + 2 O : -0.028104591 0.024937195 -0.029810506 + 3 O : 0.019411483 -0.013468814 0.026877980 + 4 H : -0.011507954 0.023269808 0.032750426 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000181323 0.0000017541 -0.0000162412 + +Norm of the Cartesian gradient ... 0.0884956369 +RMS gradient ... 0.0255464899 +MAX gradient ... 0.0347381892 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.127 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.0%) +RI-J Coulomb gradient .... 0.058 sec ( 45.7%) +XC gradient .... 0.020 sec ( 15.8%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.489375375 Eh +Current gradient norm .... 0.088495637 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999430784 +Lowest eigenvalues of augmented Hessian: + -0.000196055 0.166074373 0.394464957 0.446789162 0.677631126 +Length of the computed step .... 0.033755057 +The final length of the internal step .... 0.033755057 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0137804442 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0110235400 RMS(Int)= 0.0137668844 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000098139 +Previously predicted energy change .... -0.000172696 +Actually observed energy change .... -0.000244780 +Ratio of predicted to observed change .... 1.417407140 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0002447804 0.0000050000 NO + RMS gradient 0.0025069608 0.0001000000 NO + MAX gradient 0.0050499357 0.0003000000 NO + RMS step 0.0137804442 0.0020000000 NO + MAX step 0.0320107057 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0043 Max(Angles) 1.83 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3369 0.001672 -0.0017 1.3352 + 2. B(O 2,O 1) 1.2906 0.002927 -0.0043 1.2864 + 3. B(H 3,N 0) 1.0317 0.000880 -0.0033 1.0284 + 4. A(O 1,N 0,H 3) 105.47 -0.005050 1.83 107.31 + 5. A(N 0,O 1,O 2) 115.76 0.000263 0.03 115.78 + 6. D(O 2,O 1,N 0,H 3) -96.92 0.078348 0.00 -96.92 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 7.806 %) +Internal coordinates : 0.000 s ( 2.961 %) +B/P matrices and projection : 0.000 s (14.805 %) +Hessian update/contruction : 0.000 s (40.781 %) +Making the step : 0.000 s ( 4.980 %) +Converting the step to Cartesian: 0.000 s ( 3.769 %) +Storing new data : 0.000 s ( 3.096 %) +Checking convergence : 0.000 s ( 1.211 %) +Final printing : 0.000 s (20.188 %) +Total time : 0.001 s + +Time for energy+gradient : 4.293 s +Time for complete geometry iter : 5.073 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.566525 -0.501987 -0.241453 + O 0.403670 0.392424 -0.444897 + O 0.343150 1.457015 0.274643 + H -0.199003 -1.209607 0.407999 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.070578 -0.948618 -0.456279 + 1 O 8.0000 0 15.999 0.762826 0.741574 -0.840734 + 2 O 8.0000 0 15.999 0.648460 2.753359 0.518999 + 3 H 1.0000 0 1.008 -0.376061 -2.285827 0.771007 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.335155472996 0.00000000 0.00000000 + O 2 1 0 1.286372226572 115.78394415 0.00000000 + H 1 2 3 1.028390164912 107.30648290 263.07692328 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.523078190169 0.00000000 0.00000000 + O 2 1 0 2.430891214503 115.78394415 0.00000000 + H 1 2 3 1.943375770503 107.30648290 263.07692328 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1679 + la=0 lb=0: 146 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.236801619366 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.759e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22307 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.4960162702168418 0.00e+00 2.94e-04 3.46e-03 8.44e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.4961430784732102 -1.27e-04 2.33e-04 1.71e-03 7.49e-04 0.0 + 3 -205.4961736904527925 -3.06e-05 4.88e-04 3.69e-03 7.63e-04 0.0 + 4 -205.4961524039361507 2.13e-05 1.67e-04 1.52e-03 2.57e-03 0.0 + 5 -205.4961906597915799 -3.83e-05 2.09e-04 2.33e-03 1.06e-03 0.0 + 6 -205.4961678150885405 2.28e-05 1.65e-04 1.68e-03 2.34e-03 0.0 + 7 -205.4962020242354015 -3.42e-05 4.19e-05 2.85e-04 7.86e-05 0.0 + 8 -205.4962025250700890 -5.01e-07 6.60e-05 5.02e-04 4.33e-05 0.0 + 9 -205.4962028250482149 -3.00e-07 6.43e-06 8.42e-05 2.70e-05 0.0 + 10 -205.4962028469444135 -2.19e-08 3.13e-06 3.02e-05 1.03e-05 0.0 + 11 -205.4962028510817618 -4.14e-09 8.88e-07 1.09e-05 2.94e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49620285108176 Eh -5591.83596 eV + +Components: +Nuclear Repulsion : 69.23680161936642 Eh 1884.02915 eV +Electronic Energy : -274.73300447044824 Eh -7475.86512 eV +One Electron Energy: -418.13754546700716 Eh -11378.10106 eV +Two Electron Energy: 143.40454099655895 Eh 3902.23595 eV + +Virial components: +Potential Energy : -410.28213036153602 Eh -11164.34435 eV +Kinetic Energy : 204.78592751045423 Eh 5572.50839 eV +Virial Ratio : 2.00346837963557 + +DFT components: +N(Alpha) : 11.999997823094 electrons +N(Beta) : 11.999997823094 electrons +N(Total) : 23.999995646188 electrons +E(X) : -23.314650901768 Eh +E(C) : -0.803605223370 Eh +E(XC) : -24.118256125138 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 4.1373e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.0890e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 8.8781e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.9711e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.9366e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.8687e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 13.7 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361975 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007062823 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.489502002966 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000807 -0.000006518 0.000001382 + 2 O : 0.000000616 0.000000518 -0.000000650 + 3 O : 0.000002422 0.000007684 0.000001061 + 4 H : -0.000002231 -0.000001684 -0.000001793 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000110984 +RMS gradient ... 0.0000032038 +MAX gradient ... 0.0000076838 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.020523981 -0.036048201 -0.027581489 + 2 O : -0.026410521 0.028678329 -0.027501710 + 3 O : 0.018820918 -0.015020460 0.024196852 + 4 H : -0.012934379 0.022390332 0.030886347 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000131457 0.0000104593 -0.0000230279 + +Norm of the Cartesian gradient ... 0.0868658258 +RMS gradient ... 0.0250760040 +MAX gradient ... 0.0360482011 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.112 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.5%) +RI-J Coulomb gradient .... 0.054 sec ( 48.4%) +XC gradient .... 0.018 sec ( 15.7%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.489502003 Eh +Current gradient norm .... 0.086865826 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999726265 +Lowest eigenvalues of augmented Hessian: + -0.000072039 0.101903482 0.397339854 0.454942812 0.718800562 +Length of the computed step .... 0.023402876 +The final length of the internal step .... 0.023402876 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0095541843 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0068548661 RMS(Int)= 0.0095517561 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000036039 +Previously predicted energy change .... -0.000098139 +Actually observed energy change .... -0.000126628 +Ratio of predicted to observed change .... 1.290292700 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0001266281 0.0000050000 NO + RMS gradient 0.0018214617 0.0001000000 NO + MAX gradient 0.0041356820 0.0003000000 NO + RMS step 0.0095541843 0.0020000000 NO + MAX step 0.0208149870 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0051 Max(Angles) 1.19 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3352 0.004136 -0.0051 1.3301 + 2. B(O 2,O 1) 1.2864 0.000221 -0.0019 1.2845 + 3. B(H 3,N 0) 1.0284 -0.000523 -0.0009 1.0275 + 4. A(O 1,N 0,H 3) 107.31 -0.001505 1.19 108.50 + 5. A(N 0,O 1,O 2) 115.78 -0.000465 0.16 115.94 + 6. D(O 2,O 1,N 0,H 3) -96.92 0.074714 -0.00 -96.92 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.272 %) +Internal coordinates : 0.000 s ( 3.138 %) +B/P matrices and projection : 0.000 s (12.268 %) +Hessian update/contruction : 0.000 s (32.953 %) +Making the step : 0.000 s ( 5.849 %) +Converting the step to Cartesian: 0.000 s ( 5.278 %) +Storing new data : 0.000 s ( 3.424 %) +Checking convergence : 0.000 s ( 1.427 %) +Final printing : 0.000 s (26.106 %) +Total time : 0.001 s + +Time for energy+gradient : 4.178 s +Time for complete geometry iter : 4.991 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 4 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.559612 -0.500161 -0.238042 + O 0.401590 0.395498 -0.445541 + O 0.343388 1.458883 0.272603 + H -0.204074 -1.216376 0.407272 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.057514 -0.945167 -0.449834 + 1 O 8.0000 0 15.999 0.758896 0.747384 -0.841951 + 2 O 8.0000 0 15.999 0.648909 2.756889 0.515145 + 3 H 1.0000 0 1.008 -0.385644 -2.298618 0.769633 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.330102480195 0.00000000 0.00000000 + O 2 1 0 1.284486246775 115.94457915 0.00000000 + H 1 2 3 1.027522304006 108.49909380 263.07692328 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.513529417619 0.00000000 0.00000000 + O 2 1 0 2.427327229194 115.94457915 0.00000000 + H 1 2 3 1.941735751066 108.49909380 263.07692328 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1679 + la=0 lb=0: 146 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.370610031401 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.732e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22307 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.4961261353487600 0.00e+00 2.19e-04 2.53e-03 5.07e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.4961912131755923 -6.51e-05 1.82e-04 1.50e-03 5.32e-04 0.0 + 3 -205.4962041858287023 -1.30e-05 3.11e-04 2.14e-03 1.03e-03 0.0 + 4 -205.4962173112521953 -1.31e-05 1.30e-04 9.76e-04 6.55e-04 0.0 + 5 -205.4962156364246368 1.67e-06 1.07e-04 1.01e-03 1.32e-03 0.0 + 6 -205.4962254758224560 -9.84e-06 6.75e-05 7.85e-04 3.62e-04 0.0 + 7 -205.4962273849443761 -1.91e-06 3.01e-05 2.50e-04 1.40e-04 0.0 + 8 -205.4962278087053562 -4.24e-07 1.32e-05 1.06e-04 3.69e-05 0.0 + 9 -205.4962278688844606 -6.02e-08 8.11e-06 4.98e-05 1.69e-05 0.0 + 10 -205.4962278831810920 -1.43e-08 2.63e-06 2.39e-05 6.17e-06 0.0 + 11 -205.4962278843896968 -1.21e-09 7.08e-07 5.54e-06 1.63e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49622788438970 Eh -5591.83664 eV + +Components: +Nuclear Repulsion : 69.37061003140062 Eh 1887.67027 eV +Electronic Energy : -274.86683791579037 Eh -7479.50691 eV +One Electron Energy: -418.39474453851699 Eh -11385.09981 eV +Two Electron Energy: 143.52790662272665 Eh 3905.59290 eV + +Virial components: +Potential Energy : -410.28618653136164 Eh -11164.45473 eV +Kinetic Energy : 204.78995864697194 Eh 5572.61808 eV +Virial Ratio : 2.00344874935316 + +DFT components: +N(Alpha) : 11.999997737694 electrons +N(Beta) : 11.999997737694 electrons +N(Total) : 23.999995475387 electrons +E(X) : -23.317502053030 Eh +E(C) : -0.803958531756 Eh +E(XC) : -24.121460584786 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.2086e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.5438e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 7.0821e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.4880e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.6284e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.6196e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 13.9 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361928 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007029380 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.489560432017 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000820 -0.000006532 0.000001382 + 2 O : 0.000000612 0.000000539 -0.000000656 + 3 O : 0.000002420 0.000007716 0.000001041 + 4 H : -0.000002212 -0.000001723 -0.000001766 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000111265 +RMS gradient ... 0.0000032119 +MAX gradient ... 0.0000077163 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.020376158 -0.034945783 -0.026879439 + 2 O : -0.025749483 0.029801339 -0.025349827 + 3 O : 0.018184077 -0.015983837 0.022202754 + 4 H : -0.012810752 0.021128281 0.030026512 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000049877 0.0000062583 -0.0000231601 + +Norm of the Cartesian gradient ... 0.0845215139 +RMS gradient ... 0.0243992594 +MAX gradient ... 0.0349457829 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.138 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.9%) +RI-J Coulomb gradient .... 0.064 sec ( 46.0%) +XC gradient .... 0.020 sec ( 14.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.489560432 Eh +Current gradient norm .... 0.084521514 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.998230733 +Lowest eigenvalues of augmented Hessian: + -0.000161842 0.038780599 0.397549063 0.459528350 0.625319881 +Length of the computed step .... 0.059564650 +The final length of the internal step .... 0.059564650 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0243171664 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0162062282 RMS(Int)= 0.0243086231 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000081208 +Previously predicted energy change .... -0.000036039 +Actually observed energy change .... -0.000058429 +Ratio of predicted to observed change .... 1.621259981 +New trust radius .... 0.200000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000584291 0.0000050000 NO + RMS gradient 0.0019431685 0.0001000000 NO + MAX gradient 0.0043260903 0.0003000000 NO + RMS step 0.0243171664 0.0020000000 NO + MAX step 0.0489163822 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0167 Max(Angles) 2.80 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3301 0.004326 -0.0167 1.3134 + 2. B(O 2,O 1) 1.2845 -0.001642 -0.0013 1.2832 + 3. B(H 3,N 0) 1.0275 -0.000301 -0.0024 1.0251 + 4. A(O 1,N 0,H 3) 108.50 -0.000391 2.80 111.30 + 5. A(N 0,O 1,O 2) 115.94 -0.001001 0.66 116.61 + 6. D(O 2,O 1,N 0,H 3) -96.92 0.071600 -0.00 -96.92 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.821 %) +Internal coordinates : 0.000 s ( 2.999 %) +B/P matrices and projection : 0.000 s (12.256 %) +Hessian update/contruction : 0.000 s (31.291 %) +Making the step : 0.000 s ( 6.389 %) +Converting the step to Cartesian: 0.000 s ( 4.172 %) +Storing new data : 0.000 s ( 3.520 %) +Checking convergence : 0.000 s ( 1.434 %) +Final printing : 0.000 s (26.728 %) +Total time : 0.001 s + +Time for energy+gradient : 4.143 s +Time for complete geometry iter : 4.957 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 5 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.542173 -0.495928 -0.230739 + O 0.394176 0.399713 -0.445524 + O 0.344864 1.465167 0.267957 + H -0.215575 -1.231108 0.404599 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -1.024558 -0.937168 -0.436034 + 1 O 8.0000 0 15.999 0.744885 0.755348 -0.841919 + 2 O 8.0000 0 15.999 0.651698 2.768764 0.506365 + 3 H 1.0000 0 1.008 -0.407378 -2.326456 0.764581 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.313413260184 0.00000000 0.00000000 + O 2 1 0 1.283229511184 116.60713510 0.00000000 + H 1 2 3 1.025090106750 111.30179608 263.07692328 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.481991362408 0.00000000 0.00000000 + O 2 1 0 2.424952343104 116.60713510 0.00000000 + H 1 2 3 1.937139564349 111.30179608 263.07692328 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 555 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1682 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.701357885998 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.690e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22310 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.4955094387916574 0.00e+00 1.79e-04 1.94e-03 7.16e-03 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.001) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.4956624423395510 -1.53e-04 2.20e-04 2.18e-03 5.59e-03 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.4958057409369303 -1.43e-04 1.89e-04 1.59e-03 3.99e-03 0.700 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 4 -205.4959136409037797 -1.08e-04 5.42e-04 4.17e-03 2.89e-03 0.0 + *** Restarting incremental Fock matrix formation *** + 5 -205.4961824422130690 -2.69e-04 2.76e-04 1.59e-03 9.00e-04 0.1 + 6 -205.4962160116454584 -3.36e-05 1.49e-03 1.02e-02 8.87e-04 0.0 + 7 -205.4962444834932853 -2.85e-05 3.86e-04 3.79e-03 1.74e-03 0.0 + 8 -205.4962652208592999 -2.07e-05 4.34e-04 2.83e-03 9.83e-04 0.0 + 9 -205.4962627994702871 2.42e-06 2.65e-04 1.72e-03 1.29e-03 0.0 + 10 -205.4962782177976237 -1.54e-05 4.90e-05 3.97e-04 1.27e-04 0.0 + 11 -205.4962785228902362 -3.05e-07 2.59e-05 1.81e-04 8.41e-05 0.0 + 12 -205.4962787040416856 -1.81e-07 2.61e-06 2.26e-05 1.22e-05 0.0 + 13 -205.4962787080767725 -4.04e-09 2.25e-06 2.03e-05 5.92e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 13 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49627870807677 Eh -5591.83803 eV + +Components: +Nuclear Repulsion : 69.70135788599755 Eh 1896.67037 eV +Electronic Energy : -275.19763659407431 Eh -7488.50840 eV +One Electron Energy: -419.03357745704693 Eh -11402.48333 eV +Two Electron Energy: 143.83594086297262 Eh 3913.97493 eV + +Virial components: +Potential Energy : -410.29706836169805 Eh -11164.75084 eV +Kinetic Energy : 204.80078965362125 Eh 5572.91281 eV +Virial Ratio : 2.00339592955492 + +DFT components: +N(Alpha) : 11.999997290050 electrons +N(Beta) : 11.999997290050 electrons +N(Total) : 23.999994580099 electrons +E(X) : -23.324980233487 Eh +E(C) : -0.804918799216 Eh +E(XC) : -24.129899032703 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 4.0351e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.0302e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.2457e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.8894e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 5.9211e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 6.2892e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.1 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 14.0 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361797 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006944750 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.489695755405 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000856 -0.000006568 0.000001375 + 2 O : 0.000000598 0.000000568 -0.000000666 + 3 O : 0.000002420 0.000007815 0.000001000 + 4 H : -0.000002162 -0.000001815 -0.000001710 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000112116 +RMS gradient ... 0.0000032365 +MAX gradient ... 0.0000078147 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.018728149 -0.030049625 -0.024719674 + 2 O : -0.023615921 0.028775360 -0.019167112 + 3 O : 0.015874167 -0.016605422 0.017189110 + 4 H : -0.010986395 0.017879687 0.026697675 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000320438 -0.0000208211 -0.0000051252 + +Norm of the Cartesian gradient ... 0.0747946636 +RMS gradient ... 0.0215913596 +MAX gradient ... 0.0300496252 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.129 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.1%) +RI-J Coulomb gradient .... 0.062 sec ( 48.3%) +XC gradient .... 0.018 sec ( 14.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.489695755 Eh +Current gradient norm .... 0.074794664 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.200 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.978748657 +Lowest eigenvalues of augmented Hessian: + -0.000487631 0.010202385 0.396711535 0.449635170 0.578064114 +Length of the computed step .... 0.209516063 +Warning: the length of the step is outside the trust region - taking restricted step instead +The input lambda is .... 0.008753 + iter: 5 x= 0.003049 g= 83.807085 f(x)= 0.160670 + iter: 10 x= -0.000976 g= 7.447033 f(x)= 0.000001 +The output lambda is .... -0.000976 (12 iterations) +The final length of the internal step .... 0.200000000 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0816496581 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0541213319 RMS(Int)= 0.0815605979 + Iter 5: RMS(Cart)= 0.0000004705 RMS(Int)= 0.0000005942 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000253104 +Previously predicted energy change .... -0.000081208 +Actually observed energy change .... -0.000135323 +Ratio of predicted to observed change .... 1.666375249 +New trust radius .... 0.133333333 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0001353234 0.0000050000 NO + RMS gradient 0.0024573512 0.0001000000 NO + MAX gradient 0.0048426006 0.0003000000 NO + RMS step 0.0816496581 0.0020000000 NO + MAX step 0.1627172324 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0561 Max(Angles) 9.32 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3134 0.003103 -0.0561 1.2573 + 2. B(O 2,O 1) 1.2832 -0.004843 0.0033 1.2865 + 3. B(H 3,N 0) 1.0251 0.000227 -0.0092 1.0159 + 4. A(O 1,N 0,H 3) 111.30 -0.000164 9.32 120.62 + 5. A(N 0,O 1,O 2) 116.61 -0.001753 2.52 119.13 + 6. D(O 2,O 1,N 0,H 3) -96.92 0.061289 0.00 -96.92 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.148 %) +Internal coordinates : 0.000 s ( 2.851 %) +B/P matrices and projection : 0.000 s (10.718 %) +Hessian update/contruction : 0.000 s (28.620 %) +Making the step : 0.000 s (11.288 %) +Converting the step to Cartesian: 0.000 s ( 4.219 %) +Storing new data : 0.000 s ( 3.307 %) +Checking convergence : 0.000 s ( 1.140 %) +Final printing : 0.000 s (27.480 %) +Total time : 0.001 s + +Time for energy+gradient : 4.320 s +Time for complete geometry iter : 5.123 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 6 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.484072 -0.485649 -0.205157 + O 0.367573 0.408219 -0.442939 + O 0.350978 1.490123 0.253049 + H -0.253188 -1.274849 0.391339 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.914763 -0.917743 -0.387691 + 1 O 8.0000 0 15.999 0.694612 0.771422 -0.837033 + 2 O 8.0000 0 15.999 0.663253 2.815924 0.478193 + 3 H 1.0000 0 1.008 -0.478455 -2.409116 0.739524 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.257313494055 0.00000000 0.00000000 + O 2 1 0 1.286542204134 119.13094595 0.00000000 + H 1 2 3 1.015851149090 120.62480627 263.07692328 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.375978168247 0.00000000 0.00000000 + O 2 1 0 2.431212425544 119.13094595 0.00000000 + H 1 2 3 1.919680464609 120.62480627 263.07692328 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 555 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1686 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.684417621058 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.622e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.003 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22299 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5575 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.4866556994583107 0.00e+00 6.45e-04 6.40e-03 2.58e-02 0.700 0.1 +Warning: op=0 Small HOMO/LUMO gap ( 0.007) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.4886449806019186 -1.99e-03 7.87e-04 7.56e-03 2.02e-02 0.700 0.1 + ***Turning on AO-DIIS*** + 3 -205.4904458284332236 -1.80e-03 6.50e-04 5.51e-03 1.47e-02 0.700 0.0 + 4 -205.4917653215723021 -1.32e-03 1.81e-03 1.51e-02 1.05e-02 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.4949821897899369 -3.22e-03 3.86e-04 3.24e-03 2.12e-03 0.0 + *** Restarting incremental Fock matrix formation *** + 6 -205.4951244955653351 -1.42e-04 9.02e-04 8.12e-03 3.03e-03 0.0 + 7 -205.4951433089169086 -1.88e-05 1.45e-03 1.02e-02 9.06e-03 0.0 + 8 -205.4956674840169626 -5.24e-04 6.70e-04 6.06e-03 1.20e-03 0.0 + 9 -205.4956825787316461 -1.51e-05 2.20e-04 2.49e-03 2.56e-03 0.0 + 10 -205.4957230473916638 -4.05e-05 1.73e-04 1.98e-03 7.56e-04 0.0 + 11 -205.4957318803404291 -8.83e-06 5.70e-05 6.86e-04 1.75e-04 0.0 + 12 -205.4957334466781731 -1.57e-06 1.93e-05 1.50e-04 4.65e-05 0.0 + 13 -205.4957335186449541 -7.20e-08 4.76e-06 5.41e-05 2.40e-05 0.0 + 14 -205.4957335428432543 -2.42e-08 2.94e-06 3.08e-05 9.87e-06 0.0 + 15 -205.4957335460824197 -3.24e-09 8.72e-07 9.35e-06 4.55e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 15 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49573354608242 Eh -5591.82319 eV + +Components: +Nuclear Repulsion : 70.68441762105772 Eh 1923.42079 eV +Electronic Energy : -276.18015116714014 Eh -7515.24398 eV +One Electron Energy: -420.95916488514331 Eh -11454.88123 eV +Two Electron Energy: 144.77901371800320 Eh 3939.63725 eV + +Virial components: +Potential Energy : -410.37559300366490 Eh -11166.88760 eV +Kinetic Energy : 204.87985945758246 Eh 5575.06441 eV +Virial Ratio : 2.00300602553189 + +DFT components: +N(Alpha) : 11.999996505595 electrons +N(Beta) : 11.999996505595 electrons +N(Total) : 23.999993011189 electrons +E(X) : -23.354361951304 Eh +E(C) : -0.807973850993 Eh +E(XC) : -24.162335802297 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.2392e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 9.3550e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 8.7220e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.1198e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.5492e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.2704e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 1.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 14.2 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361256 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006668526 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.489426276203 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001014 -0.000006709 0.000001325 + 2 O : 0.000000559 0.000000639 -0.000000693 + 3 O : 0.000002444 0.000008196 0.000000888 + 4 H : -0.000001989 -0.000002126 -0.000001520 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000115635 +RMS gradient ... 0.0000033381 +MAX gradient ... 0.0000081958 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.022563903 -0.000277542 -0.016544642 + 2 O : -0.025966674 0.009687408 0.006738686 + 3 O : 0.007829439 -0.017037806 -0.001368729 + 4 H : -0.004426668 0.007627940 0.011174685 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0001141498 -0.0001032947 0.0000605334 + +Norm of the Cartesian gradient ... 0.0463958040 +RMS gradient ... 0.0133933150 +MAX gradient ... 0.0259666736 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.137 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.006 sec ( 4.2%) +RI-J Coulomb gradient .... 0.060 sec ( 43.7%) +XC gradient .... 0.020 sec ( 14.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.489426276 Eh +Current gradient norm .... 0.046395804 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.133 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.989116960 +Lowest eigenvalues of augmented Hessian: + -0.001568278 0.046195751 0.396047363 0.476980458 0.632135557 +Length of the computed step .... 0.148750224 +Warning: the length of the step is outside the trust region - taking restricted step instead +The input lambda is .... 0.044193 + iter: 5 x= 0.037641 g= 728.528647 f(x)= 1.822666 + iter: 10 x= 0.001716 g= 2.478185 f(x)= 0.024502 + iter: 15 x= -0.007159 g= 0.655817 f(x)= 0.000000 +The output lambda is .... -0.007159 (16 iterations) +The final length of the internal step .... 0.133333333 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0544331054 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0333386179 RMS(Int)= 0.0544765932 + Iter 5: RMS(Cart)= 0.0000000301 RMS(Int)= 0.0000000315 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000002 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000792343 +Previously predicted energy change .... -0.000253104 +Actually observed energy change .... 0.000269479 +Ratio of predicted to observed change .... 1.064698856 +New trust radius .... 0.100000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change 0.0002694792 0.0000050000 NO + RMS gradient 0.0098270640 0.0001000000 NO + MAX gradient 0.0185198457 0.0003000000 NO + RMS step 0.0544331054 0.0020000000 NO + MAX step 0.1064139410 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0389 Max(Angles) 6.10 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2573 -0.018520 0.0389 1.2962 + 2. B(O 2,O 1) 1.2865 -0.015182 0.0018 1.2883 + 3. B(H 3,N 0) 1.0159 -0.000362 0.0067 1.0226 + 4. A(O 1,N 0,H 3) 120.62 -0.000297 -6.10 114.53 + 5. A(N 0,O 1,O 2) 119.13 0.002393 -1.69 117.44 + 6. D(O 2,O 1,N 0,H 3) -96.92 0.023517 0.00 -96.92 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (11.010 %) +Internal coordinates : 0.000 s ( 3.238 %) +B/P matrices and projection : 0.000 s (12.565 %) +Hessian update/contruction : 0.000 s (29.275 %) +Making the step : 0.000 s ( 9.067 %) +Converting the step to Cartesian: 0.000 s ( 4.145 %) +Storing new data : 0.000 s ( 3.109 %) +Checking convergence : 0.000 s ( 1.166 %) +Final printing : 0.000 s (26.036 %) +Total time : 0.001 s + +Time for energy+gradient : 4.674 s +Time for complete geometry iter : 5.476 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 7 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.522964 -0.493560 -0.222290 + O 0.385857 0.403138 -0.446308 + O 0.347688 1.477396 0.263866 + H -0.229289 -1.249129 0.401024 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.988258 -0.932694 -0.420068 + 1 O 8.0000 0 15.999 0.729164 0.761820 -0.843399 + 2 O 8.0000 0 15.999 0.657036 2.791874 0.498635 + 3 H 1.0000 0 1.008 -0.433294 -2.360512 0.757825 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.296227690494 0.00000000 0.00000000 + O 2 1 0 1.288345921384 117.43775816 0.00000000 + H 1 2 3 1.022570122544 114.52773654 263.07692327 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.449515342239 0.00000000 0.00000000 + O 2 1 0 2.434620957170 117.43775816 0.00000000 + H 1 2 3 1.932377484338 114.52773654 263.07692327 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 555 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1684 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.868960200159 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.705e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22308 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.4928301318159356 0.00e+00 4.10e-04 3.71e-03 1.71e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.000) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.4936793340219197 -8.49e-04 4.64e-04 4.25e-03 1.33e-02 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.4943826662074002 -7.03e-04 3.71e-04 3.07e-03 9.89e-03 0.700 0.0 + 4 -205.4948828217531513 -5.00e-04 9.80e-04 8.01e-03 7.00e-03 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.4960884464206856 -1.21e-03 1.93e-04 1.66e-03 1.18e-03 0.0 + *** Restarting incremental Fock matrix formation *** + 6 -205.4961229874978699 -3.45e-05 4.54e-04 4.07e-03 1.51e-03 0.0 + 7 -205.4960957691632188 2.72e-05 5.16e-04 3.73e-03 5.49e-03 0.0 + 8 -205.4962720295463328 -1.76e-04 8.11e-04 6.33e-03 8.91e-04 0.0 + 9 -205.4963188155918488 -4.68e-05 6.74e-04 4.74e-03 1.98e-03 0.0 + 10 -205.4963459269388295 -2.71e-05 2.33e-04 1.89e-03 7.63e-04 0.0 + 11 -205.4963571109373106 -1.12e-05 5.36e-05 4.29e-04 1.28e-04 0.0 + 12 -205.4963576505648462 -5.40e-07 2.45e-05 1.95e-04 8.27e-05 0.0 + 13 -205.4963578768621346 -2.26e-07 1.10e-05 9.35e-05 2.67e-05 0.0 + 14 -205.4963579088303618 -3.20e-08 3.84e-06 4.64e-05 9.59e-06 0.0 + 15 -205.4963579119901738 -3.16e-09 5.08e-07 3.91e-06 3.47e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 15 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49635791199017 Eh -5591.84018 eV + +Components: +Nuclear Repulsion : 69.86896020015941 Eh 1901.23106 eV +Electronic Energy : -275.36531811214957 Eh -7493.07125 eV +One Electron Energy: -419.36714098575999 Eh -11411.56006 eV +Two Electron Energy: 144.00182287361045 Eh 3918.48881 eV + +Virial components: +Potential Energy : -410.29785004803591 Eh -11164.77211 eV +Kinetic Energy : 204.80149213604571 Eh 5572.93192 eV +Virial Ratio : 2.00339287457673 + +DFT components: +N(Alpha) : 11.999996857031 electrons +N(Beta) : 11.999996857031 electrons +N(Total) : 23.999993714061 electrons +E(X) : -23.329230127163 Eh +E(C) : -0.805658433298 Eh +E(XC) : -24.134888560461 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.1598e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.9070e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 5.0769e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.1832e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.4706e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.0828e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.1 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 14.4 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361523 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006845271 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.489874163343 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000919 -0.000006641 0.000001353 + 2 O : 0.000000585 0.000000592 -0.000000685 + 3 O : 0.000002445 0.000008014 0.000000971 + 4 H : -0.000002111 -0.000001964 -0.000001640 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000114056 +RMS gradient ... 0.0000032925 +MAX gradient ... 0.0000080137 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.015039224 -0.023507693 -0.021079755 + 2 O : -0.019457785 0.023205100 -0.013082183 + 3 O : 0.012595780 -0.013177111 0.012608197 + 4 H : -0.008177219 0.013479704 0.021553741 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000689710 -0.0000611312 0.0000355458 + +Norm of the Cartesian gradient ... 0.0592938543 +RMS gradient ... 0.0171166614 +MAX gradient ... 0.0235076931 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.121 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.0%) +RI-J Coulomb gradient .... 0.058 sec ( 48.1%) +XC gradient .... 0.018 sec ( 14.8%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.489874163 Eh +Current gradient norm .... 0.059293854 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.100 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999597319 +Lowest eigenvalues of augmented Hessian: + -0.000077489 0.062889503 0.396119835 0.475720556 0.662564336 +Length of the computed step .... 0.028387490 +The final length of the internal step .... 0.028387490 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0115891444 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0078701004 RMS(Int)= 0.0115865434 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000038776 +Previously predicted energy change .... -0.000792343 +Actually observed energy change .... -0.000447887 +Ratio of predicted to observed change .... 0.565269508 +New trust radius .... 0.100000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0004478871 0.0000050000 NO + RMS gradient 0.0021065347 0.0001000000 NO + MAX gradient 0.0044184420 0.0003000000 NO + RMS step 0.0115891444 0.0020000000 NO + MAX step 0.0232660838 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0072 Max(Angles) 1.33 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2962 0.002212 -0.0072 1.2891 + 2. B(O 2,O 1) 1.2883 -0.004418 0.0033 1.2917 + 3. B(H 3,N 0) 1.0226 0.000835 -0.0016 1.0210 + 4. A(O 1,N 0,H 3) 114.53 -0.000461 1.33 115.86 + 5. A(N 0,O 1,O 2) 117.44 -0.001141 0.33 117.76 + 6. D(O 2,O 1,N 0,H 3) -96.92 0.046929 0.00 -96.92 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (11.382 %) +Internal coordinates : 0.000 s ( 2.981 %) +B/P matrices and projection : 0.000 s (11.247 %) +Hessian update/contruction : 0.000 s (30.352 %) +Making the step : 0.000 s ( 4.743 %) +Converting the step to Cartesian: 0.000 s ( 3.659 %) +Storing new data : 0.000 s ( 2.981 %) +Checking convergence : 0.000 s ( 1.355 %) +Final printing : 0.000 s (30.894 %) +Total time : 0.001 s + +Time for energy+gradient : 4.097 s +Time for complete geometry iter : 4.930 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 8 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.514985 -0.492917 -0.218586 + O 0.382397 0.403902 -0.446826 + O 0.348835 1.482866 0.262494 + H -0.234954 -1.256007 0.399210 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.973181 -0.931478 -0.413067 + 1 O 8.0000 0 15.999 0.722626 0.763264 -0.844379 + 2 O 8.0000 0 15.999 0.659202 2.802211 0.496042 + 3 H 1.0000 0 1.008 -0.444000 -2.373509 0.754397 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.289058943689 0.00000000 0.00000000 + O 2 1 0 1.291675653630 117.76371212 0.00000000 + H 1 2 3 1.020977184184 115.86078492 263.07692328 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.435968374054 0.00000000 0.00000000 + O 2 1 0 2.440913239214 117.76371212 0.00000000 + H 1 2 3 1.929367267090 115.86078492 263.07692328 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1674 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.916287458761 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.723e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22307 +Total number of batches ... 352 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.4962005068429960 0.00e+00 8.91e-05 8.32e-04 3.44e-03 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.002) - skipping pre-diagonalization + Will do a full diagonalization + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 2 -205.4962414346753974 -4.09e-05 3.50e-04 3.23e-03 2.69e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 3 -205.4963570305042992 -1.16e-04 1.91e-04 1.90e-03 6.17e-04 0.0 + 4 -205.4963432987161980 1.37e-05 1.46e-04 1.24e-03 2.79e-03 0.0 + 5 -205.4963754895698855 -3.22e-05 1.72e-04 1.26e-03 2.75e-04 0.0 + 6 -205.4963812367023763 -5.75e-06 2.62e-04 1.95e-03 3.54e-04 0.0 + 7 -205.4963838595746495 -2.62e-06 3.88e-05 3.93e-04 5.07e-04 0.0 + 8 -205.4963860012120165 -2.14e-06 3.19e-05 2.67e-04 1.03e-04 0.0 + 9 -205.4963862702752238 -2.69e-07 1.44e-05 8.95e-05 5.42e-05 0.0 + 10 -205.4963863294014175 -5.91e-08 5.92e-06 4.17e-05 1.45e-05 0.0 + 11 -205.4963863376219990 -8.22e-09 2.33e-06 2.97e-05 6.90e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49638633762200 Eh -5591.84096 eV + +Components: +Nuclear Repulsion : 69.91628745876145 Eh 1902.51890 eV +Electronic Energy : -275.41267379638344 Eh -7494.35986 eV +One Electron Energy: -419.46445921274676 Eh -11414.20822 eV +Two Electron Energy: 144.05178541636332 Eh 3919.84836 eV + +Virial components: +Potential Energy : -410.29992703002199 Eh -11164.82862 eV +Kinetic Energy : 204.80354069240002 Eh 5572.98767 eV +Virial Ratio : 2.00338297689034 + +DFT components: +N(Alpha) : 11.999996793437 electrons +N(Beta) : 11.999996793437 electrons +N(Total) : 23.999993586873 electrons +E(X) : -23.330957280553 Eh +E(C) : -0.805927180033 Eh +E(XC) : -24.136884460586 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 8.2206e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.9709e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.3348e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.6906e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 6.8961e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 9.0120e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.1 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 14.6 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361397 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006805279 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.489942456492 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000946 -0.000006674 0.000001343 + 2 O : 0.000000580 0.000000598 -0.000000694 + 3 O : 0.000002456 0.000008101 0.000000963 + 4 H : -0.000002090 -0.000002025 -0.000001612 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000114920 +RMS gradient ... 0.0000033175 +MAX gradient ... 0.0000081012 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.014086427 -0.020546333 -0.019189368 + 2 O : -0.018121627 0.019854803 -0.010700768 + 3 O : 0.011202983 -0.011365331 0.010915781 + 4 H : -0.007167784 0.012056861 0.018974355 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000794772 -0.0000805168 0.0000444580 + +Norm of the Cartesian gradient ... 0.0525026391 +RMS gradient ... 0.0151562064 +MAX gradient ... 0.0205463331 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.124 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.2%) +RI-J Coulomb gradient .... 0.058 sec ( 46.7%) +XC gradient .... 0.018 sec ( 14.4%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.489942456 Eh +Current gradient norm .... 0.052502639 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.100 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.996573660 +Lowest eigenvalues of augmented Hessian: + -0.000171617 0.021955321 0.396706089 0.481532873 0.551320086 +Length of the computed step .... 0.082994347 +The final length of the internal step .... 0.082994347 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0338823003 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0234230211 RMS(Int)= 0.0338550619 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000086399 +Previously predicted energy change .... -0.000038776 +Actually observed energy change .... -0.000068293 +Ratio of predicted to observed change .... 1.761236151 +New trust radius .... 0.100000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000682931 0.0000050000 NO + RMS gradient 0.0016654097 0.0001000000 NO + MAX gradient 0.0038000165 0.0003000000 NO + RMS step 0.0338823003 0.0020000000 NO + MAX step 0.0694099658 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0195 Max(Angles) 3.98 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2891 0.001056 -0.0195 1.2696 + 2. B(O 2,O 1) 1.2917 -0.003800 0.0109 1.3026 + 3. B(H 3,N 0) 1.0210 0.000510 -0.0040 1.0170 + 4. A(O 1,N 0,H 3) 115.86 -0.000572 3.98 119.84 + 5. A(N 0,O 1,O 2) 117.76 -0.000706 0.87 118.63 + 6. D(O 2,O 1,N 0,H 3) -96.92 0.040959 0.00 -96.92 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (11.883 %) +Internal coordinates : 0.000 s ( 3.071 %) +B/P matrices and projection : 0.000 s (12.283 %) +Hessian update/contruction : 0.000 s (32.577 %) +Making the step : 0.000 s ( 4.673 %) +Converting the step to Cartesian: 0.000 s ( 4.005 %) +Storing new data : 0.000 s ( 3.071 %) +Checking convergence : 0.000 s ( 1.335 %) +Final printing : 0.000 s (26.702 %) +Total time : 0.001 s + +Time for energy+gradient : 4.388 s +Time for complete geometry iter : 5.150 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 9 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.491703 -0.491569 -0.207206 + O 0.372784 0.406171 -0.449054 + O 0.352080 1.499438 0.258842 + H -0.251869 -1.276196 0.393711 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.929184 -0.928932 -0.391563 + 1 O 8.0000 0 15.999 0.704459 0.767553 -0.848589 + 2 O 8.0000 0 15.999 0.665335 2.833527 0.489140 + 3 H 1.0000 0 1.008 -0.475964 -2.411661 0.744005 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.269553314465 0.00000000 0.00000000 + O 2 1 0 1.302603744430 118.62937765 0.00000000 + H 1 2 3 1.016985652415 119.83768322 263.07692328 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.399108076751 0.00000000 0.00000000 + O 2 1 0 2.461564337993 118.62937765 0.00000000 + H 1 2 3 1.921824365191 119.83768322 263.07692328 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1669 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.004455520435 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.793e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22302 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.4947737695903243 0.00e+00 2.63e-04 2.64e-03 1.03e-02 0.700 0.1 +Warning: op=0 Small HOMO/LUMO gap ( 0.006) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.4951272831896745 -3.54e-04 3.05e-04 2.76e-03 8.06e-03 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.4954355411470601 -3.08e-04 2.45e-04 2.12e-03 6.05e-03 0.700 0.0 + 4 -205.4956574187617662 -2.22e-04 6.72e-04 5.71e-03 4.32e-03 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.4961902679905847 -5.33e-04 1.39e-04 1.12e-03 8.61e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -205.4962066831191123 -1.64e-05 3.39e-04 3.29e-03 1.08e-03 0.0 + 7 -205.4961744203826015 3.23e-05 3.18e-04 2.49e-03 4.59e-03 0.0 + 8 -205.4962711213532884 -9.67e-05 3.42e-04 2.45e-03 4.23e-04 0.0 + 9 -205.4962883050482674 -1.72e-05 3.34e-04 2.51e-03 5.08e-04 0.0 + 10 -205.4962861950542106 2.11e-06 1.05e-04 9.67e-04 7.75e-04 0.0 + 11 -205.4962940278430779 -7.83e-06 1.09e-05 1.05e-04 8.16e-05 0.0 + 12 -205.4962941291971106 -1.01e-07 1.00e-05 7.11e-05 2.52e-05 0.0 + 13 -205.4962941574396496 -2.82e-08 2.81e-06 4.22e-05 2.09e-05 0.0 + 14 -205.4962941603463946 -2.91e-09 1.30e-06 1.10e-05 4.66e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 14 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49629416034639 Eh -5591.83845 eV + +Components: +Nuclear Repulsion : 70.00445552043504 Eh 1904.91808 eV +Electronic Energy : -275.50074968078138 Eh -7496.75653 eV +One Electron Energy: -419.65666911438399 Eh -11419.43852 eV +Two Electron Energy: 144.15591943360258 Eh 3922.68199 eV + +Virial components: +Potential Energy : -410.30989135113902 Eh -11165.09977 eV +Kinetic Energy : 204.81359719079262 Eh 5573.26132 eV +Virial Ratio : 2.00333325999307 + +DFT components: +N(Alpha) : 11.999996977462 electrons +N(Beta) : 11.999996977462 electrons +N(Total) : 23.999993954925 electrons +E(X) : -23.335771239017 Eh +E(C) : -0.806587564385 Eh +E(XC) : -24.142358803402 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.9067e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.1037e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.2961e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.6111e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.6552e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.7838e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 1.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 14.8 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361005 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006693424 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.489961741045 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001033 -0.000006772 0.000001306 + 2 O : 0.000000570 0.000000612 -0.000000723 + 3 O : 0.000002491 0.000008372 0.000000943 + 4 H : -0.000002028 -0.000002211 -0.000001525 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000117628 +RMS gradient ... 0.0000033956 +MAX gradient ... 0.0000083717 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.014210649 -0.011382318 -0.014505122 + 2 O : -0.016966428 0.009505710 -0.004478218 + 3 O : 0.007977677 -0.006425847 0.006722717 + 4 H : -0.005221898 0.008302454 0.012260622 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000931561 -0.0001102093 0.0000705757 + +Norm of the Cartesian gradient ... 0.0365625828 +RMS gradient ... 0.0105547085 +MAX gradient ... 0.0169664276 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.128 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.6%) +RI-J Coulomb gradient .... 0.059 sec ( 46.0%) +XC gradient .... 0.020 sec ( 15.8%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.489961741 Eh +Current gradient norm .... 0.036562583 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.100 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999116502 +Lowest eigenvalues of augmented Hessian: + -0.000105574 0.045421626 0.396703823 0.480904322 0.548293879 +Length of the computed step .... 0.042063526 +The final length of the internal step .... 0.042063526 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0171723625 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0114267522 RMS(Int)= 0.0171781053 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000003 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000052880 +Previously predicted energy change .... -0.000086399 +Actually observed energy change .... -0.000019285 +Ratio of predicted to observed change .... 0.223202597 +New trust radius .... 0.100000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000192846 0.0000050000 NO + RMS gradient 0.0020463804 0.0001000000 NO + MAX gradient 0.0043636091 0.0003000000 NO + RMS step 0.0171723625 0.0020000000 NO + MAX step 0.0352681709 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0105 Max(Angles) 2.02 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2696 -0.004364 0.0105 1.2801 + 2. B(O 2,O 1) 1.3026 -0.001879 -0.0033 1.2993 + 3. B(H 3,N 0) 1.0170 -0.000385 0.0020 1.0190 + 4. A(O 1,N 0,H 3) 119.84 0.000454 -2.02 117.82 + 5. A(N 0,O 1,O 2) 118.63 0.001483 -0.50 118.13 + 6. D(O 2,O 1,N 0,H 3) -96.92 0.026165 -0.00 -96.92 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (12.355 %) +Internal coordinates : 0.000 s ( 3.343 %) +B/P matrices and projection : 0.000 s (12.791 %) +Hessian update/contruction : 0.000 s (29.070 %) +Making the step : 0.000 s ( 5.087 %) +Converting the step to Cartesian: 0.000 s ( 3.924 %) +Storing new data : 0.000 s ( 3.343 %) +Checking convergence : 0.000 s ( 1.453 %) +Final printing : 0.000 s (28.343 %) +Total time : 0.001 s + +Time for energy+gradient : 4.449 s +Time for complete geometry iter : 5.233 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 10 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.503802 -0.492651 -0.212969 + O 0.378070 0.404692 -0.448900 + O 0.350507 1.492314 0.261407 + H -0.243483 -1.266511 0.396754 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.952048 -0.930976 -0.402453 + 1 O 8.0000 0 15.999 0.714449 0.764757 -0.848299 + 2 O 8.0000 0 15.999 0.662362 2.820065 0.493988 + 3 H 1.0000 0 1.008 -0.460116 -2.393359 0.749757 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.280073405677 0.00000000 0.00000000 + O 2 1 0 1.299314784244 118.12671105 0.00000000 + H 1 2 3 1.019013186802 117.81696603 263.07692328 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.418988168045 0.00000000 0.00000000 + O 2 1 0 2.455349103976 118.12671105 0.00000000 + H 1 2 3 1.925655849909 117.81696603 263.07692328 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.888586812228 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.780e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22305 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.4960326474492547 0.00e+00 1.29e-04 1.15e-03 5.44e-03 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.004) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.4961193526395675 -8.67e-05 1.48e-04 1.39e-03 4.24e-03 0.700 0.0 + ***Turning on AO-DIIS*** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 3 -205.4961929545350756 -7.36e-05 3.93e-04 3.46e-03 3.15e-03 0.0 + *** Restarting incremental Fock matrix formation *** + 4 -205.4963650035412286 -1.72e-04 1.57e-04 1.37e-03 4.66e-04 0.0 + 5 -205.4963701875296636 -5.18e-06 2.93e-04 2.45e-03 9.72e-04 0.0 + 6 -205.4963857337297384 -1.55e-05 4.12e-04 3.03e-03 6.90e-04 0.0 + 7 -205.4963735795359696 1.22e-05 1.73e-04 1.55e-03 1.57e-03 0.0 + 8 -205.4963940364868620 -2.05e-05 3.05e-05 4.17e-04 1.53e-04 0.0 + 9 -205.4963943573630161 -3.21e-07 2.08e-05 1.61e-04 8.35e-05 0.0 + 10 -205.4963946052667154 -2.48e-07 1.16e-05 8.10e-05 3.05e-05 0.0 + 11 -205.4963946404155024 -3.51e-08 4.04e-06 5.00e-05 9.92e-06 0.0 + 12 -205.4963946442603344 -3.84e-09 5.88e-07 4.52e-06 3.02e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49639464426033 Eh -5591.84118 eV + +Components: +Nuclear Repulsion : 69.88858681222806 Eh 1901.76513 eV +Electronic Energy : -275.38498145648839 Eh -7493.60631 eV +One Electron Energy: -419.42368762553093 Eh -11413.09877 eV +Two Electron Energy: 144.03870616904254 Eh 3919.49246 eV + +Virial components: +Potential Energy : -410.29698112639005 Eh -11164.74846 eV +Kinetic Energy : 204.80058648212969 Eh 5572.90728 eV +Virial Ratio : 2.00339749106232 + +DFT components: +N(Alpha) : 11.999996910160 electrons +N(Beta) : 11.999996910160 electrons +N(Total) : 23.999993820320 electrons +E(X) : -23.331280751796 Eh +E(C) : -0.806119848856 Eh +E(XC) : -24.137400600653 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.8448e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.5222e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 5.8798e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.1527e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.0200e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 9.9211e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 14.9 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361174 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006751087 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.490004731312 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000992 -0.000006731 0.000001322 + 2 O : 0.000000576 0.000000601 -0.000000713 + 3 O : 0.000002478 0.000008258 0.000000959 + 4 H : -0.000002062 -0.000002128 -0.000001568 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000116501 +RMS gradient ... 0.0000033631 +MAX gradient ... 0.0000082577 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.012852853 -0.016937552 -0.016437147 + 2 O : -0.016083761 0.014329262 -0.008815298 + 3 O : 0.009337181 -0.007501050 0.009687088 + 4 H : -0.006106274 0.010109340 0.015565358 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000905612 -0.0000999783 0.0000629299 + +Norm of the Cartesian gradient ... 0.0433939511 +RMS gradient ... 0.0125267547 +MAX gradient ... 0.0169375524 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.117 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 4.0%) +RI-J Coulomb gradient .... 0.054 sec ( 46.0%) +XC gradient .... 0.019 sec ( 15.9%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.490004731 Eh +Current gradient norm .... 0.043393951 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.100 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999979276 +Lowest eigenvalues of augmented Hessian: + -0.000004268 0.054301750 0.396714598 0.468788636 0.566802044 +Length of the computed step .... 0.006438099 +The final length of the internal step .... 0.006438099 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0026283429 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0018224711 RMS(Int)= 0.0026281567 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000002134 +Previously predicted energy change .... -0.000052880 +Actually observed energy change .... -0.000042990 +Ratio of predicted to observed change .... 0.812975328 +New trust radius .... 0.150000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000429903 0.0000050000 NO + RMS gradient 0.0004919767 0.0001000000 NO + MAX gradient 0.0011929449 0.0003000000 NO + RMS step 0.0026283429 0.0020000000 NO + MAX step 0.0051174996 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0016 Max(Angles) 0.29 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2801 -0.000016 -0.0012 1.2788 + 2. B(O 2,O 1) 1.2993 -0.001193 0.0016 1.3009 + 3. B(H 3,N 0) 1.0190 0.000083 -0.0003 1.0188 + 4. A(O 1,N 0,H 3) 117.82 -0.000123 0.29 118.11 + 5. A(N 0,O 1,O 2) 118.13 -0.000083 0.04 118.17 + 6. D(O 2,O 1,N 0,H 3) -96.92 0.033281 -0.00 -96.92 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (12.150 %) +Internal coordinates : 0.000 s ( 2.937 %) +B/P matrices and projection : 0.000 s (15.220 %) +Hessian update/contruction : 0.000 s (29.372 %) +Making the step : 0.000 s ( 6.676 %) +Converting the step to Cartesian: 0.000 s ( 4.139 %) +Storing new data : 0.000 s ( 3.071 %) +Checking convergence : 0.000 s ( 1.335 %) +Final printing : 0.000 s (24.967 %) +Total time : 0.001 s + +Time for energy+gradient : 4.338 s +Time for complete geometry iter : 5.278 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 11 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.502171 -0.492693 -0.212122 + O 0.377482 0.404711 -0.449377 + O 0.350767 1.493954 0.261381 + H -0.244786 -1.268128 0.396409 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.948966 -0.931054 -0.400852 + 1 O 8.0000 0 15.999 0.713338 0.764792 -0.849199 + 2 O 8.0000 0 15.999 0.662853 2.823164 0.493938 + 3 H 1.0000 0 1.008 -0.462578 -2.396415 0.749105 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.278832701772 0.00000000 0.00000000 + O 2 1 0 1.300900138205 118.16904233 0.00000000 + H 1 2 3 1.018752849751 118.11017716 263.07692328 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.416643577452 0.00000000 0.00000000 + O 2 1 0 2.458344988789 118.16904233 0.00000000 + H 1 2 3 1.925163884182 118.11017716 263.07692328 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.871754942919 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.793e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22305 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.4963803301845928 0.00e+00 7.37e-05 9.19e-04 1.20e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.4963878783628957 -7.55e-06 5.76e-05 5.71e-04 2.86e-04 0.1 + 3 -205.4963855615787338 2.32e-06 4.27e-05 4.54e-04 1.00e-03 0.0 + 4 -205.4963894194635259 -3.86e-06 2.34e-05 1.94e-04 6.19e-05 0.0 + 5 -205.4963896579296261 -2.38e-07 5.71e-05 3.95e-04 4.97e-05 0.0 + 6 -205.4963898910182820 -2.33e-07 1.40e-05 1.10e-04 3.24e-05 0.0 + 7 -205.4963898771636082 1.39e-08 5.16e-06 5.92e-05 6.67e-05 0.0 + 8 -205.4963899171804087 -4.00e-08 1.80e-06 2.00e-05 8.54e-06 0.0 + 9 -205.4963899186879530 -1.51e-09 1.55e-06 1.92e-05 3.59e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49638991868795 Eh -5591.84105 eV + +Components: +Nuclear Repulsion : 69.87175494291897 Eh 1901.30711 eV +Electronic Energy : -275.36814486160694 Eh -7493.14817 eV +One Electron Energy: -419.39334890784329 Eh -11412.27321 eV +Two Electron Energy: 144.02520404623635 Eh 3919.12505 eV + +Virial components: +Potential Energy : -410.29569793583721 Eh -11164.71354 eV +Kinetic Energy : 204.79930801714926 Eh 5572.87249 eV +Virial Ratio : 2.00340373172296 + +DFT components: +N(Alpha) : 11.999996956725 electrons +N(Beta) : 11.999996956725 electrons +N(Total) : 23.999993913450 electrons +E(X) : -23.331009262526 Eh +E(C) : -0.806123350476 Eh +E(XC) : -24.137132613002 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.5075e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.9245e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.5513e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.2851e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.5932e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 5.3247e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 15.1 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361135 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006743423 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.490007631324 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001000 -0.000006741 0.000001318 + 2 O : 0.000000575 0.000000601 -0.000000717 + 3 O : 0.000002482 0.000008285 0.000000960 + 4 H : -0.000002058 -0.000002145 -0.000001562 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000116784 +RMS gradient ... 0.0000033713 +MAX gradient ... 0.0000082854 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.012654819 -0.016488523 -0.016019482 + 2 O : -0.015744341 0.013389466 -0.008737616 + 3 O : 0.009071275 -0.006737088 0.009668449 + 4 H : -0.005981754 0.009836145 0.015088650 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000897679 -0.0001010973 0.0000616024 + +Norm of the Cartesian gradient ... 0.0421129603 +RMS gradient ... 0.0121569645 +MAX gradient ... 0.0164885228 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.141 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.7%) +RI-J Coulomb gradient .... 0.064 sec ( 45.3%) +XC gradient .... 0.023 sec ( 16.2%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.490007631 Eh +Current gradient norm .... 0.042112960 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.150 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999995793 +Lowest eigenvalues of augmented Hessian: + -0.000001021 0.049034349 0.383930427 0.397195275 0.518503807 +Length of the computed step .... 0.002900556 +The final length of the internal step .... 0.002900556 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0011841471 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0007899521 RMS(Int)= 0.0011841192 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000511 +Previously predicted energy change .... -0.000002134 +Actually observed energy change .... -0.000002900 +Ratio of predicted to observed change .... 1.359000076 +New trust radius .... 0.150000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000029000 0.0000050000 YES + RMS gradient 0.0002302275 0.0001000000 NO + MAX gradient 0.0005564108 0.0003000000 NO + RMS step 0.0011841471 0.0020000000 YES + MAX step 0.0019759969 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0010 Max(Angles) 0.11 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2788 -0.000088 -0.0005 1.2784 + 2. B(O 2,O 1) 1.3009 -0.000556 0.0010 1.3019 + 3. B(H 3,N 0) 1.0188 0.000022 -0.0001 1.0187 + 4. A(O 1,N 0,H 3) 118.11 -0.000012 0.11 118.22 + 5. A(N 0,O 1,O 2) 118.17 -0.000000 0.01 118.18 + 6. D(O 2,O 1,N 0,H 3) -96.92 0.032231 -0.00 -96.92 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (12.376 %) +Internal coordinates : 0.000 s ( 3.094 %) +B/P matrices and projection : 0.000 s (14.480 %) +Hessian update/contruction : 0.000 s (29.455 %) +Making the step : 0.000 s ( 5.322 %) +Converting the step to Cartesian: 0.000 s ( 4.084 %) +Storing new data : 0.000 s ( 3.713 %) +Checking convergence : 0.000 s ( 1.238 %) +Final printing : 0.000 s (25.866 %) +Total time : 0.001 s + +Time for energy+gradient : 4.590 s +Time for complete geometry iter : 5.438 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 12 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.501565 -0.492764 -0.211800 + O 0.377282 0.404607 -0.449693 + O 0.350883 1.494798 0.261488 + H -0.245308 -1.268796 0.396296 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.947821 -0.931189 -0.400244 + 1 O 8.0000 0 15.999 0.712960 0.764596 -0.849796 + 2 O 8.0000 0 15.999 0.663072 2.824758 0.494141 + 3 H 1.0000 0 1.008 -0.463565 -2.397677 0.748892 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.278373775433 0.00000000 0.00000000 + O 2 1 0 1.301918558153 118.17793121 0.00000000 + H 1 2 3 1.018663286842 118.22339344 263.07692328 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.415776332355 0.00000000 0.00000000 + O 2 1 0 2.460269523579 118.17793121 0.00000000 + H 1 2 3 1.924994634812 118.22339344 263.07692328 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.854910537111 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.802e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22305 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.5 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.4963855942173154 0.00e+00 3.74e-05 5.06e-04 6.09e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.4963873500511227 -1.76e-06 2.78e-05 2.73e-04 1.42e-04 0.1 + 3 -205.4963866190702220 7.31e-07 1.93e-05 2.20e-04 5.31e-04 0.0 + 4 -205.4963876436520991 -1.02e-06 9.24e-06 7.03e-05 2.59e-05 0.0 + 5 -205.4963876736089787 -3.00e-08 2.15e-05 1.65e-04 2.55e-05 0.0 + 6 -205.4963877040710827 -3.05e-08 7.41e-06 6.10e-05 2.76e-05 0.0 + 7 -205.4963877167984379 -1.27e-08 2.76e-06 3.93e-05 7.61e-06 0.0 + 8 -205.4963877193068811 -2.51e-09 1.09e-06 1.12e-05 3.81e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49638771930688 Eh -5591.84099 eV + +Components: +Nuclear Repulsion : 69.85491053711088 Eh 1900.84875 eV +Electronic Energy : -275.35129825641775 Eh -7492.68975 eV +One Electron Energy: -419.36206404877561 Eh -11411.42191 eV +Two Electron Energy: 144.01076579235786 Eh 3918.73216 eV + +Virial components: +Potential Energy : -410.29428152636342 Eh -11164.67500 eV +Kinetic Energy : 204.79789380705657 Eh 5572.83401 eV +Virial Ratio : 2.00341064988153 + +DFT components: +N(Alpha) : 11.999996992323 electrons +N(Beta) : 11.999996992323 electrons +N(Total) : 23.999993984645 electrons +E(X) : -23.330645523794 Eh +E(C) : -0.806106026544 Eh +E(XC) : -24.136751550338 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.5084e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.1221e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.0867e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.0707e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.8144e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.3766e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 15.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361116 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006740663 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.490008171648 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001003 -0.000006746 0.000001316 + 2 O : 0.000000575 0.000000599 -0.000000719 + 3 O : 0.000002484 0.000008300 0.000000962 + 4 H : -0.000002057 -0.000002154 -0.000001559 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000116932 +RMS gradient ... 0.0000033755 +MAX gradient ... 0.0000082999 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.012507800 -0.016390595 -0.015840481 + 2 O : -0.015528184 0.012899469 -0.008867965 + 3 O : 0.008957202 -0.006246430 0.009797610 + 4 H : -0.005936818 0.009737556 0.014910836 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000905054 -0.0001061019 0.0000597318 + +Norm of the Cartesian gradient ... 0.0415911102 +RMS gradient ... 0.0120063193 +MAX gradient ... 0.0163905949 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.137 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.8%) +RI-J Coulomb gradient .... 0.061 sec ( 44.6%) +XC gradient .... 0.021 sec ( 15.6%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.490008172 Eh +Current gradient norm .... 0.041591110 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.150 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999930 +Lowest eigenvalues of augmented Hessian: + -0.000000023 0.054475592 0.330580765 0.396948857 0.514106013 +Length of the computed step .... 0.000374193 +The final length of the internal step .... 0.000374193 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0001527636 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001045478 RMS(Int)= 0.0001527641 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000011 +Previously predicted energy change .... -0.000000511 +Actually observed energy change .... -0.000000540 +Ratio of predicted to observed change .... 1.058277189 +New trust radius .... 0.225000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000005403 0.0000050000 YES + RMS gradient 0.0000329449 0.0001000000 YES + MAX gradient 0.0000719984 0.0003000000 YES + RMS step 0.0001527636 0.0020000000 YES + MAX step 0.0003190903 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.02 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2784 -0.000014 0.0001 1.2784 + 2. B(O 2,O 1) 1.3019 -0.000072 0.0001 1.3020 + 3. B(H 3,N 0) 1.0187 -0.000003 0.0000 1.0187 + 4. A(O 1,N 0,H 3) 118.22 0.000032 -0.02 118.21 + 5. A(N 0,O 1,O 2) 118.18 0.000009 -0.00 118.17 + 6. D(O 2,O 1,N 0,H 3) -96.92 0.031842 -0.00 -96.92 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (12.970 %) +Internal coordinates : 0.000 s ( 2.773 %) +B/P matrices and projection : 0.000 s (10.823 %) +Hessian update/contruction : 0.000 s (30.680 %) +Making the step : 0.000 s ( 5.277 %) +Converting the step to Cartesian: 0.000 s ( 3.757 %) +Storing new data : 0.000 s ( 2.952 %) +Checking convergence : 0.000 s ( 1.342 %) +Final printing : 0.000 s (29.249 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 12 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.501669 -0.492778 -0.211859 + O 0.377318 0.404546 -0.449709 + O 0.350875 1.494784 0.261537 + H -0.245232 -1.268707 0.396323 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.948017 -0.931216 -0.400356 + 1 O 8.0000 0 15.999 0.713027 0.764482 -0.849826 + 2 O 8.0000 0 15.999 0.663058 2.824731 0.494233 + 3 H 1.0000 0 1.008 -0.463421 -2.397509 0.748942 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.278429347326 0.00000000 0.00000000 + O 2 1 0 1.301993403317 118.17348291 0.00000000 + H 1 2 3 1.018681165352 118.20511091 263.07692328 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.415881348014 0.00000000 0.00000000 + O 2 1 0 2.460410960441 118.17348291 0.00000000 + H 1 2 3 1.925028420300 118.20511091 263.07692328 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.852172341856 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.803e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22305 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.8521723419 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.4963882285781835 0.00e+00 3.81e-06 3.18e-05 7.33e-06 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.4963882478770358 -1.93e-08 2.69e-06 2.01e-05 6.62e-06 0.0 + 3 -205.4963882500341867 -2.16e-09 3.51e-06 3.01e-05 1.79e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 3 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49638825003419 Eh -5591.84101 eV + +Components: +Nuclear Repulsion : 69.85217234185555 Eh 1900.77424 eV +Electronic Energy : -275.34856059188974 Eh -7492.61525 eV +One Electron Energy: -419.35709894517936 Eh -11411.28680 eV +Two Electron Energy: 144.00853835328965 Eh 3918.67155 eV + +Virial components: +Potential Energy : -410.29423911808038 Eh -11164.67385 eV +Kinetic Energy : 204.79785086804620 Eh 5572.83284 eV +Virial Ratio : 2.00341086285343 + +DFT components: +N(Alpha) : 11.999996996046 electrons +N(Beta) : 11.999996996046 electrons +N(Total) : 23.999993992093 electrons +E(X) : -23.330593920669 Eh +E(C) : -0.806100102635 Eh +E(XC) : -24.136694023305 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.1572e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.0075e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.5132e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 4.4395e-05 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.7937e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 8.3306e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.204428 -522.5791 + 1 2.0000 -19.049252 -518.3565 + 2 2.0000 -14.219511 -386.9326 + 3 2.0000 -1.255310 -34.1587 + 4 2.0000 -0.967123 -26.3168 + 5 2.0000 -0.708063 -19.2674 + 6 2.0000 -0.574276 -15.6269 + 7 2.0000 -0.521415 -14.1884 + 8 2.0000 -0.512737 -13.9523 + 9 2.0000 -0.325358 -8.8534 + 10 2.0000 -0.279506 -7.6058 + 11 2.0000 -0.226825 -6.1722 + 12 0.0000 -0.222433 -6.0527 + 13 0.0000 0.042447 1.1550 + 14 0.0000 0.115187 3.1344 + 15 0.0000 0.138126 3.7586 + 16 0.0000 0.243756 6.6329 + 17 0.0000 0.261976 7.1287 + 18 0.0000 0.319989 8.7074 + 19 0.0000 0.328942 8.9510 + 20 0.0000 0.349528 9.5111 + 21 0.0000 0.381627 10.3846 + 22 0.0000 0.390429 10.6241 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.432095 + 1 O : 0.193277 + 2 O : -0.071737 + 3 H : 0.310555 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.736636 s : 3.736636 + pz : 1.375072 p : 3.650608 + px : 1.139193 + py : 1.136343 + dz2 : 0.005340 d : 0.044850 + dxz : 0.006689 + dyz : 0.008820 + dx2y2 : 0.009823 + dxy : 0.014178 + + 1 O s : 3.771005 s : 3.771005 + pz : 1.440826 p : 3.911779 + px : 1.354140 + py : 1.116813 + dz2 : 0.022460 d : 0.123939 + dxz : 0.028107 + dyz : 0.022337 + dx2y2 : 0.018417 + dxy : 0.032618 + + 2 O s : 3.924782 s : 3.924782 + pz : 1.396854 p : 4.129456 + px : 1.544931 + py : 1.187671 + dz2 : 0.004835 d : 0.017499 + dxz : 0.002269 + dyz : 0.003708 + dx2y2 : 0.003105 + dxy : 0.003580 + + 3 H s : 0.654068 s : 0.654068 + pz : 0.014398 p : 0.035378 + px : 0.006778 + py : 0.014201 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.171446 + 1 O : -0.156948 + 2 O : 0.033494 + 3 H : 0.294899 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.237119 s : 3.237119 + pz : 1.289384 p : 3.634289 + px : 1.186560 + py : 1.158345 + dz2 : 0.028004 d : 0.300037 + dxz : 0.042956 + dyz : 0.055930 + dx2y2 : 0.085269 + dxy : 0.087879 + + 1 O s : 3.369193 s : 3.369193 + pz : 1.393377 p : 3.999885 + px : 1.354509 + py : 1.251998 + dz2 : 0.079819 d : 0.787870 + dxz : 0.088690 + dyz : 0.197840 + dx2y2 : 0.223318 + dxy : 0.198203 + + 2 O s : 3.611502 s : 3.611502 + pz : 1.367033 p : 4.104692 + px : 1.460193 + py : 1.277465 + dz2 : 0.043526 d : 0.250312 + dxz : 0.020346 + dyz : 0.082586 + dx2y2 : 0.051070 + dxy : 0.052784 + + 3 H s : 0.618775 s : 0.618775 + pz : 0.034752 p : 0.086326 + px : 0.017541 + py : 0.034033 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.4321 7.0000 -0.4321 2.5895 2.5895 -0.0000 + 1 O 7.8067 8.0000 0.1933 2.6855 2.6855 -0.0000 + 2 O 8.0717 8.0000 -0.0717 1.6725 1.6725 -0.0000 + 3 H 0.6894 1.0000 0.3106 0.8949 0.8949 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4280 B( 0-N , 2-O ) : 0.3726 B( 0-N , 3-H ) : 0.7888 +B( 1-O , 2-O ) : 1.2256 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.731 sec +Sum of individual times .... 0.721 sec ( 98.6%) + +SCF preparation .... 0.445 sec ( 60.8%) +Fock matrix formation .... 0.075 sec ( 10.2%) + Startup .... 0.005 sec ( 6.6% of F) + Split-RI-J .... 0.010 sec ( 13.8% of F) + XC integration .... 0.050 sec ( 67.0% of F) + Basis function eval. .... 0.003 sec ( 5.9% of XC) + Density eval. .... 0.004 sec ( 8.7% of XC) + XC-Functional eval. .... 0.002 sec ( 4.9% of XC) + XC-Potential eval. .... 0.004 sec ( 8.8% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.004 sec ( 0.6%) +Total Energy calculation .... 0.006 sec ( 0.8%) +Population analysis .... 0.162 sec ( 22.1%) +Orbital Transformation .... 0.006 sec ( 0.8%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.009 sec ( 1.2%) +SOSCF solution .... 0.015 sec ( 2.1%) +Finished LeanSCF after 0.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 15.6 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000361116 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006741182 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.490008183854 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.010.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.010.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.175908 0.892595 -0.224235 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.4963882500341867 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.555222582 0.952962167 -0.328752446 +Nuclear contribution : -0.312661349 -1.624606602 0.483358780 + ----------------------------------------- +Total Dipole Moment : 0.242561233 -0.671644435 0.154606333 + ----------------------------------------- +Magnitude (a.u.) : 0.730647190 +Magnitude (Debye) : 1.857157567 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.085922 0.421215 0.382435 +Rotational constants in MHz : 92513.604739 12627.710539 11465.114068 + +Dipole components along the rotational axes: +x,y,z [a.u.] : 0.495814 0.099284 0.527406 +x,y,z [Debye]: 1.260259 0.252359 1.340558 + + + +Dipole moment calculation done in 0.1 sec + +Maximum memory used throughout the entire PROP-calculation: 8.8 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 11 * + * * + * Dihedral ( 2, 1, 0, 3) : -87.69230769 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2789 0.755120 + 2. B(O 2,O 1) 1.3039 0.692502 + 3. B(H 3,N 0) 1.0218 0.419126 + 4. A(O 1,N 0,H 3) 118.0252 0.366597 + 5. A(N 0,O 1,O 2) 118.0741 0.446813 + 6. D(O 2,O 1,N 0,H 3) -87.6923 0.045336 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.493241 -0.507668 -0.243566 + O 0.362197 0.413578 -0.478192 + O 0.355182 1.467442 0.289531 + H -0.242847 -1.235508 0.428519 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.932090 -0.959354 -0.460272 + 1 O 8.0000 0 15.999 0.684453 0.781550 -0.903653 + 2 O 8.0000 0 15.999 0.671198 2.773063 0.547135 + 3 H 1.0000 0 1.008 -0.458914 -2.334771 0.809783 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.278429347326 0.00000000 0.00000000 + O 2 1 0 1.301993403317 118.17348291 0.00000000 + H 1 2 3 1.018681165352 118.20511091 263.07692328 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.415881348014 0.00000000 0.00000000 + O 2 1 0 2.460410960441 118.17348291 0.00000000 + H 1 2 3 1.925028420300 118.20511091 263.07692328 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.820649985361 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.802e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.8206499854 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.4875673923895079 0.00e+00 5.51e-04 4.48e-03 2.17e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( -0.002) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.4887810769318435 -1.21e-03 8.76e-04 6.25e-03 1.68e-02 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.4902617412616905 -1.48e-03 8.23e-04 6.03e-03 1.19e-02 0.700 0.0 + 4 -205.4914684179278197 -1.21e-03 2.55e-03 1.68e-02 8.48e-03 0.000 0.0 + 5 -205.4946604724594295 -3.19e-03 6.09e-04 4.72e-03 3.49e-03 0.000 0.0 + 6 -205.4950676506910554 -4.07e-04 5.49e-04 3.64e-03 4.09e-03 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 7 -205.4954942444142034 -4.27e-04 4.86e-04 4.60e-03 2.99e-03 0.0 + *** Restarting incremental Fock matrix formation *** + 8 -205.4957552533841749 -2.61e-04 1.20e-03 7.93e-03 4.49e-03 0.0 + 9 -205.4964173639607452 -6.62e-04 4.45e-03 2.96e-02 3.29e-03 0.0 + 10 -205.4958650242896852 5.52e-04 1.15e-03 1.02e-02 1.84e-02 0.0 + 11 -205.4972359614616266 -1.37e-03 8.16e-04 9.31e-03 8.23e-03 0.0 + 12 -205.4968319394408809 4.04e-04 9.61e-04 7.77e-03 8.82e-03 0.0 + 13 -205.4975950787863894 -7.63e-04 6.87e-05 8.87e-04 1.11e-03 0.0 + 14 -205.4976035495530482 -8.47e-06 2.94e-05 2.97e-04 2.05e-04 0.0 + 15 -205.4976044460267417 -8.96e-07 2.09e-05 2.56e-04 5.56e-05 0.0 + 16 -205.4976045911094502 -1.45e-07 8.89e-06 8.29e-05 4.14e-05 0.0 + 17 -205.4976046256778659 -3.46e-08 3.13e-06 2.04e-05 8.54e-06 0.0 + 18 -205.4976046282455968 -2.57e-09 6.50e-07 5.67e-06 6.80e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 18 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49760462824560 Eh -5591.87411 eV + +Components: +Nuclear Repulsion : 69.82064998536150 Eh 1899.91648 eV +Electronic Energy : -275.31825461360711 Eh -7491.79058 eV +One Electron Energy: -419.28883174409424 Eh -11409.42916 eV +Two Electron Energy: 143.97057713048713 Eh 3917.63857 eV + +Virial components: +Potential Energy : -410.31829148588457 Eh -11165.32835 eV +Kinetic Energy : 204.82068685763898 Eh 5573.45424 eV +Virial Ratio : 2.00330492872078 + +DFT components: +N(Alpha) : 11.999997990066 electrons +N(Beta) : 11.999997990066 electrons +N(Total) : 23.999995980132 electrons +E(X) : -23.331249942617 Eh +E(C) : -0.805995722738 Eh +E(XC) : -24.137245665355 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.5677e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.6666e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 6.4980e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.9924e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 6.8023e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.3432e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.204320 -522.5761 + 1 2.0000 -19.046562 -518.2833 + 2 2.0000 -14.223461 -387.0401 + 3 2.0000 -1.255077 -34.1524 + 4 2.0000 -0.965510 -26.2729 + 5 2.0000 -0.710247 -19.3268 + 6 2.0000 -0.575630 -15.6637 + 7 2.0000 -0.524160 -14.2631 + 8 2.0000 -0.507799 -13.8179 + 9 2.0000 -0.325713 -8.8631 + 10 2.0000 -0.279279 -7.5996 + 11 2.0000 -0.229544 -6.2462 + 12 0.0000 -0.223422 -6.0796 + 13 0.0000 0.042675 1.1612 + 14 0.0000 0.111437 3.0324 + 15 0.0000 0.136497 3.7143 + 16 0.0000 0.243378 6.6227 + 17 0.0000 0.260778 7.0961 + 18 0.0000 0.319138 8.6842 + 19 0.0000 0.328917 8.9503 + 20 0.0000 0.355834 9.6827 + 21 0.0000 0.377609 10.2753 + 22 0.0000 0.390344 10.6218 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.405885 + 1 O : 0.194567 + 2 O : -0.094339 + 3 H : 0.305657 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.734817 s : 3.734817 + pz : 1.577010 p : 3.623693 + px : 0.964047 + py : 1.082637 + dz2 : 0.008394 d : 0.047375 + dxz : 0.005629 + dyz : 0.009388 + dx2y2 : 0.011289 + dxy : 0.012676 + + 1 O s : 3.766371 s : 3.766371 + pz : 1.475668 p : 3.908957 + px : 1.289879 + py : 1.143410 + dz2 : 0.027372 d : 0.130105 + dxz : 0.027147 + dyz : 0.022270 + dx2y2 : 0.025544 + dxy : 0.027772 + + 2 O s : 3.928052 s : 3.928052 + pz : 1.465753 p : 4.151543 + px : 1.547550 + py : 1.138240 + dz2 : 0.004621 d : 0.014745 + dxz : 0.002147 + dyz : 0.002766 + dx2y2 : 0.003610 + dxy : 0.001602 + + 3 H s : 0.659638 s : 0.659638 + pz : 0.014911 p : 0.034704 + px : 0.005806 + py : 0.013987 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.163242 + 1 O : -0.149037 + 2 O : 0.019785 + 3 H : 0.292494 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.245261 s : 3.245261 + pz : 1.481796 p : 3.615249 + px : 1.016429 + py : 1.117024 + dz2 : 0.032069 d : 0.302732 + dxz : 0.041724 + dyz : 0.072208 + dx2y2 : 0.070338 + dxy : 0.086393 + + 1 O s : 3.371788 s : 3.371788 + pz : 1.453758 p : 4.001650 + px : 1.281260 + py : 1.266632 + dz2 : 0.102215 d : 0.775598 + dxz : 0.079729 + dyz : 0.201564 + dx2y2 : 0.200890 + dxy : 0.191199 + + 2 O s : 3.610552 s : 3.610552 + pz : 1.425290 p : 4.119051 + px : 1.469913 + py : 1.223848 + dz2 : 0.046152 d : 0.250612 + dxz : 0.020673 + dyz : 0.083397 + dx2y2 : 0.047005 + dxy : 0.053385 + + 3 H s : 0.622344 s : 0.622344 + pz : 0.037545 p : 0.085161 + px : 0.014706 + py : 0.032911 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.4059 7.0000 -0.4059 2.6612 2.6612 -0.0000 + 1 O 7.8054 8.0000 0.1946 2.6582 2.6582 -0.0000 + 2 O 8.0943 8.0000 -0.0943 1.6872 1.6872 -0.0000 + 3 H 0.6943 1.0000 0.3057 0.8975 0.8975 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4288 B( 0-N , 2-O ) : 0.4299 B( 0-N , 3-H ) : 0.8025 +B( 1-O , 2-O ) : 1.1959 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.284 sec +Sum of individual times .... 1.266 sec ( 98.6%) + +SCF preparation .... 0.448 sec ( 34.9%) +Fock matrix formation .... 0.407 sec ( 31.7%) + Startup .... 0.018 sec ( 4.3% of F) + Split-RI-J .... 0.059 sec ( 14.5% of F) + XC integration .... 0.265 sec ( 65.2% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.017 sec ( 6.4% of XC) + Density eval. .... 0.025 sec ( 9.5% of XC) + XC-Functional eval. .... 0.015 sec ( 5.5% of XC) + XC-Potential eval. .... 0.024 sec ( 9.0% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.029 sec ( 2.3%) +Total Energy calculation .... 0.035 sec ( 2.7%) +Population analysis .... 0.184 sec ( 14.3%) +Orbital Transformation .... 0.013 sec ( 1.0%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.089 sec ( 6.9%) +SOSCF solution .... 0.061 sec ( 4.7%) +Finished LeanSCF after 1.5 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 16.0 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000361578 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006761528 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.491204678305 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001002 -0.000006582 0.000001435 + 2 O : 0.000000549 0.000000606 -0.000000772 + 3 O : 0.000002440 0.000007955 0.000001109 + 4 H : -0.000001987 -0.000001979 -0.000001772 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000113634 +RMS gradient ... 0.0000032803 +MAX gradient ... 0.0000079552 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.023002565 0.032069499 0.026177693 + 2 O : 0.032249404 -0.018377060 0.004001872 + 3 O : -0.020396660 0.000766984 -0.011325937 + 4 H : 0.011149821 -0.014459423 -0.018853628 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000689194 -0.0000749997 0.0000019289 + +Norm of the Cartesian gradient ... 0.0697878157 +RMS gradient ... 0.0201460071 +MAX gradient ... 0.0322494035 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.137 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.9%) +RI-J Coulomb gradient .... 0.065 sec ( 47.3%) +XC gradient .... 0.022 sec ( 16.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.491204678 Eh +Current gradient norm .... 0.069787816 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.998631212 +Lowest eigenvalues of augmented Hessian: + -0.001249572 0.365776652 0.414301141 0.447295738 0.687796229 +Length of the computed step .... 0.052375638 +The final length of the internal step .... 0.052375638 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0213822647 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0233457518 RMS(Int)= 0.0214151288 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000005 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0097933046 0.0001000000 NO + MAX gradient 0.0229108033 0.0003000000 NO + RMS step 0.0213822647 0.0020000000 NO + MAX step 0.0512119564 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0046 Max(Angles) 2.93 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2789 -0.003413 0.0024 1.2813 + 2. B(O 2,O 1) 1.3039 -0.005946 0.0046 1.3084 + 3. B(H 3,N 0) 1.0218 0.000639 -0.0008 1.0210 + 4. A(O 1,N 0,H 3) 118.03 -0.001770 0.28 118.30 + 5. A(N 0,O 1,O 2) 118.07 -0.022911 2.93 121.01 + 6. D(O 2,O 1,N 0,H 3) -87.69 -0.044700 0.00 -87.69 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.264 %) +Internal coordinates : 0.000 s ( 3.666 %) +B/P matrices and projection : 0.000 s (17.889 %) +Hessian update/contruction : 0.000 s (26.686 %) +Making the step : 0.000 s ( 6.158 %) +Converting the step to Cartesian: 0.000 s ( 5.279 %) +Storing new data : 0.000 s ( 3.959 %) +Checking convergence : 0.000 s ( 0.000 %) +Final printing : 0.000 s (25.660 %) +Total time : 0.001 s + +Time for energy+gradient : 5.113 s +Time for complete geometry iter : 5.953 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.493064 -0.521171 -0.246807 + O 0.353412 0.416462 -0.461196 + O 0.368241 1.493883 0.281065 + H -0.247297 -1.251330 0.423230 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.931756 -0.984871 -0.466397 + 1 O 8.0000 0 15.999 0.667852 0.786999 -0.871534 + 2 O 8.0000 0 15.999 0.695875 2.823030 0.531136 + 3 H 1.0000 0 1.008 -0.467324 -2.364671 0.799788 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.281265420477 0.00000000 0.00000000 + O 2 1 0 1.308437154362 121.00827932 0.00000000 + H 1 2 3 1.021019900478 118.30163398 272.30769219 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.421240749566 0.00000000 0.00000000 + O 2 1 0 2.472587885192 121.00827932 0.00000000 + H 1 2 3 1.929447989187 118.30163398 272.30769219 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.426917601391 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.800e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22305 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.4969925890790137 0.00e+00 2.57e-04 1.83e-03 9.27e-03 0.700 0.1 +Warning: op=0 Small HOMO/LUMO gap ( 0.008) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.4972913015488416 -2.99e-04 2.91e-04 2.44e-03 7.26e-03 0.700 0.1 + ***Turning on AO-DIIS*** + 3 -205.4975301135496579 -2.39e-04 2.15e-04 1.91e-03 5.03e-03 0.700 0.1 + 4 -205.4976928308399238 -1.63e-04 5.27e-04 4.82e-03 3.47e-03 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.4980771960128436 -3.84e-04 5.87e-05 8.96e-04 7.76e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -205.4980760602555847 1.14e-06 1.77e-04 1.97e-03 8.84e-04 0.0 + 7 -205.4980190865277336 5.70e-05 1.37e-04 1.65e-03 4.16e-03 0.0 + 8 -205.4980804742482974 -6.14e-05 2.53e-05 2.11e-04 6.93e-05 0.0 + 9 -205.4980806017330224 -1.27e-07 2.82e-05 2.09e-04 1.30e-04 0.0 + 10 -205.4980809036769642 -3.02e-07 1.06e-05 7.08e-05 2.30e-05 0.0 + 11 -205.4980809308665357 -2.72e-08 8.60e-06 6.02e-05 1.26e-05 0.0 + 12 -205.4980809431960438 -1.23e-08 4.59e-06 3.29e-05 9.46e-06 0.0 + 13 -205.4980809464874483 -3.29e-09 7.84e-07 1.00e-05 1.75e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 13 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49808094648745 Eh -5591.88707 eV + +Components: +Nuclear Repulsion : 69.42691760139108 Eh 1889.20247 eV +Electronic Energy : -274.92499854787854 Eh -7481.08954 eV +One Electron Energy: -418.51752665860516 Eh -11388.44088 eV +Two Electron Energy: 143.59252811072665 Eh 3907.35134 eV + +Virial components: +Potential Energy : -410.29873656621851 Eh -11164.79623 eV +Kinetic Energy : 204.80065561973103 Eh 5572.90916 eV +Virial Ratio : 2.00340538620175 + +DFT components: +N(Alpha) : 11.999997568888 electrons +N(Beta) : 11.999997568888 electrons +N(Total) : 23.999995137775 electrons +E(X) : -23.325926020652 Eh +E(C) : -0.805498444283 Eh +E(XC) : -24.131424464934 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.2914e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.0043e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 7.8372e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.7567e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.7468e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.2405e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 1.3 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 16.1 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360895 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006638235 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.491803607380 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001106 -0.000006802 0.000001378 + 2 O : 0.000000537 0.000000606 -0.000000758 + 3 O : 0.000002602 0.000008438 0.000001122 + 4 H : -0.000002032 -0.000002242 -0.000001742 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000119179 +RMS gradient ... 0.0000034404 +MAX gradient ... 0.0000084375 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.024627777 0.024771507 0.021523357 + 2 O : 0.027361269 -0.019671939 0.014635036 + 3 O : -0.014494343 0.009356323 -0.014799738 + 4 H : 0.011760851 -0.014455892 -0.021358656 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000468773 -0.0000543905 -0.0000124944 + +Norm of the Cartesian gradient ... 0.0659799972 +RMS gradient ... 0.0190467846 +MAX gradient ... 0.0273612693 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.145 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.7%) +RI-J Coulomb gradient .... 0.066 sec ( 45.3%) +XC gradient .... 0.021 sec ( 14.2%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.491803607 Eh +Current gradient norm .... 0.065979997 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999993480 +Lowest eigenvalues of augmented Hessian: + -0.000006368 0.361488244 0.411017681 0.465151040 0.680871620 +Length of the computed step .... 0.003611044 +The final length of the internal step .... 0.003611044 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0014742026 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0009285496 RMS(Int)= 0.0014743496 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000003184 +Previously predicted energy change .... -0.000626500 +Actually observed energy change .... -0.000598929 +Ratio of predicted to observed change .... 0.955991904 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0005989291 0.0000050000 NO + RMS gradient 0.0007521979 0.0001000000 NO + MAX gradient 0.0009786617 0.0003000000 NO + RMS step 0.0014742026 0.0020000000 YES + MAX step 0.0022165100 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0011 Max(Angles) 0.13 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2813 0.000979 -0.0007 1.2806 + 2. B(O 2,O 1) 1.3084 -0.000860 0.0007 1.3091 + 3. B(H 3,N 0) 1.0210 -0.000841 0.0011 1.0221 + 4. A(O 1,N 0,H 3) 118.30 -0.000817 0.13 118.43 + 5. A(N 0,O 1,O 2) 121.01 0.000567 -0.06 120.95 + 6. D(O 2,O 1,N 0,H 3) -87.69 -0.048133 -0.00 -87.69 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 7.518 %) +Internal coordinates : 0.000 s ( 2.745 %) +B/P matrices and projection : 0.000 s (12.053 %) +Hessian update/contruction : 0.000 s (42.005 %) +Making the step : 0.000 s ( 5.609 %) +Converting the step to Cartesian: 0.000 s ( 3.699 %) +Storing new data : 0.000 s ( 2.983 %) +Checking convergence : 0.000 s ( 1.313 %) +Final printing : 0.000 s (21.957 %) +Total time : 0.001 s + +Time for energy+gradient : 4.673 s +Time for complete geometry iter : 5.481 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.492464 -0.520511 -0.246609 + O 0.353401 0.416555 -0.461931 + O 0.368111 1.494157 0.281254 + H -0.247756 -1.252356 0.423578 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.930621 -0.983624 -0.466023 + 1 O 8.0000 0 15.999 0.667831 0.787174 -0.872923 + 2 O 8.0000 0 15.999 0.695629 2.823547 0.531492 + 3 H 1.0000 0 1.008 -0.468191 -2.366610 0.800446 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.280602534467 0.00000000 0.00000000 + O 2 1 0 1.309108626274 120.95088969 0.00000000 + H 1 2 3 1.022070840592 118.42863065 272.30769219 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.419988076549 0.00000000 0.00000000 + O 2 1 0 2.473856783213 120.95088969 0.00000000 + H 1 2 3 1.931433978185 118.42863065 272.30769219 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.423142032598 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.807e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22305 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.4980844128634772 0.00e+00 3.65e-05 3.89e-04 6.13e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.4980862886067712 -1.88e-06 2.10e-05 2.08e-04 1.26e-04 0.1 + 3 -205.4980861676856421 1.21e-07 1.00e-05 1.35e-04 1.88e-04 0.0 + 4 -205.4980865305146835 -3.63e-07 4.48e-06 3.35e-05 1.51e-05 0.0 + 5 -205.4980865428396442 -1.23e-08 5.84e-06 5.17e-05 1.22e-05 0.0 + 6 -205.4980865444542246 -1.61e-09 7.21e-06 5.34e-05 3.74e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 6 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49808654445422 Eh -5591.88722 eV + +Components: +Nuclear Repulsion : 69.42314203259842 Eh 1889.09973 eV +Electronic Energy : -274.92122857705266 Eh -7480.98696 eV +One Electron Energy: -418.51270680579671 Eh -11388.30972 eV +Two Electron Energy: 143.59147822874405 Eh 3907.32277 eV + +Virial components: +Potential Energy : -410.29711610926461 Eh -11164.75213 eV +Kinetic Energy : 204.79902956481041 Eh 5572.86491 eV +Virial Ratio : 2.00341338033256 + +DFT components: +N(Alpha) : 11.999997585705 electrons +N(Beta) : 11.999997585705 electrons +N(Total) : 23.999995171411 electrons +E(X) : -23.325505872374 Eh +E(C) : -0.805497885077 Eh +E(XC) : -24.131003757451 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.6146e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.3389e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 7.2131e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.7827e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.7356e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.5859e-04 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 16.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360894 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006638999 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.491808439436 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001108 -0.000006801 0.000001377 + 2 O : 0.000000537 0.000000607 -0.000000761 + 3 O : 0.000002601 0.000008443 0.000001122 + 4 H : -0.000002030 -0.000002250 -0.000001737 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000119216 +RMS gradient ... 0.0000034415 +MAX gradient ... 0.0000084434 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.024524497 0.025582834 0.021035039 + 2 O : 0.027240629 -0.019918771 0.014099622 + 3 O : -0.014540432 0.009402143 -0.014475698 + 4 H : 0.011824301 -0.015066205 -0.020658963 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000243555 -0.0000565508 -0.0000429320 + +Norm of the Cartesian gradient ... 0.0658709460 +RMS gradient ... 0.0190153042 +MAX gradient ... 0.0272406289 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.113 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.0%) +RI-J Coulomb gradient .... 0.054 sec ( 47.8%) +XC gradient .... 0.017 sec ( 15.4%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.491808439 Eh +Current gradient norm .... 0.065870946 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999977776 +Lowest eigenvalues of augmented Hessian: + -0.000007470 0.157603848 0.436292938 0.540281692 0.655144544 +Length of the computed step .... 0.006667112 +The final length of the internal step .... 0.006667112 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0027218372 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0017252387 RMS(Int)= 0.0027217143 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000003735 +Previously predicted energy change .... -0.000003184 +Actually observed energy change .... -0.000004832 +Ratio of predicted to observed change .... 1.517678084 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000048321 0.0000050000 YES + RMS gradient 0.0004932898 0.0001000000 NO + MAX gradient 0.0007532510 0.0003000000 NO + RMS step 0.0027218372 0.0020000000 NO + MAX step 0.0052065387 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0015 Max(Angles) 0.30 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2806 0.000753 -0.0015 1.2791 + 2. B(O 2,O 1) 1.3091 -0.000644 0.0015 1.3106 + 3. B(H 3,N 0) 1.0221 0.000080 0.0005 1.0225 + 4. A(O 1,N 0,H 3) 118.43 -0.000675 0.30 118.73 + 5. A(N 0,O 1,O 2) 120.95 0.000127 -0.06 120.90 + 6. D(O 2,O 1,N 0,H 3) -87.69 -0.047861 -0.00 -87.69 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.738 %) +Internal coordinates : 0.000 s ( 3.523 %) +B/P matrices and projection : 0.000 s (14.262 %) +Hessian update/contruction : 0.000 s (29.362 %) +Making the step : 0.000 s ( 5.705 %) +Converting the step to Cartesian: 0.000 s ( 4.362 %) +Storing new data : 0.000 s ( 3.356 %) +Checking convergence : 0.000 s ( 1.678 %) +Final printing : 0.000 s (26.678 %) +Total time : 0.001 s + +Time for energy+gradient : 4.251 s +Time for complete geometry iter : 4.975 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 4 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.490900 -0.519764 -0.245712 + O 0.353063 0.416535 -0.462961 + O 0.368038 1.495092 0.281416 + H -0.248910 -1.254019 0.423548 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.927666 -0.982212 -0.464328 + 1 O 8.0000 0 15.999 0.667192 0.787137 -0.874869 + 2 O 8.0000 0 15.999 0.695492 2.825314 0.531799 + 3 H 1.0000 0 1.008 -0.470371 -2.369752 0.800390 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.279111642323 0.00000000 0.00000000 + O 2 1 0 1.310574357722 120.89562769 0.00000000 + H 1 2 3 1.022544887637 118.72694334 272.30769219 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.417170698700 0.00000000 0.00000000 + O 2 1 0 2.476626614234 120.89562769 0.00000000 + H 1 2 3 1.932329797274 118.72694334 272.30769219 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.419462657755 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.821e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22305 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.4980800506501168 0.00e+00 6.93e-05 4.64e-04 1.12e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.4980877073569445 -7.66e-06 4.27e-05 3.81e-04 1.80e-04 0.0 + 3 -205.4980866670196633 1.04e-06 3.36e-05 4.19e-04 6.29e-04 0.0 + 4 -205.4980884823230554 -1.82e-06 2.46e-05 2.91e-04 1.62e-04 0.0 + 5 -205.4980878537361377 6.29e-07 1.63e-05 2.18e-04 3.02e-04 0.0 + 6 -205.4980888115412654 -9.58e-07 7.97e-06 6.09e-05 2.32e-05 0.0 + 7 -205.4980888378589725 -2.63e-08 1.28e-05 9.71e-05 1.42e-05 0.0 + 8 -205.4980888584851755 -2.06e-08 3.56e-06 2.15e-05 4.82e-06 0.0 + 9 -205.4980888607822180 -2.30e-09 8.65e-07 9.13e-06 2.95e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49808886078222 Eh -5591.88728 eV + +Components: +Nuclear Repulsion : 69.41946265775471 Eh 1888.99961 eV +Electronic Energy : -274.91755151853692 Eh -7480.88690 eV +One Electron Energy: -418.50886813232739 Eh -11388.20527 eV +Two Electron Energy: 143.59131661379044 Eh 3907.31837 eV + +Virial components: +Potential Energy : -410.29578347037648 Eh -11164.71587 eV +Kinetic Energy : 204.79769460959423 Eh 5572.82859 eV +Virial Ratio : 2.00341993230209 + +DFT components: +N(Alpha) : 11.999997647123 electrons +N(Beta) : 11.999997647123 electrons +N(Total) : 23.999995294246 electrons +E(X) : -23.325241998440 Eh +E(C) : -0.805516670395 Eh +E(XC) : -24.130758668835 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.2970e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 9.1271e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 8.6514e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.0373e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.9463e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.1514e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 16.5 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360877 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006635872 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.491813866461 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001112 -0.000006803 0.000001373 + 2 O : 0.000000537 0.000000607 -0.000000766 + 3 O : 0.000002601 0.000008460 0.000001122 + 4 H : -0.000002026 -0.000002263 -0.000001729 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000119355 +RMS gradient ... 0.0000034455 +MAX gradient ... 0.0000084597 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.024037124 0.026084436 0.020751882 + 2 O : 0.026826295 -0.020248569 0.013307566 + 3 O : -0.014468495 0.009538192 -0.013933405 + 4 H : 0.011679324 -0.015374059 -0.020126044 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000493651 -0.0000587138 -0.0000124760 + +Norm of the Cartesian gradient ... 0.0653287677 +RMS gradient ... 0.0188587908 +MAX gradient ... 0.0268262954 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.116 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.0%) +RI-J Coulomb gradient .... 0.053 sec ( 45.9%) +XC gradient .... 0.018 sec ( 15.7%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.491813866 Eh +Current gradient norm .... 0.065328768 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999976449 +Lowest eigenvalues of augmented Hessian: + -0.000004572 0.082748817 0.434163155 0.551543824 0.701964472 +Length of the computed step .... 0.006863235 +The final length of the internal step .... 0.006863235 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0028019041 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0017523176 RMS(Int)= 0.0028014461 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000002286 +Previously predicted energy change .... -0.000003735 +Actually observed energy change .... -0.000005427 +Ratio of predicted to observed change .... 1.452940910 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000054270 0.0000050000 NO + RMS gradient 0.0003753642 0.0001000000 NO + MAX gradient 0.0006377352 0.0003000000 NO + RMS step 0.0028019041 0.0020000000 NO + MAX step 0.0055540004 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0016 Max(Angles) 0.32 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2791 0.000420 -0.0016 1.2775 + 2. B(O 2,O 1) 1.3106 -0.000234 0.0014 1.3119 + 3. B(H 3,N 0) 1.0225 0.000638 -0.0004 1.0221 + 4. A(O 1,N 0,H 3) 118.73 -0.000407 0.32 119.05 + 5. A(N 0,O 1,O 2) 120.90 -0.000205 -0.02 120.88 + 6. D(O 2,O 1,N 0,H 3) -87.69 -0.047251 0.00 -87.69 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (12.405 %) +Internal coordinates : 0.000 s ( 3.026 %) +B/P matrices and projection : 0.000 s (12.708 %) +Hessian update/contruction : 0.000 s (30.711 %) +Making the step : 0.000 s ( 5.749 %) +Converting the step to Cartesian: 0.000 s ( 3.933 %) +Storing new data : 0.000 s ( 3.328 %) +Checking convergence : 0.000 s ( 1.362 %) +Final printing : 0.000 s (26.475 %) +Total time : 0.001 s + +Time for energy+gradient : 4.471 s +Time for complete geometry iter : 5.231 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 5 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.489149 -0.519334 -0.244553 + O 0.352539 0.416436 -0.463670 + O 0.368071 1.496167 0.281409 + H -0.250169 -1.255425 0.423106 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.924358 -0.981399 -0.462139 + 1 O 8.0000 0 15.999 0.666202 0.786951 -0.876208 + 2 O 8.0000 0 15.999 0.695553 2.827345 0.531785 + 3 H 1.0000 0 1.008 -0.472750 -2.372410 0.799555 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.277543168188 0.00000000 0.00000000 + O 2 1 0 1.311945422687 120.87866155 0.00000000 + H 1 2 3 1.022111342070 119.04516412 272.30769219 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.414206712137 0.00000000 0.00000000 + O 2 1 0 2.479217551529 120.87866155 0.00000000 + H 1 2 3 1.931510514886 119.04516412 272.30769219 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.421509321306 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.833e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.4980764512778819 0.00e+00 6.99e-05 6.62e-04 1.20e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.4980843676761424 -7.92e-06 5.66e-05 5.24e-04 2.98e-04 0.0 + 3 -205.4980807299425578 3.64e-06 4.16e-05 5.34e-04 1.13e-03 0.0 + 4 -205.4980856051058140 -4.88e-06 1.45e-05 1.32e-04 5.61e-05 0.0 + 5 -205.4980855862381759 1.89e-08 1.28e-05 1.08e-04 1.22e-04 0.0 + 6 -205.4980857829480101 -1.97e-07 1.18e-05 8.24e-05 2.15e-05 0.0 + 7 -205.4980858161856645 -3.32e-08 9.93e-06 7.43e-05 9.59e-06 0.0 + 8 -205.4980858278490246 -1.17e-08 2.01e-06 1.80e-05 8.30e-06 0.0 + 9 -205.4980858300207274 -2.17e-09 1.20e-06 1.34e-05 3.70e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49808583002073 Eh -5591.88720 eV + +Components: +Nuclear Repulsion : 69.42150932130619 Eh 1889.05531 eV +Electronic Energy : -274.91959515132692 Eh -7480.94251 eV +One Electron Energy: -418.51537443703012 Eh -11388.38231 eV +Two Electron Energy: 143.59577928570323 Eh 3907.43980 eV + +Virial components: +Potential Energy : -410.29601095172563 Eh -11164.72206 eV +Kinetic Energy : 204.79792512170488 Eh 5572.83486 eV +Virial Ratio : 2.00341878809514 + +DFT components: +N(Alpha) : 11.999997715922 electrons +N(Beta) : 11.999997715922 electrons +N(Total) : 23.999995431844 electrons +E(X) : -23.325449696511 Eh +E(C) : -0.805552504920 Eh +E(XC) : -24.131002201431 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.1717e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.3419e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.1975e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.8761e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.7035e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 4.2279e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.1 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 16.7 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360853 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006630092 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.491816591202 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001117 -0.000006808 0.000001371 + 2 O : 0.000000537 0.000000606 -0.000000771 + 3 O : 0.000002601 0.000008477 0.000001122 + 4 H : -0.000002021 -0.000002274 -0.000001722 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000119514 +RMS gradient ... 0.0000034501 +MAX gradient ... 0.0000084770 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.023311940 0.026034565 0.020814830 + 2 O : 0.026231595 -0.020594663 0.012694569 + 3 O : -0.014292852 0.009699654 -0.013450932 + 4 H : 0.011373197 -0.015139556 -0.020058467 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000519599 -0.0000618241 -0.0000101678 + +Norm of the Cartesian gradient ... 0.0645607112 +RMS gradient ... 0.0186370720 +MAX gradient ... 0.0262315948 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.138 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.9%) +RI-J Coulomb gradient .... 0.065 sec ( 47.0%) +XC gradient .... 0.020 sec ( 14.4%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.491816591 Eh +Current gradient norm .... 0.064560711 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999997986 +Lowest eigenvalues of augmented Hessian: + -0.000000742 0.073148103 0.434387654 0.572030977 0.629018737 +Length of the computed step .... 0.002007021 +The final length of the internal step .... 0.002007021 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0008193628 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0005464488 RMS(Int)= 0.0008193090 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000371 +Previously predicted energy change .... -0.000002286 +Actually observed energy change .... -0.000002725 +Ratio of predicted to observed change .... 1.191925443 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000027247 0.0000050000 YES + RMS gradient 0.0002367682 0.0001000000 NO + MAX gradient 0.0004666450 0.0003000000 NO + RMS step 0.0008193628 0.0020000000 YES + MAX step 0.0016431376 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0005 Max(Angles) 0.09 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2775 0.000015 -0.0003 1.2772 + 2. B(O 2,O 1) 1.3119 0.000169 0.0001 1.3121 + 3. B(H 3,N 0) 1.0221 0.000467 -0.0005 1.0216 + 4. A(O 1,N 0,H 3) 119.05 -0.000173 0.09 119.14 + 5. A(N 0,O 1,O 2) 120.88 -0.000245 0.02 120.90 + 6. D(O 2,O 1,N 0,H 3) -87.69 -0.046578 0.00 -87.69 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (11.788 %) +Internal coordinates : 0.000 s ( 3.046 %) +B/P matrices and projection : 0.000 s (12.185 %) +Hessian update/contruction : 0.000 s (30.861 %) +Making the step : 0.000 s ( 4.768 %) +Converting the step to Cartesian: 0.000 s ( 4.106 %) +Storing new data : 0.000 s ( 3.046 %) +Checking convergence : 0.000 s ( 1.325 %) +Final printing : 0.000 s (28.609 %) +Total time : 0.001 s + +Time for energy+gradient : 4.526 s +Time for complete geometry iter : 5.304 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 6 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.488625 -0.519384 -0.244132 + O 0.352337 0.416499 -0.463651 + O 0.368147 1.496501 0.281260 + H -0.250567 -1.255772 0.422815 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.923368 -0.981494 -0.461342 + 1 O 8.0000 0 15.999 0.665821 0.787069 -0.876174 + 2 O 8.0000 0 15.999 0.695696 2.827977 0.531504 + 3 H 1.0000 0 1.008 -0.473502 -2.373064 0.799005 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.277217203161 0.00000000 0.00000000 + O 2 1 0 1.312077449856 120.89729477 0.00000000 + H 1 2 3 1.021643750667 119.13930897 272.30769219 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.413590727508 0.00000000 0.00000000 + O 2 1 0 2.479467046721 120.89729477 0.00000000 + H 1 2 3 1.930626895193 119.13930897 272.30769219 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.425564562271 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.834e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.4980827028969088 0.00e+00 1.91e-05 2.61e-04 3.76e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.4980832601836482 -5.57e-07 1.54e-05 1.35e-04 8.13e-05 0.0 + 3 -205.4980830328435104 2.27e-07 1.20e-05 1.53e-04 2.97e-04 0.0 + 4 -205.4980833665355817 -3.34e-07 5.88e-06 5.13e-05 2.71e-05 0.0 + 5 -205.4980833549277008 1.16e-08 3.02e-06 3.54e-05 5.32e-05 0.0 + 6 -205.4980833855209994 -3.06e-08 3.05e-06 2.16e-05 6.15e-06 0.0 + 7 -205.4980833882183333 -2.70e-09 3.32e-06 2.46e-05 4.42e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49808338821833 Eh -5591.88714 eV + +Components: +Nuclear Repulsion : 69.42556456227133 Eh 1889.16566 eV +Electronic Energy : -274.92364795048968 Eh -7481.05279 eV +One Electron Energy: -418.52312621171069 Eh -11388.59325 eV +Two Electron Energy: 143.59947826122101 Eh 3907.54046 eV + +Virial components: +Potential Energy : -410.29672425970574 Eh -11164.74147 eV +Kinetic Energy : 204.79864087148741 Eh 5572.85434 eV +Virial Ratio : 2.00341526932872 + +DFT components: +N(Alpha) : 11.999997725303 electrons +N(Beta) : 11.999997725303 electrons +N(Total) : 23.999995450606 electrons +E(X) : -23.325688705494 Eh +E(C) : -0.805569672714 Eh +E(XC) : -24.131258378208 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.6973e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.4573e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.3188e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.3641e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.4250e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.1801e-04 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 16.9 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360844 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006627158 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.491817073456 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001119 -0.000006811 0.000001370 + 2 O : 0.000000536 0.000000606 -0.000000771 + 3 O : 0.000002602 0.000008482 0.000001121 + 4 H : -0.000002019 -0.000002277 -0.000001720 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000119568 +RMS gradient ... 0.0000034516 +MAX gradient ... 0.0000084820 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.023059829 0.025752183 0.020974782 + 2 O : 0.026034145 -0.020574761 0.012674431 + 3 O : -0.014199929 0.009697964 -0.013417397 + 4 H : 0.011225613 -0.014875386 -0.020231817 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000408263 -0.0000668148 -0.0000150408 + +Norm of the Cartesian gradient ... 0.0642568575 +RMS gradient ... 0.0185493570 +MAX gradient ... 0.0260341451 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.128 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 4.1%) +RI-J Coulomb gradient .... 0.059 sec ( 46.5%) +XC gradient .... 0.020 sec ( 15.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.491817073 Eh +Current gradient norm .... 0.064256857 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999595 +Lowest eigenvalues of augmented Hessian: + -0.000000205 0.072537771 0.389973535 0.435324723 0.638346436 +Length of the computed step .... 0.000899889 +The final length of the internal step .... 0.000899889 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0003673782 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0002499841 RMS(Int)= 0.0003673685 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000103 +Previously predicted energy change .... -0.000000371 +Actually observed energy change .... -0.000000482 +Ratio of predicted to observed change .... 1.299248064 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000004823 0.0000050000 YES + RMS gradient 0.0001105117 0.0001000000 NO + MAX gradient 0.0001894113 0.0003000000 YES + RMS step 0.0003673782 0.0020000000 YES + MAX step 0.0006742858 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0002 Max(Angles) 0.04 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2772 -0.000051 -0.0000 1.2772 + 2. B(O 2,O 1) 1.3121 0.000189 -0.0002 1.3119 + 3. B(H 3,N 0) 1.0216 0.000137 -0.0002 1.0214 + 4. A(O 1,N 0,H 3) 119.14 -0.000098 0.04 119.18 + 5. A(N 0,O 1,O 2) 120.90 -0.000080 0.01 120.91 + 6. D(O 2,O 1,N 0,H 3) -87.69 -0.046395 -0.00 -87.69 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (12.117 %) +Internal coordinates : 0.000 s ( 3.329 %) +B/P matrices and projection : 0.000 s (13.715 %) +Hessian update/contruction : 0.000 s (27.830 %) +Making the step : 0.000 s ( 6.658 %) +Converting the step to Cartesian: 0.000 s ( 3.995 %) +Storing new data : 0.000 s ( 3.329 %) +Checking convergence : 0.000 s ( 1.465 %) +Final printing : 0.000 s (27.164 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 6 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.488424 -0.519439 -0.243935 + O 0.352273 0.416634 -0.463571 + O 0.368183 1.496574 0.281124 + H -0.250740 -1.255925 0.422673 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.922988 -0.981598 -0.460969 + 1 O 8.0000 0 15.999 0.665700 0.787324 -0.876022 + 2 O 8.0000 0 15.999 0.695764 2.828116 0.531247 + 3 H 1.0000 0 1.008 -0.473829 -2.373355 0.798736 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.277202222276 0.00000000 0.00000000 + O 2 1 0 1.311904852360 120.90970614 0.00000000 + H 1 2 3 1.021406485548 119.17794269 272.30769219 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.413562417738 0.00000000 0.00000000 + O 2 1 0 2.479140884722 120.90970614 0.00000000 + H 1 2 3 1.930178529097 119.17794269 272.30769219 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.429892384647 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.832e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.4298923846 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.4980819373821532 0.00e+00 9.48e-06 1.06e-04 1.82e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.4980820541375692 -1.17e-07 4.72e-06 4.81e-05 2.25e-05 0.0 + 3 -205.4980820615373887 -7.40e-09 4.71e-06 3.92e-05 3.35e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 3 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49808206153739 Eh -5591.88710 eV + +Components: +Nuclear Repulsion : 69.42989238464658 Eh 1889.28342 eV +Electronic Energy : -274.92797444618395 Eh -7481.17052 eV +One Electron Energy: -418.53163240346078 Eh -11388.82471 eV +Two Electron Energy: 143.60365795727682 Eh 3907.65419 eV + +Virial components: +Potential Energy : -410.29700438483007 Eh -11164.74909 eV +Kinetic Energy : 204.79892232329269 Eh 5572.86200 eV +Virial Ratio : 2.00341388387357 + +DFT components: +N(Alpha) : 11.999997716793 electrons +N(Beta) : 11.999997716793 electrons +N(Total) : 23.999995433585 electrons +E(X) : -23.325893554228 Eh +E(C) : -0.805581244324 Eh +E(XC) : -24.131474798552 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 7.3998e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.9230e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.7055e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.7535e-05 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.3472e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.1222e-04 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.201082 -522.4880 + 1 2.0000 -19.045836 -518.2636 + 2 2.0000 -14.227422 -387.1478 + 3 2.0000 -1.248237 -33.9663 + 4 2.0000 -0.967432 -26.3252 + 5 2.0000 -0.710205 -19.3257 + 6 2.0000 -0.575329 -15.6555 + 7 2.0000 -0.521619 -14.1940 + 8 2.0000 -0.504798 -13.7362 + 9 2.0000 -0.325980 -8.8704 + 10 2.0000 -0.278622 -7.5817 + 11 2.0000 -0.230872 -6.2824 + 12 0.0000 -0.222286 -6.0487 + 13 0.0000 0.032793 0.8923 + 14 0.0000 0.110661 3.0112 + 15 0.0000 0.137853 3.7512 + 16 0.0000 0.243416 6.6237 + 17 0.0000 0.260666 7.0931 + 18 0.0000 0.318453 8.6655 + 19 0.0000 0.329553 8.9676 + 20 0.0000 0.352135 9.5821 + 21 0.0000 0.376892 10.2558 + 22 0.0000 0.394553 10.7363 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.396083 + 1 O : 0.196648 + 2 O : -0.105122 + 3 H : 0.304558 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.731065 s : 3.731065 + pz : 1.579563 p : 3.616739 + px : 0.973976 + py : 1.063200 + dz2 : 0.008203 d : 0.048279 + dxz : 0.005661 + dyz : 0.009948 + dx2y2 : 0.011175 + dxy : 0.013293 + + 1 O s : 3.758562 s : 3.758562 + pz : 1.490779 p : 3.916258 + px : 1.289426 + py : 1.136053 + dz2 : 0.026275 d : 0.128533 + dxz : 0.024944 + dyz : 0.023720 + dx2y2 : 0.025046 + dxy : 0.028548 + + 2 O s : 3.931359 s : 3.931359 + pz : 1.511184 p : 4.159446 + px : 1.533461 + py : 1.114801 + dz2 : 0.004594 d : 0.014317 + dxz : 0.001993 + dyz : 0.002023 + dx2y2 : 0.004236 + dxy : 0.001470 + + 3 H s : 0.660760 s : 0.660760 + pz : 0.014831 p : 0.034683 + px : 0.005809 + py : 0.014043 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.152660 + 1 O : -0.157653 + 2 O : 0.018433 + 3 H : 0.291879 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.243605 s : 3.243605 + pz : 1.483036 p : 3.607587 + px : 1.020011 + py : 1.104539 + dz2 : 0.031645 d : 0.301468 + dxz : 0.040507 + dyz : 0.073447 + dx2y2 : 0.069087 + dxy : 0.086783 + + 1 O s : 3.370799 s : 3.370799 + pz : 1.462937 p : 4.005642 + px : 1.277935 + py : 1.264770 + dz2 : 0.102140 d : 0.781212 + dxz : 0.076483 + dyz : 0.203132 + dx2y2 : 0.204674 + dxy : 0.194783 + + 2 O s : 3.616699 s : 3.616699 + pz : 1.459908 p : 4.120294 + px : 1.456631 + py : 1.203754 + dz2 : 0.043645 d : 0.244574 + dxz : 0.018361 + dyz : 0.083484 + dx2y2 : 0.048009 + dxy : 0.051075 + + 3 H s : 0.622891 s : 0.622891 + pz : 0.037509 p : 0.085229 + px : 0.014633 + py : 0.033088 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3961 7.0000 -0.3961 2.6927 2.6927 -0.0000 + 1 O 7.8034 8.0000 0.1966 2.6528 2.6528 -0.0000 + 2 O 8.1051 8.0000 -0.1051 1.6982 1.6982 0.0000 + 3 H 0.6954 1.0000 0.3046 0.8980 0.8980 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4345 B( 0-N , 2-O ) : 0.4535 B( 0-N , 3-H ) : 0.8047 +B( 1-O , 2-O ) : 1.1849 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.750 sec +Sum of individual times .... 0.739 sec ( 98.6%) + +SCF preparation .... 0.423 sec ( 56.4%) +Fock matrix formation .... 0.071 sec ( 9.4%) + Startup .... 0.005 sec ( 7.0% of F) + Split-RI-J .... 0.010 sec ( 14.1% of F) + XC integration .... 0.046 sec ( 65.3% of F) + Basis function eval. .... 0.003 sec ( 6.7% of XC) + Density eval. .... 0.003 sec ( 6.7% of XC) + XC-Functional eval. .... 0.002 sec ( 5.4% of XC) + XC-Potential eval. .... 0.004 sec ( 8.3% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.004 sec ( 0.6%) +Total Energy calculation .... 0.006 sec ( 0.7%) +Population analysis .... 0.206 sec ( 27.5%) +Orbital Transformation .... 0.006 sec ( 0.8%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.009 sec ( 1.1%) +SOSCF solution .... 0.015 sec ( 2.0%) +Finished LeanSCF after 1.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 17.2 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360840 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006625720 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.491817181361 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.011.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.011.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.178167 0.887028 -0.237545 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.4980820615373887 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.443746811 0.990729465 -0.242107018 +Nuclear contribution : -0.319033311 -1.609688931 0.514842863 + ----------------------------------------- +Total Dipole Moment : 0.124713500 -0.618959466 0.272735845 + ----------------------------------------- +Magnitude (a.u.) : 0.687785663 +Magnitude (Debye) : 1.748212224 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.221560 0.409285 0.374189 +Rotational constants in MHz : 96579.932004 12270.060282 11217.906578 + +Dipole components along the rotational axes: +x,y,z [a.u.] : 0.461286 0.124345 0.494775 +x,y,z [Debye]: 1.172497 0.316061 1.257618 + + + +Dipole moment calculation done in 0.1 sec + +Maximum memory used throughout the entire PROP-calculation: 9.6 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 12 * + * * + * Dihedral ( 2, 1, 0, 3) : -78.46153846 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2778 0.758532 + 2. B(O 2,O 1) 1.3136 0.667741 + 3. B(H 3,N 0) 1.0242 0.414951 + 4. A(O 1,N 0,H 3) 118.9949 0.366252 + 5. A(N 0,O 1,O 2) 120.7921 0.444238 + 6. D(O 2,O 1,N 0,H 3) -78.4615 0.045796 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.477200 -0.535147 -0.272262 + O 0.335630 0.426315 -0.490364 + O 0.372701 1.469584 0.307059 + H -0.249839 -1.222908 0.451858 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.901777 -1.011281 -0.514501 + 1 O 8.0000 0 15.999 0.634248 0.805619 -0.926653 + 2 O 8.0000 0 15.999 0.704303 2.777111 0.580258 + 3 H 1.0000 0 1.008 -0.472127 -2.310962 0.853888 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.277202222276 0.00000000 0.00000000 + O 2 1 0 1.311904852360 120.90970614 0.00000000 + H 1 2 3 1.021406485548 119.17794269 272.30769219 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.413562417738 0.00000000 0.00000000 + O 2 1 0 2.479140884722 120.90970614 0.00000000 + H 1 2 3 1.930178529097 119.17794269 272.30769219 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.401532592614 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.847e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22308 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.4015325926 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5020541470138653 0.00e+00 5.59e-04 4.38e-03 1.86e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.018) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5031432023136801 -1.09e-03 7.64e-04 5.25e-03 1.44e-02 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.5043017547954207 -1.16e-03 6.47e-04 5.15e-03 1.05e-02 0.700 0.0 + 4 -205.5051659801544872 -8.64e-04 1.84e-03 1.53e-02 7.57e-03 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5073358999989921 -2.17e-03 3.21e-04 2.73e-03 2.19e-03 0.0 + *** Restarting incremental Fock matrix formation *** + 6 -205.5074554909101323 -1.20e-04 8.65e-04 6.22e-03 3.18e-03 0.1 + 7 -205.5071775383626402 2.78e-04 5.91e-04 4.23e-03 1.18e-02 0.0 + 8 -205.5077476396797636 -5.70e-04 2.44e-04 2.20e-03 7.15e-04 0.0 + 9 -205.5077660382401916 -1.84e-05 1.80e-04 1.39e-03 4.69e-04 0.0 + 10 -205.5077637423976000 2.30e-06 7.22e-05 6.28e-04 8.14e-04 0.0 + 11 -205.5077699574789847 -6.22e-06 3.48e-05 3.08e-04 1.17e-04 0.0 + 12 -205.5077701729523767 -2.15e-07 1.32e-05 9.59e-05 4.99e-05 0.0 + 13 -205.5077702443685723 -7.14e-08 2.06e-06 2.51e-05 8.01e-06 0.0 + 14 -205.5077702458632700 -1.49e-09 1.11e-06 8.23e-06 4.39e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 14 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50777024586327 Eh -5592.15073 eV + +Components: +Nuclear Repulsion : 69.40153259261407 Eh 1888.51171 eV +Electronic Energy : -274.90930283847734 Eh -7480.66244 eV +One Electron Energy: -418.48700529510683 Eh -11387.61035 eV +Two Electron Energy: 143.57770245662948 Eh 3906.94791 eV + +Virial components: +Potential Energy : -410.33486448003703 Eh -11165.77932 eV +Kinetic Energy : 204.82709423417376 Eh 5573.62859 eV +Virial Ratio : 2.00332317369552 + +DFT components: +N(Alpha) : 12.000000435446 electrons +N(Beta) : 12.000000435446 electrons +N(Total) : 24.000000870891 electrons +E(X) : -23.330743452721 Eh +E(C) : -0.805006485883 Eh +E(XC) : -24.135749938605 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.4947e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.2306e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.1111e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.1934e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.3935e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.2291e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.194879 -522.3192 + 1 2.0000 -19.039558 -518.0927 + 2 2.0000 -14.240191 -387.4953 + 3 2.0000 -1.246461 -33.9179 + 4 2.0000 -0.966506 -26.3000 + 5 2.0000 -0.713996 -19.4288 + 6 2.0000 -0.574733 -15.6393 + 7 2.0000 -0.520167 -14.1545 + 8 2.0000 -0.501176 -13.6377 + 9 2.0000 -0.324579 -8.8322 + 10 2.0000 -0.275600 -7.4995 + 11 2.0000 -0.241386 -6.5685 + 12 0.0000 -0.217626 -5.9219 + 13 0.0000 0.034919 0.9502 + 14 0.0000 0.102512 2.7895 + 15 0.0000 0.136714 3.7202 + 16 0.0000 0.242802 6.6070 + 17 0.0000 0.258872 7.0443 + 18 0.0000 0.316610 8.6154 + 19 0.0000 0.329056 8.9541 + 20 0.0000 0.358233 9.7480 + 21 0.0000 0.375076 10.2063 + 22 0.0000 0.394769 10.7422 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.353092 + 1 O : 0.201807 + 2 O : -0.138843 + 3 H : 0.290128 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.763846 s : 3.763846 + pz : 1.553857 p : 3.538690 + px : 0.958742 + py : 1.026091 + dz2 : 0.010375 d : 0.050556 + dxz : 0.005102 + dyz : 0.009144 + dx2y2 : 0.012469 + dxy : 0.013465 + + 1 O s : 3.749763 s : 3.749763 + pz : 1.498420 p : 3.919073 + px : 1.283907 + py : 1.136746 + dz2 : 0.028899 d : 0.129356 + dxz : 0.023095 + dyz : 0.022756 + dx2y2 : 0.028797 + dxy : 0.025810 + + 2 O s : 3.937295 s : 3.937295 + pz : 1.529699 p : 4.187732 + px : 1.547551 + py : 1.110482 + dz2 : 0.003921 d : 0.013816 + dxz : 0.002019 + dyz : 0.002709 + dx2y2 : 0.004293 + dxy : 0.000874 + + 3 H s : 0.676759 s : 0.676759 + pz : 0.014602 p : 0.033113 + px : 0.005492 + py : 0.013018 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.124839 + 1 O : -0.161084 + 2 O : 0.000970 + 3 H : 0.284954 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.270379 s : 3.270379 + pz : 1.470294 p : 3.544405 + px : 0.998717 + py : 1.075394 + dz2 : 0.035152 d : 0.310055 + dxz : 0.037136 + dyz : 0.084502 + dx2y2 : 0.067106 + dxy : 0.086159 + + 1 O s : 3.369939 s : 3.369939 + pz : 1.483051 p : 4.022016 + px : 1.268697 + py : 1.270267 + dz2 : 0.117410 d : 0.769129 + dxz : 0.067633 + dyz : 0.201804 + dx2y2 : 0.191456 + dxy : 0.190826 + + 2 O s : 3.614740 s : 3.614740 + pz : 1.480235 p : 4.139101 + px : 1.469483 + py : 1.189383 + dz2 : 0.048718 d : 0.245189 + dxz : 0.020069 + dyz : 0.082911 + dx2y2 : 0.044256 + dxy : 0.049235 + + 3 H s : 0.631761 s : 0.631761 + pz : 0.038464 p : 0.083285 + px : 0.013893 + py : 0.030928 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3531 7.0000 -0.3531 2.7409 2.7409 0.0000 + 1 O 7.7982 8.0000 0.2018 2.6086 2.6086 -0.0000 + 2 O 8.1388 8.0000 -0.1388 1.6912 1.6912 0.0000 + 3 H 0.7099 1.0000 0.2901 0.9033 0.9033 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4193 B( 0-N , 2-O ) : 0.4890 B( 0-N , 3-H ) : 0.8326 +B( 1-O , 2-O ) : 1.1604 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.221 sec +Sum of individual times .... 1.205 sec ( 98.7%) + +SCF preparation .... 0.468 sec ( 38.4%) +Fock matrix formation .... 0.336 sec ( 27.5%) + Startup .... 0.014 sec ( 4.3% of F) + Split-RI-J .... 0.044 sec ( 13.1% of F) + XC integration .... 0.222 sec ( 66.0% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.015 sec ( 6.6% of XC) + Density eval. .... 0.020 sec ( 9.2% of XC) + XC-Functional eval. .... 0.012 sec ( 5.3% of XC) + XC-Potential eval. .... 0.020 sec ( 9.0% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.023 sec ( 1.9%) +Total Energy calculation .... 0.027 sec ( 2.2%) +Population analysis .... 0.223 sec ( 18.3%) +Orbital Transformation .... 0.013 sec ( 1.1%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.064 sec ( 5.2%) +SOSCF solution .... 0.051 sec ( 4.1%) +Finished LeanSCF after 1.5 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 17.5 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000361289 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006646201 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.501485333662 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001128 -0.000006647 0.000001475 + 2 O : 0.000000508 0.000000615 -0.000000823 + 3 O : 0.000002555 0.000008143 0.000001262 + 4 H : -0.000001935 -0.000002110 -0.000001914 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000116292 +RMS gradient ... 0.0000033571 +MAX gradient ... 0.0000081430 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.025887349 0.042949981 0.037182295 + 2 O : 0.037657568 -0.029684669 0.010758556 + 3 O : -0.023881867 0.011429636 -0.017860155 + 4 H : 0.012111647 -0.024694948 -0.030080696 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000262726 -0.0000084623 -0.0000545598 + +Norm of the Cartesian gradient ... 0.0948353482 +RMS gradient ... 0.0273766069 +MAX gradient ... 0.0429499811 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.139 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.6%) +RI-J Coulomb gradient .... 0.064 sec ( 45.7%) +XC gradient .... 0.021 sec ( 14.7%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.501485334 Eh +Current gradient norm .... 0.094835348 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999038454 +Lowest eigenvalues of augmented Hessian: + -0.000737444 0.366072044 0.410669525 0.443659763 0.663491444 +Length of the computed step .... 0.043884720 +The final length of the internal step .... 0.043884720 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0179158618 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0125785739 RMS(Int)= 0.0179377796 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000006 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0069309701 0.0001000000 NO + MAX gradient 0.0148348921 0.0003000000 NO + RMS step 0.0179158618 0.0020000000 NO + MAX step 0.0405093064 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0026 Max(Angles) 2.32 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2778 -0.003764 0.0026 1.2804 + 2. B(O 2,O 1) 1.3136 -0.002439 0.0019 1.3156 + 3. B(H 3,N 0) 1.0242 -0.001991 0.0026 1.0268 + 4. A(O 1,N 0,H 3) 118.99 0.014835 -2.32 116.67 + 5. A(N 0,O 1,O 2) 120.79 -0.006639 0.86 121.65 + 6. D(O 2,O 1,N 0,H 3) -78.46 -0.067688 0.00 -78.46 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.732 %) +Internal coordinates : 0.000 s ( 3.667 %) +B/P matrices and projection : 0.000 s (16.925 %) +Hessian update/contruction : 0.000 s (26.093 %) +Making the step : 0.000 s ( 7.193 %) +Converting the step to Cartesian: 0.000 s ( 6.770 %) +Storing new data : 0.000 s ( 3.808 %) +Checking convergence : 0.000 s ( 0.141 %) +Final printing : 0.000 s (25.247 %) +Total time : 0.001 s + +Time for energy+gradient : 5.011 s +Time for complete geometry iter : 5.837 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.487497 -0.540507 -0.282969 + O 0.334841 0.420326 -0.482858 + O 0.375147 1.470373 0.308692 + H -0.241199 -1.212348 0.453427 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.921236 -1.021410 -0.534734 + 1 O 8.0000 0 15.999 0.632758 0.794300 -0.912469 + 2 O 8.0000 0 15.999 0.708925 2.778603 0.583343 + 3 H 1.0000 0 1.008 -0.455800 -2.291006 0.856853 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.280388170967 0.00000000 0.00000000 + O 2 1 0 1.315589407854 121.64821840 0.00000000 + H 1 2 3 1.026797406908 116.67391904 281.53846167 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.419582988239 0.00000000 0.00000000 + O 2 1 0 2.486103685531 121.64821840 0.00000000 + H 1 2 3 1.940365894076 116.67391904 281.53846167 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.255512091179 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.847e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22308 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5081150923475093 0.00e+00 1.26e-04 1.18e-03 3.76e-03 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.023) - skipping pre-diagonalization + Will do a full diagonalization + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 2 -205.5081850428414327 -7.00e-05 4.49e-04 4.35e-03 2.88e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 3 -205.5083755253351683 -1.90e-04 1.42e-04 1.38e-03 4.30e-04 0.0 + 4 -205.5083731145779211 2.41e-06 1.36e-04 1.28e-03 1.60e-03 0.0 + 5 -205.5083830943051453 -9.98e-06 6.30e-05 6.83e-04 3.82e-04 0.0 + 6 -205.5083834753125416 -3.81e-07 3.04e-05 4.30e-04 4.40e-04 0.0 + 7 -205.5083848571542831 -1.38e-06 2.72e-05 1.66e-04 2.01e-04 0.0 + 8 -205.5083853552968094 -4.98e-07 1.15e-05 1.22e-04 8.61e-05 0.0 + 9 -205.5083854757799031 -1.20e-07 2.20e-06 2.20e-05 1.42e-05 0.0 + 10 -205.5083854791159865 -3.34e-09 1.02e-06 7.00e-06 6.45e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 10 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50838547911599 Eh -5592.16747 eV + +Components: +Nuclear Repulsion : 69.25551209117943 Eh 1884.53829 eV +Electronic Energy : -274.76389757029540 Eh -7476.70576 eV +One Electron Energy: -418.19752853488973 Eh -11379.73329 eV +Two Electron Energy: 143.43363096459430 Eh 3903.02752 eV + +Virial components: +Potential Energy : -410.33191091130698 Eh -11165.69895 eV +Kinetic Energy : 204.82352543219102 Eh 5573.53148 eV +Virial Ratio : 2.00334365911084 + +DFT components: +N(Alpha) : 12.000000434805 electrons +N(Beta) : 12.000000434805 electrons +N(Total) : 24.000000869611 electrons +E(X) : -23.328115973445 Eh +E(C) : -0.804650604070 Eh +E(XC) : -24.132766577515 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.3361e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.9967e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.0242e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.8765e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 6.4473e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.4006e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 17.7 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361300 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006665063 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502081716066 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001119 -0.000006663 0.000001469 + 2 O : 0.000000498 0.000000570 -0.000000802 + 3 O : 0.000002588 0.000008167 0.000001309 + 4 H : -0.000001966 -0.000002074 -0.000001977 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000116710 +RMS gradient ... 0.0000033691 +MAX gradient ... 0.0000081670 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.028991602 0.043303904 0.031399440 + 2 O : 0.036546435 -0.033956676 0.017569323 + 3 O : -0.022724005 0.015284921 -0.019411817 + 4 H : 0.015169172 -0.024632149 -0.029556946 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000224840 -0.0000042267 -0.0000637284 + +Norm of the Cartesian gradient ... 0.0966246978 +RMS gradient ... 0.0278931477 +MAX gradient ... 0.0433039037 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.145 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.006 sec ( 3.8%) +RI-J Coulomb gradient .... 0.063 sec ( 43.3%) +XC gradient .... 0.022 sec ( 15.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.502081716 Eh +Current gradient norm .... 0.096624698 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.995594014 +Lowest eigenvalues of augmented Hessian: + -0.001053043 0.117333216 0.409930762 0.523248370 0.671944593 +Length of the computed step .... 0.094183615 +The final length of the internal step .... 0.094183615 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0384502998 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0293483480 RMS(Int)= 0.0385373336 + Iter 5: RMS(Cart)= 0.0000000122 RMS(Int)= 0.0000000127 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000008 RMS(Int)= 0.0000000001 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000531192 +Previously predicted energy change .... -0.000369432 +Actually observed energy change .... -0.000596382 +Ratio of predicted to observed change .... 1.614321809 +New trust radius .... 0.200000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0005963824 0.0000050000 NO + RMS gradient 0.0047054245 0.0001000000 NO + MAX gradient 0.0103547142 0.0003000000 NO + RMS step 0.0384502998 0.0020000000 NO + MAX step 0.0913136069 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0099 Max(Angles) 5.23 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2804 -0.004851 0.0099 1.2903 + 2. B(O 2,O 1) 1.3156 -0.000175 0.0013 1.3169 + 3. B(H 3,N 0) 1.0268 -0.001437 0.0059 1.0327 + 4. A(O 1,N 0,H 3) 116.67 0.010355 -5.23 111.44 + 5. A(N 0,O 1,O 2) 121.65 -0.000017 0.41 122.05 + 6. D(O 2,O 1,N 0,H 3) -78.46 -0.071067 0.00 -78.46 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 7.572 %) +Internal coordinates : 0.000 s ( 2.885 %) +B/P matrices and projection : 0.000 s (11.178 %) +Hessian update/contruction : 0.000 s (40.625 %) +Making the step : 0.000 s ( 4.688 %) +Converting the step to Cartesian: 0.000 s ( 4.327 %) +Storing new data : 0.000 s ( 2.885 %) +Checking convergence : 0.000 s ( 1.202 %) +Final printing : 0.000 s (24.279 %) +Total time : 0.001 s + +Time for energy+gradient : 4.581 s +Time for complete geometry iter : 5.424 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.511247 -0.548717 -0.304331 + O 0.337980 0.407600 -0.475055 + O 0.374662 1.459301 0.316585 + H -0.220103 -1.180341 0.459093 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.966118 -1.036924 -0.575102 + 1 O 8.0000 0 15.999 0.638690 0.770253 -0.897724 + 2 O 8.0000 0 15.999 0.708009 2.757679 0.598259 + 3 H 1.0000 0 1.008 -0.415934 -2.230521 0.867560 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.290300955062 0.00000000 0.00000000 + O 2 1 0 1.316857435295 122.05368940 0.00000000 + H 1 2 3 1.032729173388 111.44203472 281.53846168 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.438315435405 0.00000000 0.00000000 + O 2 1 0 2.488499910125 122.05368940 0.00000000 + H 1 2 3 1.951575308214 111.44203472 281.53846168 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1674 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.025598658889 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.856e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22311 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.5 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5079204669734736 0.00e+00 2.35e-04 2.92e-03 8.95e-03 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.021) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5081957322186668 -2.75e-04 2.52e-04 3.04e-03 6.82e-03 0.700 0.1 + ***Turning on AO-DIIS*** + 3 -205.5084328438985608 -2.37e-04 1.97e-04 2.16e-03 4.97e-03 0.700 0.0 + 4 -205.5086040130157699 -1.71e-04 5.19e-04 5.57e-03 3.50e-03 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5090138571873695 -4.10e-04 8.01e-05 1.26e-03 7.03e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 6 -205.5090183651537359 -4.51e-06 2.01e-04 2.10e-03 1.05e-03 0.0 + 7 -205.5089585056180681 5.99e-05 1.60e-04 2.10e-03 4.05e-03 0.0 + 8 -205.5090328521507104 -7.43e-05 5.46e-05 6.18e-04 1.79e-04 0.0 + 9 -205.5090334185396159 -5.66e-07 5.87e-05 4.36e-04 3.15e-04 0.0 + 10 -205.5090345762821471 -1.16e-06 1.76e-05 2.04e-04 7.06e-05 0.0 + 11 -205.5090347049128354 -1.29e-07 2.49e-06 2.14e-05 2.41e-05 0.0 + 12 -205.5090347118361933 -6.92e-09 1.73e-06 1.08e-05 7.83e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50903471183619 Eh -5592.18514 eV + +Components: +Nuclear Repulsion : 69.02559865888939 Eh 1878.28203 eV +Electronic Energy : -274.53463337072560 Eh -7470.46717 eV +One Electron Energy: -417.74299444850556 Eh -11367.36478 eV +Two Electron Energy: 143.20836107777995 Eh 3896.89762 eV + +Virial components: +Potential Energy : -410.32319754000093 Eh -11165.46185 eV +Kinetic Energy : 204.81416282816477 Eh 5573.27671 eV +Virial Ratio : 2.00339269449962 + +DFT components: +N(Alpha) : 11.999999493733 electrons +N(Beta) : 11.999999493733 electrons +N(Total) : 23.999998987466 electrons +E(X) : -23.322094882668 Eh +E(C) : -0.803947945215 Eh +E(XC) : -24.126042827883 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 6.9234e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.0803e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.7312e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.0338e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 7.8309e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 5.4157e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 17.9 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361601 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006774595 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502621717996 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.0 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001059 -0.000006591 0.000001479 + 2 O : 0.000000490 0.000000483 -0.000000761 + 3 O : 0.000002589 0.000007991 0.000001408 + 4 H : -0.000002019 -0.000001883 -0.000002126 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000115104 +RMS gradient ... 0.0000033228 +MAX gradient ... 0.0000079911 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.036444758 0.043472168 0.021144601 + 2 O : 0.036824691 -0.040040096 0.027107387 + 3 O : -0.022088384 0.020390453 -0.020868666 + 4 H : 0.021708452 -0.023822525 -0.027383323 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000088374 0.0000203335 -0.0000481765 + +Norm of the Cartesian gradient ... 0.1024060833 +RMS gradient ... 0.0295620899 +MAX gradient ... 0.0434721676 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.096 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.9%) +RI-J Coulomb gradient .... 0.047 sec ( 49.0%) +XC gradient .... 0.014 sec ( 14.2%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.502621718 Eh +Current gradient norm .... 0.102406083 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.200 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999927115 +Lowest eigenvalues of augmented Hessian: + -0.000091431 0.114323858 0.410213270 0.531009904 0.676686124 +Length of the computed step .... 0.012074169 +The final length of the internal step .... 0.012074169 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0049292589 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0034436450 RMS(Int)= 0.0049268609 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000045722 +Previously predicted energy change .... -0.000531192 +Actually observed energy change .... -0.000540002 +Ratio of predicted to observed change .... 1.016584896 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0005400019 0.0000050000 NO + RMS gradient 0.0033477301 0.0001000000 NO + MAX gradient 0.0056932224 0.0003000000 NO + RMS step 0.0049292589 0.0020000000 NO + MAX step 0.0077709423 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0041 Max(Angles) 0.44 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2903 -0.005693 0.0041 1.2944 + 2. B(O 2,O 1) 1.3169 0.003126 -0.0020 1.3148 + 3. B(H 3,N 0) 1.0327 0.000449 -0.0002 1.0325 + 4. A(O 1,N 0,H 3) 111.44 -0.000879 -0.19 111.25 + 5. A(N 0,O 1,O 2) 122.05 0.004908 -0.44 121.61 + 6. D(O 2,O 1,N 0,H 3) -78.46 -0.076811 -0.00 -78.46 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.740 %) +Internal coordinates : 0.000 s ( 3.571 %) +B/P matrices and projection : 0.000 s (13.636 %) +Hessian update/contruction : 0.000 s (32.630 %) +Making the step : 0.000 s ( 5.519 %) +Converting the step to Cartesian: 0.000 s ( 4.545 %) +Storing new data : 0.000 s ( 3.409 %) +Checking convergence : 0.000 s ( 1.623 %) +Final printing : 0.000 s (25.162 %) +Total time : 0.001 s + +Time for energy+gradient : 4.812 s +Time for complete geometry iter : 5.786 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 4 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.513039 -0.548590 -0.303871 + O 0.340588 0.408876 -0.477318 + O 0.372969 1.455713 0.317542 + H -0.219226 -1.178155 0.459939 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.969503 -1.036685 -0.574233 + 1 O 8.0000 0 15.999 0.643619 0.772664 -0.902001 + 2 O 8.0000 0 15.999 0.704809 2.750900 0.600068 + 3 H 1.0000 0 1.008 -0.414278 -2.226391 0.869159 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.294413160514 0.00000000 0.00000000 + O 2 1 0 1.314808164278 121.61233251 0.00000000 + H 1 2 3 1.032513644001 111.25289628 281.53846167 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.446086377515 0.00000000 0.00000000 + O 2 1 0 2.484627349129 121.61233251 0.00000000 + H 1 2 3 1.951168016698 111.25289628 281.53846167 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1674 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.013258386481 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.848e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22312 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5090795503591323 0.00e+00 1.61e-04 1.33e-03 3.60e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5091206878342689 -4.11e-05 1.08e-04 1.04e-03 4.60e-04 0.0 + 3 -205.5091169944682576 3.69e-06 1.02e-04 1.16e-03 1.39e-03 0.0 + 4 -205.5091245012497154 -7.51e-06 6.89e-05 6.56e-04 2.89e-04 0.0 + 5 -205.5091260025619988 -1.50e-06 2.19e-05 3.09e-04 1.68e-04 0.0 + 6 -205.5091261536447007 -1.51e-07 2.09e-05 1.98e-04 2.24e-04 0.0 + 7 -205.5091264788211731 -3.25e-07 1.21e-05 1.37e-04 7.00e-05 0.0 + 8 -205.5091265735443073 -9.47e-08 4.01e-06 3.29e-05 2.59e-05 0.0 + 9 -205.5091265908417029 -1.73e-08 1.34e-06 8.57e-06 6.47e-06 0.0 + 10 -205.5091265925462665 -1.70e-09 4.92e-07 3.12e-06 1.49e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 10 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50912659254627 Eh -5592.18764 eV + +Components: +Nuclear Repulsion : 69.01325838648111 Eh 1877.94623 eV +Electronic Energy : -274.52238497902738 Eh -7470.13387 eV +One Electron Energy: -417.71910920554433 Eh -11366.71483 eV +Two Electron Energy: 143.19672422651695 Eh 3896.58096 eV + +Virial components: +Potential Energy : -410.31959895261878 Eh -11165.36392 eV +Kinetic Energy : 204.81047236007254 Eh 5573.17629 eV +Virial Ratio : 2.00341122318807 + +DFT components: +N(Alpha) : 11.999999240257 electrons +N(Beta) : 11.999999240257 electrons +N(Total) : 23.999998480514 electrons +E(X) : -23.321083660076 Eh +E(C) : -0.803863950752 Eh +E(XC) : -24.124947610828 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.7046e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.1239e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.9221e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.9314e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.4867e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.4639e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.1 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 18.1 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361665 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006793189 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502695068910 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001045 -0.000006566 0.000001487 + 2 O : 0.000000496 0.000000493 -0.000000762 + 3 O : 0.000002571 0.000007929 0.000001403 + 4 H : -0.000002022 -0.000001856 -0.000002129 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000114457 +RMS gradient ... 0.0000033041 +MAX gradient ... 0.0000079290 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.037390533 0.042198278 0.022606212 + 2 O : 0.038812029 -0.037857305 0.025384793 + 3 O : -0.022790408 0.019580229 -0.020523435 + 4 H : 0.021368912 -0.023921202 -0.027467571 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000002138 0.0000241775 -0.0000478872 + +Norm of the Cartesian gradient ... 0.1018874160 +RMS gradient ... 0.0294123635 +MAX gradient ... 0.0421982782 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.122 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.9%) +RI-J Coulomb gradient .... 0.056 sec ( 46.4%) +XC gradient .... 0.016 sec ( 13.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.502695069 Eh +Current gradient norm .... 0.101887416 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999771770 +Lowest eigenvalues of augmented Hessian: + -0.000096144 0.101250605 0.316246304 0.414055580 0.571740695 +Length of the computed step .... 0.021368592 +The final length of the internal step .... 0.021368592 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0087236910 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0056109285 RMS(Int)= 0.0087151725 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000048094 +Previously predicted energy change .... -0.000045722 +Actually observed energy change .... -0.000073351 +Ratio of predicted to observed change .... 1.604282568 +New trust radius .... 0.200000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000733509 0.0000050000 NO + RMS gradient 0.0020802758 0.0001000000 NO + MAX gradient 0.0036082505 0.0003000000 NO + RMS step 0.0087236910 0.0020000000 NO + MAX step 0.0141756612 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0075 Max(Angles) 0.57 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2944 -0.003608 0.0075 1.3019 + 2. B(O 2,O 1) 1.3148 0.002623 -0.0049 1.3099 + 3. B(H 3,N 0) 1.0325 0.000348 -0.0005 1.0320 + 4. A(O 1,N 0,H 3) 111.25 -0.000429 -0.48 110.77 + 5. A(N 0,O 1,O 2) 121.61 0.002400 -0.57 121.05 + 6. D(O 2,O 1,N 0,H 3) -78.46 -0.076787 -0.00 -78.46 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.238 %) +Internal coordinates : 0.000 s ( 2.945 %) +B/P matrices and projection : 0.000 s (12.482 %) +Hessian update/contruction : 0.000 s (34.222 %) +Making the step : 0.000 s ( 4.909 %) +Converting the step to Cartesian: 0.000 s ( 3.927 %) +Storing new data : 0.000 s ( 3.086 %) +Checking convergence : 0.000 s ( 1.262 %) +Final printing : 0.000 s (26.227 %) +Total time : 0.001 s + +Time for energy+gradient : 4.723 s +Time for complete geometry iter : 5.568 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 5 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.516658 -0.549130 -0.303804 + O 0.344623 0.411242 -0.479481 + O 0.370607 1.449670 0.318470 + H -0.217280 -1.173938 0.461106 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.976342 -1.037705 -0.574106 + 1 O 8.0000 0 15.999 0.651243 0.777135 -0.906087 + 2 O 8.0000 0 15.999 0.700346 2.739479 0.601822 + 3 H 1.0000 0 1.008 -0.410600 -2.218421 0.871364 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.301914597321 0.00000000 0.00000000 + O 2 1 0 1.309860035257 121.04576820 0.00000000 + H 1 2 3 1.032035780559 110.77476896 281.53846167 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.460262038692 0.00000000 0.00000000 + O 2 1 0 2.475276740404 121.04576820 0.00000000 + H 1 2 3 1.950264985664 110.77476896 281.53846167 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1672 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.009415364438 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.817e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22311 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5090709021168323 0.00e+00 7.82e-05 7.18e-04 3.49e-03 0.700 0.1 +Warning: op=0 Small HOMO/LUMO gap ( 0.021) - skipping pre-diagonalization + Will do a full diagonalization + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 2 -205.5091075996108430 -3.67e-05 2.82e-04 2.06e-03 2.47e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 3 -205.5092032228346852 -9.56e-05 1.27e-04 1.65e-03 4.64e-04 0.0 + 4 -205.5091832640635516 2.00e-05 8.71e-05 9.44e-04 2.33e-03 0.0 + 5 -205.5092065458641173 -2.33e-05 3.11e-05 3.55e-04 1.05e-04 0.0 + 6 -205.5092068418706504 -2.96e-07 1.78e-05 1.54e-04 8.81e-05 0.0 + 7 -205.5092071293142908 -2.87e-07 1.13e-05 1.23e-04 4.49e-05 0.0 + 8 -205.5092070804147397 4.89e-08 5.84e-06 6.21e-05 8.36e-05 0.0 + 9 -205.5092071670935638 -8.67e-08 1.17e-06 1.04e-05 6.16e-06 0.0 + 10 -205.5092071675554735 -4.62e-10 5.09e-07 3.55e-06 2.77e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 10 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50920716755547 Eh -5592.18983 eV + +Components: +Nuclear Repulsion : 69.00941536443837 Eh 1877.84166 eV +Electronic Energy : -274.51862253199386 Eh -7470.03149 eV +One Electron Energy: -417.70896876877049 Eh -11366.43890 eV +Two Electron Energy: 143.19034623677661 Eh 3896.40741 eV + +Virial components: +Potential Energy : -410.31656585553935 Eh -11165.28139 eV +Kinetic Energy : 204.80735868798388 Eh 5573.09156 eV +Virial Ratio : 2.00342687139792 + +DFT components: +N(Alpha) : 11.999998755751 electrons +N(Beta) : 11.999998755751 electrons +N(Total) : 23.999997511501 electrons +E(X) : -23.320045289241 Eh +E(C) : -0.803761373151 Eh +E(XC) : -24.123806662393 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 4.6191e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.5487e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 5.0937e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.4661e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.7715e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.3119e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 18.2 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361768 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006821930 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502747005904 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001024 -0.000006527 0.000001502 + 2 O : 0.000000506 0.000000512 -0.000000757 + 3 O : 0.000002546 0.000007826 0.000001394 + 4 H : -0.000002028 -0.000001810 -0.000002139 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000113420 +RMS gradient ... 0.0000032741 +MAX gradient ... 0.0000078262 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.038927072 0.039946511 0.024458773 + 2 O : 0.041652107 -0.033961362 0.024025868 + 3 O : -0.023718185 0.017856515 -0.020783394 + 4 H : 0.020993150 -0.023841663 -0.027701247 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000024442 0.0000412483 -0.0000404547 + +Norm of the Cartesian gradient ... 0.1013145596 +RMS gradient ... 0.0292469941 +MAX gradient ... 0.0416521073 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.135 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 4.0%) +RI-J Coulomb gradient .... 0.063 sec ( 46.9%) +XC gradient .... 0.021 sec ( 15.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.502747006 Eh +Current gradient norm .... 0.101314560 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.200 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999994056 +Lowest eigenvalues of augmented Hessian: + -0.000003889 0.098168991 0.292522135 0.412882149 0.575943817 +Length of the computed step .... 0.003447890 +The final length of the internal step .... 0.003447890 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0014075953 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0006346768 RMS(Int)= 0.0014076542 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000001944 +Previously predicted energy change .... -0.000048094 +Actually observed energy change .... -0.000051937 +Ratio of predicted to observed change .... 1.079911191 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000519370 0.0000050000 NO + RMS gradient 0.0005474011 0.0001000000 NO + MAX gradient 0.0010278562 0.0003000000 NO + RMS step 0.0014075953 0.0020000000 YES + MAX step 0.0024800937 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0013 Max(Angles) 0.06 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3019 -0.000456 0.0011 1.3030 + 2. B(O 2,O 1) 1.3099 0.001028 -0.0013 1.3085 + 3. B(H 3,N 0) 1.0320 -0.000008 0.0000 1.0320 + 4. A(O 1,N 0,H 3) 110.77 -0.000070 -0.06 110.72 + 5. A(N 0,O 1,O 2) 121.05 -0.000727 0.04 121.08 + 6. D(O 2,O 1,N 0,H 3) -78.46 -0.076847 0.00 -78.46 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (11.779 %) +Internal coordinates : 0.000 s ( 3.008 %) +B/P matrices and projection : 0.000 s (15.288 %) +Hessian update/contruction : 0.000 s (28.446 %) +Making the step : 0.000 s ( 5.138 %) +Converting the step to Cartesian: 0.000 s ( 3.885 %) +Storing new data : 0.000 s ( 3.008 %) +Checking convergence : 0.000 s ( 1.378 %) +Final printing : 0.000 s (27.820 %) +Total time : 0.001 s + +Time for energy+gradient : 4.821 s +Time for complete geometry iter : 5.622 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 6 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.517066 -0.549525 -0.303933 + O 0.344836 0.411915 -0.478967 + O 0.370701 1.449385 0.318080 + H -0.217179 -1.173931 0.461112 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.977112 -1.038451 -0.574350 + 1 O 8.0000 0 15.999 0.651645 0.778406 -0.905116 + 2 O 8.0000 0 15.999 0.700524 2.738941 0.601084 + 3 H 1.0000 0 1.008 -0.410409 -2.218408 0.871375 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.303025963221 0.00000000 0.00000000 + O 2 1 0 1.308547626184 121.08125419 0.00000000 + H 1 2 3 1.032040935492 110.71914035 281.53846167 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.462362215876 0.00000000 0.00000000 + O 2 1 0 2.472796646681 121.08125419 0.00000000 + H 1 2 3 1.950274727076 110.71914035 281.53846167 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1672 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.014423666232 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.806e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22311 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5092060525592501 0.00e+00 4.30e-05 4.12e-04 7.22e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5092090276667136 -2.98e-06 4.44e-05 5.34e-04 2.12e-04 0.0 + 3 -205.5092056132089624 3.41e-06 3.47e-05 4.02e-04 9.15e-04 0.0 + 4 -205.5092094175485613 -3.80e-06 1.20e-05 1.83e-04 7.04e-05 0.0 + 5 -205.5092091593419354 2.58e-07 9.02e-06 1.33e-04 1.83e-04 0.0 + 6 -205.5092094682977972 -3.09e-07 1.27e-06 1.04e-05 3.03e-06 0.0 + 7 -205.5092094686954738 -3.98e-10 7.29e-07 4.76e-06 1.87e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50920946869547 Eh -5592.18989 eV + +Components: +Nuclear Repulsion : 69.01442366623183 Eh 1877.97794 eV +Electronic Energy : -274.52363313492731 Eh -7470.16783 eV +One Electron Energy: -417.71744839328778 Eh -11366.66964 eV +Two Electron Energy: 143.19381525836047 Eh 3896.50181 eV + +Virial components: +Potential Energy : -410.31690869353918 Eh -11165.29072 eV +Kinetic Energy : 204.80769922484373 Eh 5573.10083 eV +Virial Ratio : 2.00342521422049 + +DFT components: +N(Alpha) : 11.999998687580 electrons +N(Beta) : 11.999998687580 electrons +N(Total) : 23.999997375159 electrons +E(X) : -23.320156926986 Eh +E(C) : -0.803767439534 Eh +E(XC) : -24.123924366521 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.9768e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.7582e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 7.2943e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.3055e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.8735e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.2957e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 18.4 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361768 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006821470 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502749766849 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001025 -0.000006528 0.000001502 + 2 O : 0.000000507 0.000000516 -0.000000754 + 3 O : 0.000002548 0.000007823 0.000001390 + 4 H : -0.000002030 -0.000001811 -0.000002139 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000113405 +RMS gradient ... 0.0000032737 +MAX gradient ... 0.0000078227 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.039129278 0.039553808 0.024407361 + 2 O : 0.041826441 -0.033226827 0.024475173 + 3 O : -0.023682796 0.017493779 -0.021187515 + 4 H : 0.020985633 -0.023820760 -0.027695019 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000015313 0.0000428195 -0.0000408914 + +Norm of the Cartesian gradient ... 0.1011656468 +RMS gradient ... 0.0292040067 +MAX gradient ... 0.0418264409 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.114 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.2%) +RI-J Coulomb gradient .... 0.052 sec ( 45.9%) +XC gradient .... 0.016 sec ( 14.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.502749767 Eh +Current gradient norm .... 0.101165647 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999996907 +Lowest eigenvalues of augmented Hessian: + -0.000001694 0.101413098 0.245058634 0.391044528 0.423447077 +Length of the computed step .... 0.002487140 +The final length of the internal step .... 0.002487140 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0010153706 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0006467839 RMS(Int)= 0.0010153601 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000847 +Previously predicted energy change .... -0.000001944 +Actually observed energy change .... -0.000002761 +Ratio of predicted to observed change .... 1.419943972 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000027609 0.0000050000 YES + RMS gradient 0.0002925670 0.0001000000 NO + MAX gradient 0.0005100488 0.0003000000 NO + RMS step 0.0010153706 0.0020000000 YES + MAX step 0.0018735784 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0010 Max(Angles) 0.08 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3030 -0.000051 0.0004 1.3035 + 2. B(O 2,O 1) 1.3085 0.000499 -0.0010 1.3076 + 3. B(H 3,N 0) 1.0320 -0.000021 0.0000 1.0321 + 4. A(O 1,N 0,H 3) 110.72 -0.000032 -0.00 110.72 + 5. A(N 0,O 1,O 2) 121.08 -0.000510 0.08 121.16 + 6. D(O 2,O 1,N 0,H 3) -78.46 -0.076839 0.00 -78.46 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (13.099 %) +Internal coordinates : 0.000 s ( 3.355 %) +B/P matrices and projection : 0.000 s (13.898 %) +Hessian update/contruction : 0.000 s (26.837 %) +Making the step : 0.000 s ( 7.029 %) +Converting the step to Cartesian: 0.000 s ( 4.153 %) +Storing new data : 0.000 s ( 3.355 %) +Checking convergence : 0.000 s ( 1.438 %) +Final printing : 0.000 s (26.358 %) +Total time : 0.001 s + +Time for energy+gradient : 4.447 s +Time for complete geometry iter : 5.243 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 7 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.517102 -0.549822 -0.304012 + O 0.344707 0.412441 -0.478284 + O 0.370975 1.449563 0.317575 + H -0.217287 -1.174338 0.461014 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.977182 -1.039013 -0.574500 + 1 O 8.0000 0 15.999 0.651401 0.779401 -0.903826 + 2 O 8.0000 0 15.999 0.701040 2.739277 0.600129 + 3 H 1.0000 0 1.008 -0.410613 -2.219178 0.871190 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.303470340094 0.00000000 0.00000000 + O 2 1 0 1.307556171183 121.16156766 0.00000000 + H 1 2 3 1.032073058421 110.71668044 281.53846167 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.463201966467 0.00000000 0.00000000 + O 2 1 0 2.470923068255 121.16156766 0.00000000 + H 1 2 3 1.950335430613 110.71668044 281.53846167 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1672 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.022934056240 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.795e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22311 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5092052794121855 0.00e+00 3.68e-05 3.48e-04 7.52e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5092070072635693 -1.73e-06 3.37e-05 4.74e-04 1.44e-04 0.0 + 3 -205.5092051650696590 1.84e-06 2.58e-05 2.78e-04 6.85e-04 0.0 + 4 -205.5092072635012528 -2.10e-06 1.00e-05 1.43e-04 5.32e-05 0.0 + 5 -205.5092071108845744 1.53e-07 6.85e-06 9.86e-05 1.43e-04 0.0 + 6 -205.5092072973222912 -1.86e-07 1.11e-06 1.56e-05 5.20e-06 0.0 + 7 -205.5092072973814084 -5.91e-11 9.72e-07 9.56e-06 2.36e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50920729738141 Eh -5592.18983 eV + +Components: +Nuclear Repulsion : 69.02293405623982 Eh 1878.20952 eV +Electronic Energy : -274.53214135362123 Eh -7470.39935 eV +One Electron Energy: -417.73272312499091 Eh -11367.08529 eV +Two Electron Energy: 143.20058177136968 Eh 3896.68593 eV + +Virial components: +Potential Energy : -410.31775991544566 Eh -11165.31388 eV +Kinetic Energy : 204.80855261806425 Eh 5573.12405 eV +Virial Ratio : 2.00342102256161 + +DFT components: +N(Alpha) : 11.999998660522 electrons +N(Beta) : 11.999998660522 electrons +N(Total) : 23.999997321045 electrons +E(X) : -23.320410793580 Eh +E(C) : -0.803787913994 Eh +E(XC) : -24.124198707573 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 5.9117e-11 Tolerance : 1.0000e-08 + Last MAX-Density change ... 9.5600e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 9.7222e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 4.7585e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.3604e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.6408e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 18.6 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361760 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006818393 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502750664471 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.0 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001026 -0.000006532 0.000001502 + 2 O : 0.000000507 0.000000520 -0.000000751 + 3 O : 0.000002550 0.000007827 0.000001387 + 4 H : -0.000002031 -0.000001815 -0.000002138 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000113465 +RMS gradient ... 0.0000032754 +MAX gradient ... 0.0000078267 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.039174084 0.039369738 0.024230226 + 2 O : 0.041762243 -0.032774794 0.025040428 + 3 O : -0.023581548 0.017218336 -0.021598246 + 4 H : 0.020993390 -0.023813280 -0.027672408 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000047053 0.0000415538 -0.0000395557 + +Norm of the Cartesian gradient ... 0.1010424943 +RMS gradient ... 0.0291684556 +MAX gradient ... 0.0417622426 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.096 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.004 sec ( 4.4%) +RI-J Coulomb gradient .... 0.047 sec ( 48.7%) +XC gradient .... 0.013 sec ( 14.1%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.502750664 Eh +Current gradient norm .... 0.101042494 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999959 +Lowest eigenvalues of augmented Hessian: + -0.000000026 0.102796915 0.249845762 0.365642355 0.417354420 +Length of the computed step .... 0.000284890 +The final length of the internal step .... 0.000284890 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0001163057 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0000815031 RMS(Int)= 0.0001163046 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000013 +Previously predicted energy change .... -0.000000847 +Actually observed energy change .... -0.000000898 +Ratio of predicted to observed change .... 1.060018954 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000008976 0.0000050000 YES + RMS gradient 0.0000424345 0.0001000000 YES + MAX gradient 0.0000734976 0.0003000000 YES + RMS step 0.0001163057 0.0020000000 YES + MAX step 0.0001958578 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3035 0.000073 -0.0001 1.3034 + 2. B(O 2,O 1) 1.3076 0.000041 -0.0000 1.3075 + 3. B(H 3,N 0) 1.0321 -0.000005 0.0000 1.0321 + 4. A(O 1,N 0,H 3) 110.72 0.000009 0.01 110.72 + 5. A(N 0,O 1,O 2) 121.16 -0.000060 0.01 121.17 + 6. D(O 2,O 1,N 0,H 3) -78.46 -0.076816 0.00 -78.46 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (13.371 %) +Internal coordinates : 0.000 s ( 3.129 %) +B/P matrices and projection : 0.000 s (12.091 %) +Hessian update/contruction : 0.000 s (30.868 %) +Making the step : 0.000 s ( 4.979 %) +Converting the step to Cartesian: 0.000 s ( 3.698 %) +Storing new data : 0.000 s ( 3.129 %) +Checking convergence : 0.000 s ( 1.422 %) +Final printing : 0.000 s (27.169 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 7 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.517051 -0.549814 -0.304016 + O 0.344645 0.412442 -0.478211 + O 0.371010 1.449613 0.317526 + H -0.217312 -1.174397 0.460993 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.977086 -1.038998 -0.574507 + 1 O 8.0000 0 15.999 0.651285 0.779402 -0.903688 + 2 O 8.0000 0 15.999 0.701107 2.739372 0.600037 + 3 H 1.0000 0 1.008 -0.410660 -2.219288 0.871151 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.303380766445 0.00000000 0.00000000 + O 2 1 0 1.307523089696 121.17278949 0.00000000 + H 1 2 3 1.032078857340 110.72244468 281.53846167 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.463032696802 0.00000000 0.00000000 + O 2 1 0 2.470860553304 121.17278949 0.00000000 + H 1 2 3 1.950346388982 110.72244468 281.53846167 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1672 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.024962258876 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.795e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22311 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.0249622589 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5092067957410222 0.00e+00 4.01e-06 3.49e-05 7.65e-06 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5092068163189651 -2.06e-08 2.18e-06 1.74e-05 6.75e-06 0.0 + 3 -205.5092068186793881 -2.36e-09 1.95e-06 1.60e-05 4.82e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 3 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50920681867939 Eh -5592.18982 eV + +Components: +Nuclear Repulsion : 69.02496225887613 Eh 1878.26471 eV +Electronic Energy : -274.53416907755553 Eh -7470.45453 eV +One Electron Energy: -417.73653214075432 Eh -11367.18894 eV +Two Electron Energy: 143.20236306319879 Eh 3896.73441 eV + +Virial components: +Potential Energy : -410.31801695454681 Eh -11165.32088 eV +Kinetic Energy : 204.80881013586739 Eh 5573.13106 eV +Virial Ratio : 2.00341975856579 + +DFT components: +N(Alpha) : 11.999998663647 electrons +N(Beta) : 11.999998663647 electrons +N(Total) : 23.999997327294 electrons +E(X) : -23.320470748312 Eh +E(C) : -0.803793113262 Eh +E(XC) : -24.124263861574 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.3604e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.6029e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.9480e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.7679e-05 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.8162e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 5.1868e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.189835 -522.1820 + 1 2.0000 -19.047468 -518.3079 + 2 2.0000 -14.244430 -387.6107 + 3 2.0000 -1.242921 -33.8216 + 4 2.0000 -0.964543 -26.2466 + 5 2.0000 -0.712377 -19.3848 + 6 2.0000 -0.568491 -15.4694 + 7 2.0000 -0.518615 -14.1122 + 8 2.0000 -0.496241 -13.5034 + 9 2.0000 -0.334192 -9.0938 + 10 2.0000 -0.278707 -7.5840 + 11 2.0000 -0.244439 -6.6515 + 12 0.0000 -0.222904 -6.0655 + 13 0.0000 0.033384 0.9084 + 14 0.0000 0.098670 2.6849 + 15 0.0000 0.133021 3.6197 + 16 0.0000 0.230747 6.2790 + 17 0.0000 0.258719 7.0401 + 18 0.0000 0.317608 8.6426 + 19 0.0000 0.327868 8.9218 + 20 0.0000 0.362691 9.8693 + 21 0.0000 0.372647 10.1402 + 22 0.0000 0.393757 10.7147 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.359447 + 1 O : 0.199467 + 2 O : -0.125424 + 3 H : 0.285404 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.818453 s : 3.818453 + pz : 1.523096 p : 3.489984 + px : 0.954178 + py : 1.012710 + dz2 : 0.011117 d : 0.051010 + dxz : 0.006658 + dyz : 0.007164 + dx2y2 : 0.012117 + dxy : 0.013955 + + 1 O s : 3.750405 s : 3.750405 + pz : 1.496809 p : 3.924768 + px : 1.291142 + py : 1.136817 + dz2 : 0.028000 d : 0.125359 + dxz : 0.023125 + dyz : 0.021646 + dx2y2 : 0.028310 + dxy : 0.024278 + + 2 O s : 3.939888 s : 3.939888 + pz : 1.512841 p : 4.171734 + px : 1.586328 + py : 1.072564 + dz2 : 0.004393 d : 0.013802 + dxz : 0.001605 + dyz : 0.002673 + dx2y2 : 0.004692 + dxy : 0.000438 + + 3 H s : 0.682874 s : 0.682874 + pz : 0.014210 p : 0.031722 + px : 0.006238 + py : 0.011275 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.120790 + 1 O : -0.171154 + 2 O : 0.008489 + 3 H : 0.283454 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.316399 s : 3.316399 + pz : 1.450620 p : 3.503355 + px : 1.000808 + py : 1.051927 + dz2 : 0.036331 d : 0.301036 + dxz : 0.037736 + dyz : 0.076926 + dx2y2 : 0.063034 + dxy : 0.087008 + + 1 O s : 3.376269 s : 3.376269 + pz : 1.482964 p : 4.034360 + px : 1.281735 + py : 1.269661 + dz2 : 0.115252 d : 0.760524 + dxz : 0.069482 + dyz : 0.196628 + dx2y2 : 0.190293 + dxy : 0.188869 + + 2 O s : 3.611534 s : 3.611534 + pz : 1.466492 p : 4.130940 + px : 1.506901 + py : 1.157547 + dz2 : 0.049148 d : 0.249037 + dxz : 0.021110 + dyz : 0.083739 + dx2y2 : 0.044221 + dxy : 0.050818 + + 3 H s : 0.636459 s : 0.636459 + pz : 0.038223 p : 0.080087 + px : 0.015538 + py : 0.026326 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3594 7.0000 -0.3594 2.7035 2.7035 -0.0000 + 1 O 7.8005 8.0000 0.1995 2.5668 2.5668 -0.0000 + 2 O 8.1254 8.0000 -0.1254 1.6879 1.6879 -0.0000 + 3 H 0.7146 1.0000 0.2854 0.9055 0.9055 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3755 B( 0-N , 2-O ) : 0.4856 B( 0-N , 3-H ) : 0.8423 +B( 1-O , 2-O ) : 1.1652 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.943 sec +Sum of individual times .... 0.930 sec ( 98.7%) + +SCF preparation .... 0.511 sec ( 54.2%) +Fock matrix formation .... 0.086 sec ( 9.1%) + Startup .... 0.005 sec ( 6.3% of F) + Split-RI-J .... 0.013 sec ( 14.8% of F) + XC integration .... 0.058 sec ( 66.9% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.003 sec ( 5.7% of XC) + Density eval. .... 0.005 sec ( 8.7% of XC) + XC-Functional eval. .... 0.003 sec ( 4.9% of XC) + XC-Potential eval. .... 0.005 sec ( 8.9% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.005 sec ( 0.5%) +Total Energy calculation .... 0.006 sec ( 0.7%) +Population analysis .... 0.288 sec ( 30.6%) +Orbital Transformation .... 0.006 sec ( 0.6%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.010 sec ( 1.0%) +SOSCF solution .... 0.018 sec ( 1.9%) +Finished LeanSCF after 1.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 18.9 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000361759 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006817898 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502750679775 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.012.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.012.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.160316 0.840333 -0.255825 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5092068186793881 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.392666667 0.965172502 -0.235025070 +Nuclear contribution : -0.278707339 -1.510075494 0.560199432 + ----------------------------------------- +Total Dipole Moment : 0.113959328 -0.544902991 0.325174362 + ----------------------------------------- +Magnitude (a.u.) : 0.644704866 +Magnitude (Debye) : 1.638709539 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.094784 0.406546 0.371500 +Rotational constants in MHz : 92779.290617 12187.928169 11137.288781 + +Dipole components along the rotational axes: +x,y,z [a.u.] : -0.363997 0.206355 -0.490477 +x,y,z [Debye]: -0.925207 0.524514 -1.246694 + + + +Dipole moment calculation done in 0.1 sec + +Maximum memory used throughout the entire PROP-calculation: 10.4 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 13 * + * * + * Dihedral ( 2, 1, 0, 3) : -69.23076923 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.3042 0.688982 + 2. B(O 2,O 1) 1.3095 0.678577 + 3. B(H 3,N 0) 1.0349 0.398997 + 4. A(O 1,N 0,H 3) 110.5617 0.357885 + 5. A(N 0,O 1,O 2) 121.0102 0.437858 + 6. D(O 2,O 1,N 0,H 3) -69.2308 0.036972 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.502891 -0.567995 -0.328280 + O 0.325094 0.423815 -0.505977 + O 0.377226 1.419509 0.342968 + H -0.218137 -1.137485 0.487581 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.950327 -1.073355 -0.620359 + 1 O 8.0000 0 15.999 0.614340 0.800894 -0.956157 + 2 O 8.0000 0 15.999 0.712853 2.682484 0.648116 + 3 H 1.0000 0 1.008 -0.412219 -2.149535 0.921394 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.303380766445 0.00000000 0.00000000 + O 2 1 0 1.307523089696 121.17278949 0.00000000 + H 1 2 3 1.032078857340 110.72244468 281.53846167 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.463032696802 0.00000000 0.00000000 + O 2 1 0 2.470860553304 121.17278949 0.00000000 + H 1 2 3 1.950346388982 110.72244468 281.53846167 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1674 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.995708796635 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.822e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22315 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5579 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 68.9957087966 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5172972002994811 0.00e+00 5.03e-04 3.73e-03 1.95e-02 0.700 0.1 +Warning: op=0 Small HOMO/LUMO gap ( 0.036) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5183743905715232 -1.08e-03 5.93e-04 4.63e-03 1.54e-02 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.5193111234038952 -9.37e-04 4.49e-04 3.25e-03 1.11e-02 0.700 0.0 + 4 -205.5199596747849569 -6.49e-04 1.14e-03 8.48e-03 7.87e-03 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5215131264887987 -1.55e-03 1.25e-04 1.22e-03 1.47e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -205.5215276276280747 -1.45e-05 4.02e-04 3.51e-03 1.46e-03 0.1 + 7 -205.5213434435981412 1.84e-04 2.49e-04 3.10e-03 6.41e-03 0.0 + 8 -205.5215538140738545 -2.10e-04 4.93e-05 4.38e-04 1.78e-04 0.0 + 9 -205.5215542781274962 -4.64e-07 4.45e-05 3.71e-04 2.90e-04 0.0 + 10 -205.5215549252508254 -6.47e-07 1.95e-05 1.63e-04 1.24e-04 0.0 + 11 -205.5215551872330479 -2.62e-07 5.69e-06 5.31e-05 3.79e-05 0.0 + 12 -205.5215552146891014 -2.75e-08 2.00e-06 1.81e-05 1.24e-05 0.0 + 13 -205.5215552167384203 -2.05e-09 4.57e-07 4.06e-06 3.76e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 13 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.52155521673842 Eh -5592.52584 eV + +Components: +Nuclear Repulsion : 68.99570879663497 Eh 1877.46869 eV +Electronic Energy : -274.51726401337339 Eh -7469.99452 eV +One Electron Energy: -417.69747699380872 Eh -11366.12619 eV +Two Electron Energy: 143.18021298043533 Eh 3896.13167 eV + +Virial components: +Potential Energy : -410.32519155220689 Eh -11165.51611 eV +Kinetic Energy : 204.80363633546844 Eh 5572.99027 eV +Virial Ratio : 2.00350540104715 + +DFT components: +N(Alpha) : 11.999998368257 electrons +N(Beta) : 11.999998368257 electrons +N(Total) : 23.999996736515 electrons +E(X) : -23.321271592883 Eh +E(C) : -0.803450571657 Eh +E(XC) : -24.124722164539 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.0493e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.0581e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.5677e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.4700e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.7619e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.3125e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.187789 -522.1263 + 1 2.0000 -19.041248 -518.1387 + 2 2.0000 -14.253689 -387.8626 + 3 2.0000 -1.241086 -33.7717 + 4 2.0000 -0.963152 -26.2087 + 5 2.0000 -0.714981 -19.4556 + 6 2.0000 -0.567133 -15.4325 + 7 2.0000 -0.516605 -14.0575 + 8 2.0000 -0.494662 -13.4604 + 9 2.0000 -0.333255 -9.0683 + 10 2.0000 -0.275742 -7.5033 + 11 2.0000 -0.255093 -6.9414 + 12 0.0000 -0.216507 -5.8915 + 13 0.0000 0.033822 0.9203 + 14 0.0000 0.094402 2.5688 + 15 0.0000 0.130882 3.5615 + 16 0.0000 0.229140 6.2352 + 17 0.0000 0.259178 7.0526 + 18 0.0000 0.315587 8.5876 + 19 0.0000 0.327127 8.9016 + 20 0.0000 0.365081 9.9344 + 21 0.0000 0.375487 10.2175 + 22 0.0000 0.394238 10.7278 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.327559 + 1 O : 0.199585 + 2 O : -0.150955 + 3 H : 0.278928 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.829416 s : 3.829416 + pz : 1.474745 p : 3.445804 + px : 0.974377 + py : 0.996682 + dz2 : 0.012158 d : 0.052340 + dxz : 0.006196 + dyz : 0.006718 + dx2y2 : 0.013290 + dxy : 0.013978 + + 1 O s : 3.748223 s : 3.748223 + pz : 1.490245 p : 3.925106 + px : 1.296562 + py : 1.138298 + dz2 : 0.030232 d : 0.127086 + dxz : 0.022071 + dyz : 0.020534 + dx2y2 : 0.031045 + dxy : 0.023204 + + 2 O s : 3.942772 s : 3.942772 + pz : 1.501829 p : 4.194579 + px : 1.584903 + py : 1.107847 + dz2 : 0.003188 d : 0.013604 + dxz : 0.001963 + dyz : 0.003932 + dx2y2 : 0.003993 + dxy : 0.000528 + + 3 H s : 0.690371 s : 0.690371 + pz : 0.014475 p : 0.030701 + px : 0.006076 + py : 0.010150 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.099878 + 1 O : -0.173764 + 2 O : -0.006548 + 3 H : 0.280190 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.330939 s : 3.330939 + pz : 1.414061 p : 3.465617 + px : 1.008530 + py : 1.043026 + dz2 : 0.039570 d : 0.303322 + dxz : 0.034242 + dyz : 0.080671 + dx2y2 : 0.062579 + dxy : 0.086261 + + 1 O s : 3.377027 s : 3.377027 + pz : 1.484395 p : 4.040021 + px : 1.281257 + py : 1.274369 + dz2 : 0.126146 d : 0.756716 + dxz : 0.065446 + dyz : 0.197364 + dx2y2 : 0.182330 + dxy : 0.185430 + + 2 O s : 3.611119 s : 3.611119 + pz : 1.463934 p : 4.146578 + px : 1.504080 + py : 1.178564 + dz2 : 0.054864 d : 0.248851 + dxz : 0.023671 + dyz : 0.082414 + dx2y2 : 0.040587 + dxy : 0.047314 + + 3 H s : 0.641328 s : 0.641328 + pz : 0.039640 p : 0.078482 + px : 0.015145 + py : 0.023698 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3276 7.0000 -0.3276 2.7398 2.7398 -0.0000 + 1 O 7.8004 8.0000 0.1996 2.5662 2.5662 -0.0000 + 2 O 8.1510 8.0000 -0.1510 1.6847 1.6847 0.0000 + 3 H 0.7211 1.0000 0.2789 0.9095 0.9095 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3838 B( 0-N , 2-O ) : 0.4991 B( 0-N , 3-H ) : 0.8569 +B( 1-O , 2-O ) : 1.1577 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.349 sec +Sum of individual times .... 1.334 sec ( 98.9%) + +SCF preparation .... 0.520 sec ( 38.6%) +Fock matrix formation .... 0.324 sec ( 24.0%) + Startup .... 0.014 sec ( 4.4% of F) + Split-RI-J .... 0.045 sec ( 14.0% of F) + XC integration .... 0.216 sec ( 66.5% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.014 sec ( 6.7% of XC) + Density eval. .... 0.020 sec ( 9.5% of XC) + XC-Functional eval. .... 0.012 sec ( 5.8% of XC) + XC-Potential eval. .... 0.019 sec ( 8.8% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.026 sec ( 1.9%) +Total Energy calculation .... 0.027 sec ( 2.0%) +Population analysis .... 0.301 sec ( 22.3%) +Orbital Transformation .... 0.013 sec ( 1.0%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.076 sec ( 5.6%) +SOSCF solution .... 0.047 sec ( 3.5%) +Finished LeanSCF after 1.7 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 19.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000362167 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006848570 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.515068813758 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001046 -0.000006339 0.000001592 + 2 O : 0.000000474 0.000000533 -0.000000803 + 3 O : 0.000002499 0.000007458 0.000001530 + 4 H : -0.000001927 -0.000001652 -0.000002318 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000109995 +RMS gradient ... 0.0000031753 +MAX gradient ... 0.0000074580 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.041773181 0.036589433 0.024774063 + 2 O : 0.046097264 -0.028376219 0.017600067 + 3 O : -0.024814026 0.017721534 -0.017918142 + 4 H : 0.020489943 -0.025934748 -0.024455989 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000147168 0.0000579054 -0.0000303177 + +Norm of the Cartesian gradient ... 0.0993924660 +RMS gradient ... 0.0286921335 +MAX gradient ... 0.0460972644 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.122 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 4.0%) +RI-J Coulomb gradient .... 0.057 sec ( 47.2%) +XC gradient .... 0.018 sec ( 14.7%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.515068814 Eh +Current gradient norm .... 0.099392466 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999793166 +Lowest eigenvalues of augmented Hessian: + -0.000169521 0.357203333 0.394874058 0.437057517 0.673628291 +Length of the computed step .... 0.020341992 +The final length of the internal step .... 0.020341992 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0083045834 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0084652943 RMS(Int)= 0.0083034106 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000009 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0035439500 0.0001000000 NO + MAX gradient 0.0066154369 0.0003000000 NO + RMS step 0.0083045834 0.0020000000 NO + MAX step 0.0185176485 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0042 Max(Angles) 1.06 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3042 0.005451 -0.0042 1.3000 + 2. B(O 2,O 1) 1.3095 0.000875 -0.0007 1.3088 + 3. B(H 3,N 0) 1.0349 0.000626 -0.0008 1.0341 + 4. A(O 1,N 0,H 3) 110.56 0.006615 -1.06 109.50 + 5. A(N 0,O 1,O 2) 121.01 -0.000849 0.11 121.12 + 6. D(O 2,O 1,N 0,H 3) -69.23 -0.075011 -0.00 -69.23 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.967 %) +Internal coordinates : 0.000 s ( 4.089 %) +B/P matrices and projection : 0.000 s (16.171 %) +Hessian update/contruction : 0.000 s (27.138 %) +Making the step : 0.000 s ( 6.877 %) +Converting the step to Cartesian: 0.000 s ( 5.576 %) +Storing new data : 0.000 s ( 4.089 %) +Checking convergence : 0.000 s ( 0.186 %) +Final printing : 0.000 s (24.535 %) +Total time : 0.001 s + +Time for energy+gradient : 5.064 s +Time for complete geometry iter : 6.084 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.505616 -0.567710 -0.332143 + O 0.324019 0.418316 -0.503462 + O 0.375964 1.413817 0.344661 + H -0.213075 -1.126580 0.487236 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.955475 -1.072817 -0.627659 + 1 O 8.0000 0 15.999 0.612307 0.790503 -0.951406 + 2 O 8.0000 0 15.999 0.710469 2.671728 0.651314 + 3 H 1.0000 0 1.008 -0.402654 -2.128927 0.920743 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.299958517071 0.00000000 0.00000000 + O 2 1 0 1.308828930858 121.12138414 0.00000000 + H 1 2 3 1.034067873495 109.50071260 290.76923058 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.456565582723 0.00000000 0.00000000 + O 2 1 0 2.473328235475 121.12138414 0.00000000 + H 1 2 3 1.954105084792 109.50071260 290.76923058 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1674 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.132588821166 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.806e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22315 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5579 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.6 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5216464703957229 0.00e+00 1.71e-04 1.26e-03 3.26e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5216832709241714 -3.68e-05 1.71e-04 2.44e-03 6.19e-04 0.0 + 3 -205.5216394099693673 4.39e-05 1.35e-04 1.38e-03 3.10e-03 0.0 + 4 -205.5216890000961882 -4.96e-05 9.12e-05 1.35e-03 4.88e-04 0.0 + 5 -205.5216768000197760 1.22e-05 6.31e-05 9.32e-04 1.32e-03 0.0 + 6 -205.5216914849216607 -1.47e-05 1.70e-05 1.78e-04 6.26e-05 0.0 + 7 -205.5216914985819301 -1.37e-08 7.80e-06 8.70e-05 6.48e-05 0.0 + 8 -205.5216915824932187 -8.39e-08 1.32e-06 1.54e-05 4.93e-06 0.0 + 9 -205.5216915833926521 -8.99e-10 7.63e-07 8.44e-06 1.85e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.52169158339265 Eh -5592.52955 eV + +Components: +Nuclear Repulsion : 69.13258882116625 Eh 1881.19338 eV +Electronic Energy : -274.65428040455890 Eh -7473.72293 eV +One Electron Energy: -417.95796139379604 Eh -11373.21433 eV +Two Electron Energy: 143.30368098923717 Eh 3899.49141 eV + +Virial components: +Potential Energy : -410.34150409598419 Eh -11165.95999 eV +Kinetic Energy : 204.81981251259157 Eh 5573.43045 eV +Virial Ratio : 2.00342681238788 + +DFT components: +N(Alpha) : 11.999997827361 electrons +N(Beta) : 11.999997827361 electrons +N(Total) : 23.999995654722 electrons +E(X) : -23.325253704694 Eh +E(C) : -0.803699719304 Eh +E(XC) : -24.128953423998 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 8.9943e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.4420e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 7.6311e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.9192e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.8515e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.9591e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 1.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 19.4 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000362318 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006875986 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.515177915603 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001016 -0.000006279 0.000001601 + 2 O : 0.000000466 0.000000502 -0.000000786 + 3 O : 0.000002472 0.000007342 0.000001543 + 4 H : -0.000001922 -0.000001565 -0.000002358 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000108724 +RMS gradient ... 0.0000031386 +MAX gradient ... 0.0000073420 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.041224594 0.038753842 0.022293026 + 2 O : 0.043781400 -0.031923489 0.021889724 + 3 O : -0.024715061 0.017439527 -0.019247851 + 4 H : 0.022158255 -0.024269881 -0.024934899 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000131725 0.0000579266 -0.0000432632 + +Norm of the Cartesian gradient ... 0.1005017526 +RMS gradient ... 0.0290123570 +MAX gradient ... 0.0437814003 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.115 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.4%) +RI-J Coulomb gradient .... 0.054 sec ( 47.2%) +XC gradient .... 0.017 sec ( 14.6%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.515177916 Eh +Current gradient norm .... 0.100501753 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999951163 +Lowest eigenvalues of augmented Hessian: + -0.000024350 0.245423263 0.400161311 0.442399600 0.671908394 +Length of the computed step .... 0.009883355 +The final length of the internal step .... 0.009883355 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0040348627 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0041292852 RMS(Int)= 0.0040353778 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000004 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000012176 +Previously predicted energy change .... -0.000084795 +Actually observed energy change .... -0.000109102 +Ratio of predicted to observed change .... 1.286647529 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0001091018 0.0000050000 NO + RMS gradient 0.0010177532 0.0001000000 NO + MAX gradient 0.0023018263 0.0003000000 NO + RMS step 0.0040348627 0.0020000000 NO + MAX step 0.0095783510 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0010 Max(Angles) 0.55 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3000 0.000831 -0.0010 1.2989 + 2. B(O 2,O 1) 1.3088 -0.000185 0.0002 1.3090 + 3. B(H 3,N 0) 1.0341 -0.000375 0.0007 1.0347 + 4. A(O 1,N 0,H 3) 109.50 0.002302 -0.55 108.95 + 5. A(N 0,O 1,O 2) 121.12 0.000225 -0.04 121.08 + 6. D(O 2,O 1,N 0,H 3) -69.23 -0.075942 0.00 -69.23 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 7.461 %) +Internal coordinates : 0.000 s ( 3.010 %) +B/P matrices and projection : 0.000 s (11.911 %) +Hessian update/contruction : 0.000 s (40.838 %) +Making the step : 0.000 s ( 4.712 %) +Converting the step to Cartesian: 0.000 s ( 3.927 %) +Storing new data : 0.000 s ( 4.188 %) +Checking convergence : 0.000 s ( 1.440 %) +Final printing : 0.000 s (22.382 %) +Total time : 0.001 s + +Time for energy+gradient : 5.074 s +Time for complete geometry iter : 5.844 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.507470 -0.567585 -0.334294 + O 0.324054 0.415933 -0.503061 + O 0.375171 1.410967 0.345939 + H -0.210463 -1.121471 0.487708 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.958979 -1.072580 -0.631724 + 1 O 8.0000 0 15.999 0.612374 0.786000 -0.950647 + 2 O 8.0000 0 15.999 0.708971 2.666341 0.653729 + 3 H 1.0000 0 1.008 -0.397718 -2.119274 0.921635 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.298931434799 0.00000000 0.00000000 + O 2 1 0 1.309009110572 121.08375720 0.00000000 + H 1 2 3 1.034741733695 108.95191350 290.76923058 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.454624678511 0.00000000 0.00000000 + O 2 1 0 2.473668725790 121.08375720 0.00000000 + H 1 2 3 1.955378496022 108.95191350 290.76923058 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.164517563600 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.807e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22315 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5579 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5217107369491600 0.00e+00 8.48e-05 8.86e-04 2.13e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5217205703565924 -9.83e-06 6.73e-05 1.04e-03 2.62e-04 0.0 + 3 -205.5217171188737666 3.45e-06 5.86e-05 5.67e-04 9.87e-04 0.0 + 4 -205.5217218412419697 -4.72e-06 5.15e-05 6.78e-04 2.94e-04 0.0 + 5 -205.5217184425679307 3.40e-06 3.34e-05 5.27e-04 7.26e-04 0.0 + 6 -205.5217228693422840 -4.43e-06 8.58e-06 7.48e-05 2.51e-05 0.0 + 7 -205.5217228807083529 -1.14e-08 3.36e-06 3.63e-05 2.29e-05 0.0 + 8 -205.5217228945513170 -1.38e-08 5.65e-07 6.14e-06 2.91e-06 0.0 + 9 -205.5217228945925854 -4.13e-11 2.51e-07 2.61e-06 1.07e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.52172289459259 Eh -5592.53040 eV + +Components: +Nuclear Repulsion : 69.16451756360014 Eh 1882.06221 eV +Electronic Energy : -274.68624045819274 Eh -7474.59260 eV +One Electron Energy: -418.01898414503682 Eh -11374.87485 eV +Two Electron Energy: 143.33274368684408 Eh 3900.28224 eV + +Virial components: +Potential Energy : -410.34495223493479 Eh -11166.05382 eV +Kinetic Energy : 204.82322934034221 Eh 5573.52342 eV +Virial Ratio : 2.00341022625461 + +DFT components: +N(Alpha) : 11.999997572551 electrons +N(Beta) : 11.999997572551 electrons +N(Total) : 23.999995145101 electrons +E(X) : -23.325872830077 Eh +E(C) : -0.803743255068 Eh +E(XC) : -24.129616085146 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 4.1268e-11 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.6116e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.5099e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.8677e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.0719e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 8.2448e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 1.5 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 19.6 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000362391 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006894293 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.515190993047 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001001 -0.000006250 0.000001605 + 2 O : 0.000000463 0.000000489 -0.000000781 + 3 O : 0.000002459 0.000007289 0.000001552 + 4 H : -0.000001921 -0.000001527 -0.000002377 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000108150 +RMS gradient ... 0.0000031220 +MAX gradient ... 0.0000072887 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.041444892 0.039724569 0.020743603 + 2 O : 0.043081237 -0.033386356 0.023220740 + 3 O : -0.024726639 0.017546968 -0.019451737 + 4 H : 0.023090294 -0.023885180 -0.024512606 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000149493 0.0000574810 -0.0000506262 + +Norm of the Cartesian gradient ... 0.1011833297 +RMS gradient ... 0.0292091113 +MAX gradient ... 0.0430812366 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.132 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.1%) +RI-J Coulomb gradient .... 0.063 sec ( 47.9%) +XC gradient .... 0.019 sec ( 14.2%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.515190993 Eh +Current gradient norm .... 0.101183330 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999997929 +Lowest eigenvalues of augmented Hessian: + -0.000001471 0.205369103 0.400580167 0.442579323 0.673016139 +Length of the computed step .... 0.002035307 +The final length of the internal step .... 0.002035307 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0008309106 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0006632841 RMS(Int)= 0.0008309328 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000735 +Previously predicted energy change .... -0.000012176 +Actually observed energy change .... -0.000013077 +Ratio of predicted to observed change .... 1.074039330 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000130774 0.0000050000 NO + RMS gradient 0.0003581552 0.0001000000 NO + MAX gradient 0.0007360655 0.0003000000 NO + RMS step 0.0008309106 0.0020000000 YES + MAX step 0.0016028339 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0005 Max(Angles) 0.09 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2989 -0.000736 0.0005 1.2994 + 2. B(O 2,O 1) 1.3090 -0.000239 0.0002 1.3092 + 3. B(H 3,N 0) 1.0347 -0.000062 0.0001 1.0348 + 4. A(O 1,N 0,H 3) 108.95 0.000294 -0.09 108.86 + 5. A(N 0,O 1,O 2) 121.08 0.000284 -0.04 121.04 + 6. D(O 2,O 1,N 0,H 3) -69.23 -0.076343 -0.00 -69.23 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.274 %) +Internal coordinates : 0.000 s ( 3.226 %) +B/P matrices and projection : 0.000 s (12.097 %) +Hessian update/contruction : 0.000 s (35.215 %) +Making the step : 0.000 s ( 5.242 %) +Converting the step to Cartesian: 0.000 s ( 4.032 %) +Storing new data : 0.000 s ( 3.226 %) +Checking convergence : 0.000 s ( 1.478 %) +Final printing : 0.000 s (25.806 %) +Total time : 0.001 s + +Time for energy+gradient : 5.269 s +Time for complete geometry iter : 6.212 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 4 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.507974 -0.567769 -0.334566 + O 0.324330 0.415761 -0.503281 + O 0.375015 1.410602 0.346279 + H -0.210079 -1.120751 0.487860 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.959931 -1.072927 -0.632238 + 1 O 8.0000 0 15.999 0.612895 0.785675 -0.951063 + 2 O 8.0000 0 15.999 0.708675 2.665652 0.654373 + 3 H 1.0000 0 1.008 -0.396992 -2.117912 0.921921 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.299432699994 0.00000000 0.00000000 + O 2 1 0 1.309209306495 121.04359829 0.00000000 + H 1 2 3 1.034849816486 108.86007788 290.76923058 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.455571932450 0.00000000 0.00000000 + O 2 1 0 2.474047041256 121.04359829 0.00000000 + H 1 2 3 1.955582742897 108.86007788 290.76923058 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.151855627166 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.809e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22315 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5579 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.5 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5217270133628062 0.00e+00 2.20e-05 2.15e-04 4.92e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5217276945298863 -6.81e-07 1.31e-05 1.12e-04 4.80e-05 0.1 + 3 -205.5217277957777355 -1.01e-07 1.08e-05 9.62e-05 3.85e-05 0.0 + 4 -205.5217277656714714 3.01e-08 5.68e-06 5.85e-05 7.04e-05 0.0 + 5 -205.5217278134288108 -4.78e-08 7.40e-06 1.03e-04 3.64e-05 0.0 + 6 -205.5217277243348235 8.91e-08 5.71e-06 9.36e-05 1.16e-04 0.0 + 7 -205.5217278218693764 -9.75e-08 1.57e-06 1.67e-05 6.76e-06 0.0 + 8 -205.5217278222184518 -3.49e-10 7.62e-07 8.29e-06 5.82e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.52172782221845 Eh -5592.53053 eV + +Components: +Nuclear Repulsion : 69.15185562716603 Eh 1881.71766 eV +Electronic Energy : -274.67358344938447 Eh -7474.24819 eV +One Electron Energy: -417.99447441952265 Eh -11374.20790 eV +Two Electron Energy: 143.32089097013818 Eh 3899.95971 eV + +Virial components: +Potential Energy : -410.34370781862322 Eh -11166.01996 eV +Kinetic Energy : 204.82197999640476 Eh 5573.48943 eV +Virial Ratio : 2.00341637077147 + +DFT components: +N(Alpha) : 11.999997520992 electrons +N(Beta) : 11.999997520992 electrons +N(Total) : 23.999995041984 electrons +E(X) : -23.325437526044 Eh +E(C) : -0.803711690330 Eh +E(XC) : -24.129149216375 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.4908e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.2861e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 7.6195e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.4903e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 5.8227e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.4101e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.3 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 19.8 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000362397 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006898126 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.515192093672 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001000 -0.000006248 0.000001605 + 2 O : 0.000000464 0.000000488 -0.000000781 + 3 O : 0.000002459 0.000007283 0.000001555 + 4 H : -0.000001922 -0.000001523 -0.000002379 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000108102 +RMS gradient ... 0.0000031206 +MAX gradient ... 0.0000072835 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.041677767 0.039525506 0.020648893 + 2 O : 0.043238895 -0.033360212 0.023066740 + 3 O : -0.024736391 0.017688722 -0.019284452 + 4 H : 0.023175263 -0.023854015 -0.024431181 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000159583 0.0000577551 -0.0000498292 + +Norm of the Cartesian gradient ... 0.1011924822 +RMS gradient ... 0.0292117534 +MAX gradient ... 0.0432388951 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.132 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.7%) +RI-J Coulomb gradient .... 0.058 sec ( 43.9%) +XC gradient .... 0.021 sec ( 15.8%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.515192094 Eh +Current gradient norm .... 0.101192482 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999997826 +Lowest eigenvalues of augmented Hessian: + -0.000000966 0.158423128 0.396585479 0.407526547 0.528380800 +Length of the computed step .... 0.002085241 +The final length of the internal step .... 0.002085241 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0008512960 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0005562198 RMS(Int)= 0.0008512941 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000483 +Previously predicted energy change .... -0.000000735 +Actually observed energy change .... -0.000001101 +Ratio of predicted to observed change .... 1.496834629 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000011006 0.0000050000 YES + RMS gradient 0.0002181302 0.0001000000 NO + MAX gradient 0.0005046268 0.0003000000 NO + RMS step 0.0008512960 0.0020000000 YES + MAX step 0.0014550113 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0008 Max(Angles) 0.07 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2994 -0.000505 0.0008 1.3002 + 2. B(O 2,O 1) 1.3092 -0.000025 0.0001 1.3093 + 3. B(H 3,N 0) 1.0348 -0.000000 0.0000 1.0349 + 4. A(O 1,N 0,H 3) 108.86 0.000087 -0.07 108.79 + 5. A(N 0,O 1,O 2) 121.04 0.000150 -0.05 121.00 + 6. D(O 2,O 1,N 0,H 3) -69.23 -0.076359 -0.00 -69.23 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.582 %) +Internal coordinates : 0.000 s ( 3.175 %) +B/P matrices and projection : 0.000 s (14.815 %) +Hessian update/contruction : 0.000 s (31.481 %) +Making the step : 0.000 s ( 5.820 %) +Converting the step to Cartesian: 0.000 s ( 4.233 %) +Storing new data : 0.000 s ( 3.439 %) +Checking convergence : 0.000 s ( 1.455 %) +Final printing : 0.000 s (24.735 %) +Total time : 0.001 s + +Time for energy+gradient : 5.043 s +Time for complete geometry iter : 5.850 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 5 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.508458 -0.568021 -0.334712 + O 0.324685 0.415797 -0.503532 + O 0.374874 1.410307 0.346548 + H -0.209810 -1.120239 0.487988 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.960846 -1.073405 -0.632513 + 1 O 8.0000 0 15.999 0.613566 0.785743 -0.951538 + 2 O 8.0000 0 15.999 0.708410 2.665095 0.654881 + 3 H 1.0000 0 1.008 -0.396483 -2.116945 0.922163 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.300202658811 0.00000000 0.00000000 + O 2 1 0 1.309277054552 120.99837750 0.00000000 + H 1 2 3 1.034876442828 108.78784584 290.76923058 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.457026943748 0.00000000 0.00000000 + O 2 1 0 2.474175066530 120.99837750 0.00000000 + H 1 2 3 1.955633059392 108.78784584 290.76923058 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1674 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.136388544544 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.811e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22315 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5579 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5217305646041268 0.00e+00 2.32e-05 1.95e-04 4.30e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5217314157964097 -8.51e-07 1.58e-05 1.27e-04 5.43e-05 0.0 + 3 -205.5217313964136565 1.94e-08 1.55e-05 2.17e-04 1.38e-04 0.0 + 4 -205.5217314324938798 -3.61e-08 1.38e-05 1.53e-04 9.91e-05 0.0 + 5 -205.5217313915558748 4.09e-08 8.32e-06 1.06e-04 1.36e-04 0.0 + 6 -205.5217315303532359 -1.39e-07 7.28e-06 7.41e-05 4.00e-05 0.0 + 7 -205.5217315470979429 -1.67e-08 2.75e-06 2.74e-05 1.96e-05 0.0 + 8 -205.5217315546348686 -7.54e-09 6.40e-07 4.59e-06 4.83e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.52173155463487 Eh -5592.53063 eV + +Components: +Nuclear Repulsion : 69.13638854454432 Eh 1881.29678 eV +Electronic Energy : -274.65812009917920 Eh -7473.82741 eV +One Electron Energy: -417.96489724091589 Eh -11373.40307 eV +Two Electron Energy: 143.30677714173666 Eh 3899.57566 eV + +Virial components: +Potential Energy : -410.34215840225636 Eh -11165.97780 eV +Kinetic Energy : 204.82042684762146 Eh 5573.44716 eV +Virial Ratio : 2.00342399787857 + +DFT components: +N(Alpha) : 11.999997473124 electrons +N(Beta) : 11.999997473124 electrons +N(Total) : 23.999994946249 electrons +E(X) : -23.324979812020 Eh +E(C) : -0.803675701721 Eh +E(XC) : -24.128655513740 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 7.5369e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.5919e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 6.3952e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.9359e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.8274e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.2634e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.1 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 20.0 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000362400 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006901345 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.515192609956 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000999 -0.000006247 0.000001605 + 2 O : 0.000000465 0.000000487 -0.000000781 + 3 O : 0.000002458 0.000007280 0.000001557 + 4 H : -0.000001924 -0.000001521 -0.000002380 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000108075 +RMS gradient ... 0.0000031199 +MAX gradient ... 0.0000072800 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.041945604 0.039171014 0.020688846 + 2 O : 0.043505930 -0.033134582 0.022823745 + 3 O : -0.024755085 0.017789940 -0.019117595 + 4 H : 0.023194759 -0.023826373 -0.024394997 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000123771 0.0000571193 -0.0000506771 + +Norm of the Cartesian gradient ... 0.1011385566 +RMS gradient ... 0.0291961864 +MAX gradient ... 0.0435059301 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.115 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.3%) +RI-J Coulomb gradient .... 0.052 sec ( 44.8%) +XC gradient .... 0.018 sec ( 15.7%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.515192610 Eh +Current gradient norm .... 0.101138557 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999942 +Lowest eigenvalues of augmented Hessian: + -0.000000054 0.153849355 0.388434890 0.406921936 0.489442313 +Length of the computed step .... 0.000341792 +The final length of the internal step .... 0.000341792 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0001395359 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0000608959 RMS(Int)= 0.0001395356 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000027 +Previously predicted energy change .... -0.000000483 +Actually observed energy change .... -0.000000516 +Ratio of predicted to observed change .... 1.068582130 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000005163 0.0000050000 YES + RMS gradient 0.0000725270 0.0001000000 YES + MAX gradient 0.0001560232 0.0003000000 YES + RMS step 0.0001395359 0.0020000000 YES + MAX step 0.0002398198 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3002 -0.000080 0.0001 1.3003 + 2. B(O 2,O 1) 1.3093 0.000156 -0.0001 1.3092 + 3. B(H 3,N 0) 1.0349 0.000012 -0.0000 1.0349 + 4. A(O 1,N 0,H 3) 108.79 -0.000005 -0.01 108.78 + 5. A(N 0,O 1,O 2) 121.00 -0.000026 -0.00 121.00 + 6. D(O 2,O 1,N 0,H 3) -69.23 -0.076344 0.00 -69.23 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (11.005 %) +Internal coordinates : 0.000 s ( 2.989 %) +B/P matrices and projection : 0.000 s (12.364 %) +Hessian update/contruction : 0.000 s (31.522 %) +Making the step : 0.000 s ( 5.299 %) +Converting the step to Cartesian: 0.000 s ( 3.804 %) +Storing new data : 0.000 s ( 4.076 %) +Checking convergence : 0.000 s ( 1.359 %) +Final printing : 0.000 s (27.310 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 5 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.508499 -0.568060 -0.334711 + O 0.324722 0.415865 -0.503506 + O 0.374870 1.410267 0.346520 + H -0.209802 -1.120228 0.487989 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.960923 -1.073478 -0.632512 + 1 O 8.0000 0 15.999 0.613636 0.785871 -0.951488 + 2 O 8.0000 0 15.999 0.708402 2.665018 0.654828 + 3 H 1.0000 0 1.008 -0.396468 -2.116924 0.922165 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.300329565996 0.00000000 0.00000000 + O 2 1 0 1.309157563617 120.99820129 0.00000000 + H 1 2 3 1.034864407379 108.78278779 290.76923058 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.457266763574 0.00000000 0.00000000 + O 2 1 0 2.473949261389 120.99820129 0.00000000 + H 1 2 3 1.955610315690 108.78278779 290.76923058 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1674 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.136526985998 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.810e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22315 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5579 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.1365269860 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5217316282531783 0.00e+00 4.03e-06 3.93e-05 6.27e-06 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5217316573506423 -2.91e-08 4.99e-06 5.91e-05 2.17e-05 0.0 + 3 -205.5217316104461815 4.69e-08 4.03e-06 4.89e-05 9.95e-05 0.0 + 4 -205.5217316613656067 -5.09e-08 1.56e-06 2.42e-05 9.37e-06 0.0 + 5 -205.5217316574622259 3.90e-09 1.15e-06 1.79e-05 2.49e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.52173165746223 Eh -5592.53064 eV + +Components: +Nuclear Repulsion : 69.13652698599832 Eh 1881.30054 eV +Electronic Energy : -274.65825864346061 Eh -7473.83118 eV +One Electron Energy: -417.96494205534856 Eh -11373.40429 eV +Two Electron Energy: 143.30668341188797 Eh 3899.57311 eV + +Virial components: +Potential Energy : -410.34214163704559 Eh -11165.97734 eV +Kinetic Energy : 204.82040997958336 Eh 5573.44670 eV +Virial Ratio : 2.00342408101785 + +DFT components: +N(Alpha) : 11.999997467709 electrons +N(Beta) : 11.999997467709 electrons +N(Total) : 23.999994935417 electrons +E(X) : -23.324969640280 Eh +E(C) : -0.803676033060 Eh +E(XC) : -24.128645673341 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -3.9034e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.7925e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.1481e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.8783e-05 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.4914e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.0555e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.187394 -522.1155 + 1 2.0000 -19.041243 -518.1386 + 2 2.0000 -14.254171 -387.8757 + 3 2.0000 -1.242934 -33.8220 + 4 2.0000 -0.965098 -26.2617 + 5 2.0000 -0.714097 -19.4316 + 6 2.0000 -0.567233 -15.4352 + 7 2.0000 -0.517514 -14.0823 + 8 2.0000 -0.494699 -13.4614 + 9 2.0000 -0.334779 -9.1098 + 10 2.0000 -0.275941 -7.5087 + 11 2.0000 -0.255379 -6.9492 + 12 0.0000 -0.216526 -5.8920 + 13 0.0000 0.035083 0.9547 + 14 0.0000 0.094193 2.5631 + 15 0.0000 0.133046 3.6204 + 16 0.0000 0.229813 6.2535 + 17 0.0000 0.258525 7.0348 + 18 0.0000 0.315820 8.5939 + 19 0.0000 0.326347 8.8804 + 20 0.0000 0.365558 9.9473 + 21 0.0000 0.375595 10.2205 + 22 0.0000 0.394598 10.7376 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.326330 + 1 O : 0.198815 + 2 O : -0.151456 + 3 H : 0.278971 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.833310 s : 3.833310 + pz : 1.468319 p : 3.439760 + px : 0.974164 + py : 0.997277 + dz2 : 0.012377 d : 0.053261 + dxz : 0.006631 + dyz : 0.006493 + dx2y2 : 0.013584 + dxy : 0.014174 + + 1 O s : 3.746775 s : 3.746775 + pz : 1.489663 p : 3.927396 + px : 1.297359 + py : 1.140374 + dz2 : 0.030193 d : 0.127014 + dxz : 0.022371 + dyz : 0.020379 + dx2y2 : 0.031085 + dxy : 0.022987 + + 2 O s : 3.942416 s : 3.942416 + pz : 1.497651 p : 4.195458 + px : 1.596262 + py : 1.101545 + dz2 : 0.003233 d : 0.013582 + dxz : 0.001910 + dyz : 0.003958 + dx2y2 : 0.003965 + dxy : 0.000516 + + 3 H s : 0.690355 s : 0.690355 + pz : 0.014513 p : 0.030674 + px : 0.006286 + py : 0.009875 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.097461 + 1 O : -0.177122 + 2 O : -0.006057 + 3 H : 0.280640 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.332791 s : 3.332791 + pz : 1.407176 p : 3.459996 + px : 1.010385 + py : 1.042435 + dz2 : 0.040211 d : 0.304675 + dxz : 0.035032 + dyz : 0.079620 + dx2y2 : 0.062805 + dxy : 0.087006 + + 1 O s : 3.374588 s : 3.374588 + pz : 1.483461 p : 4.042894 + px : 1.284303 + py : 1.275130 + dz2 : 0.125531 d : 0.759640 + dxz : 0.067255 + dyz : 0.198160 + dx2y2 : 0.183427 + dxy : 0.185266 + + 2 O s : 3.610610 s : 3.610610 + pz : 1.459889 p : 4.146840 + px : 1.514176 + py : 1.172775 + dz2 : 0.054693 d : 0.248607 + dxz : 0.023901 + dyz : 0.082272 + dx2y2 : 0.040369 + dxy : 0.047372 + + 3 H s : 0.641203 s : 0.641203 + pz : 0.039739 p : 0.078157 + px : 0.015633 + py : 0.022784 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3263 7.0000 -0.3263 2.7386 2.7386 0.0000 + 1 O 7.8012 8.0000 0.1988 2.5644 2.5644 -0.0000 + 2 O 8.1515 8.0000 -0.1515 1.6814 1.6814 0.0000 + 3 H 0.7210 1.0000 0.2790 0.9100 0.9100 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3834 B( 0-N , 2-O ) : 0.4966 B( 0-N , 3-H ) : 0.8586 +B( 1-O , 2-O ) : 1.1572 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.022 sec +Sum of individual times .... 1.009 sec ( 98.7%) + +SCF preparation .... 0.479 sec ( 46.9%) +Fock matrix formation .... 0.127 sec ( 12.4%) + Startup .... 0.007 sec ( 5.4% of F) + Split-RI-J .... 0.017 sec ( 13.6% of F) + XC integration .... 0.085 sec ( 66.8% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.005 sec ( 5.8% of XC) + Density eval. .... 0.008 sec ( 9.1% of XC) + XC-Functional eval. .... 0.004 sec ( 4.8% of XC) + XC-Potential eval. .... 0.007 sec ( 8.7% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.008 sec ( 0.7%) +Total Energy calculation .... 0.010 sec ( 0.9%) +Population analysis .... 0.345 sec ( 33.8%) +Orbital Transformation .... 0.006 sec ( 0.6%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.009 sec ( 0.9%) +SOSCF solution .... 0.025 sec ( 2.5%) +Finished LeanSCF after 1.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 20.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000362400 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006901410 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.515192647415 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.013.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.013.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.155106 0.809153 -0.269634 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5217316574622259 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.344287068 0.883251178 -0.279053189 +Nuclear contribution : -0.269168597 -1.443828918 0.592523841 + ----------------------------------------- +Total Dipole Moment : 0.075118471 -0.560577740 0.313470653 + ----------------------------------------- +Magnitude (a.u.) : 0.646648310 +Magnitude (Debye) : 1.643649382 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.028446 0.411161 0.373242 +Rotational constants in MHz : 90790.520093 12326.297894 11189.501679 + +Dipole components along the rotational axes: +x,y,z [a.u.] : -0.381736 0.266891 -0.448554 +x,y,z [Debye]: -0.970297 0.678383 -1.140133 + + + +Dipole moment calculation done in 0.2 sec + +Maximum memory used throughout the entire PROP-calculation: 11.1 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 14 * + * * + * Dihedral ( 2, 1, 0, 3) : -60.00000000 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.3013 0.696748 + 2. B(O 2,O 1) 1.3111 0.674515 + 3. B(H 3,N 0) 1.0376 0.394935 + 4. A(O 1,N 0,H 3) 108.6094 0.357945 + 5. A(N 0,O 1,O 2) 120.8174 0.438269 + 6. D(O 2,O 1,N 0,H 3) -60.0000 0.037900 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.491613 -0.587510 -0.356323 + O 0.303131 0.428344 -0.528930 + O 0.382148 1.379643 0.369816 + H -0.212375 -1.082633 0.511729 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.929013 -1.110234 -0.673352 + 1 O 8.0000 0 15.999 0.572835 0.809453 -0.999533 + 2 O 8.0000 0 15.999 0.722156 2.607148 0.698850 + 3 H 1.0000 0 1.008 -0.401330 -2.045879 0.967028 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.300329565996 0.00000000 0.00000000 + O 2 1 0 1.309157563617 120.99820129 0.00000000 + H 1 2 3 1.034864407379 108.78278779 290.76923058 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.457266763574 0.00000000 0.00000000 + O 2 1 0 2.473949261389 120.99820129 0.00000000 + H 1 2 3 1.955610315690 108.78278779 290.76923058 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1674 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.109184549689 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.860e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22315 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5579 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.1091845497 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5295462661209740 0.00e+00 4.75e-04 3.47e-03 1.90e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.054) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5306102551031131 -1.06e-03 5.45e-04 4.13e-03 1.50e-02 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.5315007163917471 -8.90e-04 4.04e-04 2.88e-03 1.07e-02 0.700 0.0 + 4 -205.5321144771327226 -6.14e-04 1.00e-03 7.43e-03 7.53e-03 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5335698992332141 -1.46e-03 1.05e-04 1.57e-03 1.43e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -205.5335738072280378 -3.91e-06 4.02e-04 4.26e-03 1.39e-03 0.1 + 7 -205.5332894331520492 2.84e-04 3.04e-04 3.86e-03 6.92e-03 0.0 + 8 -205.5335912876635689 -3.02e-04 2.87e-05 2.95e-04 1.07e-04 0.0 + 9 -205.5335915319075184 -2.44e-07 2.38e-05 2.48e-04 1.62e-04 0.0 + 10 -205.5335915909324740 -5.90e-08 1.27e-05 1.01e-04 1.05e-04 0.0 + 11 -205.5335917457180699 -1.55e-07 3.52e-06 3.75e-05 1.94e-05 0.0 + 12 -205.5335917523635203 -6.65e-09 1.30e-06 1.46e-05 6.95e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.53359175236352 Eh -5592.85337 eV + +Components: +Nuclear Repulsion : 69.10918454968949 Eh 1880.55652 eV +Electronic Energy : -274.64277630205299 Eh -7473.40988 eV +One Electron Energy: -417.92591273257318 Eh -11372.34224 eV +Two Electron Energy: 143.28313643052016 Eh 3898.93236 eV + +Virial components: +Potential Energy : -410.33933749624043 Eh -11165.90104 eV +Kinetic Energy : 204.80574574387694 Eh 5573.04767 eV +Virial Ratio : 2.00355383588406 + +DFT components: +N(Alpha) : 11.999996122399 electrons +N(Beta) : 11.999996122399 electrons +N(Total) : 23.999992244798 electrons +E(X) : -23.324364691453 Eh +E(C) : -0.803402975639 Eh +E(XC) : -24.127767667092 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 6.6455e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.4632e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.2978e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.4265e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 6.9534e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.8152e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.187282 -522.1125 + 1 2.0000 -19.036119 -517.9991 + 2 2.0000 -14.261141 -388.0654 + 3 2.0000 -1.241722 -33.7890 + 4 2.0000 -0.963590 -26.2206 + 5 2.0000 -0.716469 -19.4961 + 6 2.0000 -0.565635 -15.3917 + 7 2.0000 -0.516111 -14.0441 + 8 2.0000 -0.494004 -13.4425 + 9 2.0000 -0.334059 -9.0902 + 10 2.0000 -0.273577 -7.4444 + 11 2.0000 -0.264841 -7.2067 + 12 0.0000 -0.210274 -5.7219 + 13 0.0000 0.034009 0.9254 + 14 0.0000 0.091886 2.5004 + 15 0.0000 0.130853 3.5607 + 16 0.0000 0.227254 6.1839 + 17 0.0000 0.260473 7.0878 + 18 0.0000 0.313555 8.5323 + 19 0.0000 0.326152 8.8751 + 20 0.0000 0.363316 9.8863 + 21 0.0000 0.381554 10.3826 + 22 0.0000 0.394926 10.7465 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.302069 + 1 O : 0.199231 + 2 O : -0.171767 + 3 H : 0.274604 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.838754 s : 3.838754 + pz : 1.431529 p : 3.409646 + px : 0.994210 + py : 0.983907 + dz2 : 0.013058 d : 0.053670 + dxz : 0.005996 + dyz : 0.006023 + dx2y2 : 0.014479 + dxy : 0.014114 + + 1 O s : 3.746765 s : 3.746765 + pz : 1.479281 p : 3.924485 + px : 1.303519 + py : 1.141685 + dz2 : 0.032103 d : 0.129519 + dxz : 0.021465 + dyz : 0.020051 + dx2y2 : 0.033069 + dxy : 0.022831 + + 2 O s : 3.943809 s : 3.943809 + pz : 1.474359 p : 4.213954 + px : 1.587413 + py : 1.152182 + dz2 : 0.002092 d : 0.014004 + dxz : 0.002513 + dyz : 0.005282 + dx2y2 : 0.003221 + dxy : 0.000896 + + 3 H s : 0.695512 s : 0.695512 + pz : 0.014995 p : 0.029884 + px : 0.006083 + py : 0.008806 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.081880 + 1 O : -0.177855 + 2 O : -0.019172 + 3 H : 0.278906 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.342839 s : 3.342839 + pz : 1.379338 p : 3.434115 + px : 1.016674 + py : 1.038103 + dz2 : 0.043667 d : 0.304926 + dxz : 0.031342 + dyz : 0.081276 + dx2y2 : 0.062668 + dxy : 0.085974 + + 1 O s : 3.376024 s : 3.376024 + pz : 1.480604 p : 4.043834 + px : 1.283326 + py : 1.279904 + dz2 : 0.135321 d : 0.757997 + dxz : 0.064803 + dyz : 0.199376 + dx2y2 : 0.176519 + dxy : 0.181978 + + 2 O s : 3.610583 s : 3.610583 + pz : 1.447006 p : 4.160261 + px : 1.504956 + py : 1.208299 + dz2 : 0.060404 d : 0.248327 + dxz : 0.026560 + dyz : 0.080563 + dx2y2 : 0.037124 + dxy : 0.043676 + + 3 H s : 0.644328 s : 0.644328 + pz : 0.041468 p : 0.076765 + px : 0.015111 + py : 0.020186 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3021 7.0000 -0.3021 2.7626 2.7626 -0.0000 + 1 O 7.8008 8.0000 0.1992 2.5763 2.5763 0.0000 + 2 O 8.1718 8.0000 -0.1718 1.6820 1.6820 -0.0000 + 3 H 0.7254 1.0000 0.2746 0.9139 0.9139 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3942 B( 0-N , 2-O ) : 0.5011 B( 0-N , 3-H ) : 0.8673 +B( 1-O , 2-O ) : 1.1581 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.447 sec +Sum of individual times .... 1.432 sec ( 98.9%) + +SCF preparation .... 0.540 sec ( 37.3%) +Fock matrix formation .... 0.328 sec ( 22.7%) + Startup .... 0.014 sec ( 4.1% of F) + Split-RI-J .... 0.046 sec ( 14.0% of F) + XC integration .... 0.222 sec ( 67.6% of F) + Basis function eval. .... 0.013 sec ( 5.7% of XC) + Density eval. .... 0.017 sec ( 7.7% of XC) + XC-Functional eval. .... 0.012 sec ( 5.3% of XC) + XC-Potential eval. .... 0.018 sec ( 8.3% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.022 sec ( 1.5%) +Total Energy calculation .... 0.025 sec ( 1.7%) +Population analysis .... 0.387 sec ( 26.8%) +Orbital Transformation .... 0.014 sec ( 1.0%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.070 sec ( 4.9%) +SOSCF solution .... 0.046 sec ( 3.1%) +Finished LeanSCF after 1.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 20.7 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000362752 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006940331 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.527014173186 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001031 -0.000006044 0.000001682 + 2 O : 0.000000429 0.000000503 -0.000000829 + 3 O : 0.000002406 0.000006921 0.000001690 + 4 H : -0.000001804 -0.000001381 -0.000002543 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000104745 +RMS gradient ... 0.0000030237 +MAX gradient ... 0.0000069211 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.044335514 0.031810180 0.019083629 + 2 O : 0.046375178 -0.025913593 0.013550996 + 3 O : -0.024245603 0.017918152 -0.013453042 + 4 H : 0.022205940 -0.023814738 -0.019181583 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000238992 0.0000131073 -0.0000177885 + +Norm of the Cartesian gradient ... 0.0941572279 +RMS gradient ... 0.0271808504 +MAX gradient ... 0.0463751777 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.134 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.7%) +RI-J Coulomb gradient .... 0.060 sec ( 45.0%) +XC gradient .... 0.021 sec ( 15.4%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.527014173 Eh +Current gradient norm .... 0.094157228 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999860756 +Lowest eigenvalues of augmented Hessian: + -0.000140658 0.357167407 0.390975971 0.437429102 0.669749796 +Length of the computed step .... 0.016689727 +The final length of the internal step .... 0.016689727 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0068135527 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0071138187 RMS(Int)= 0.0068119782 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000014 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0036187618 0.0001000000 NO + MAX gradient 0.0072592150 0.0003000000 NO + RMS step 0.0068135527 0.0020000000 NO + MAX step 0.0120052407 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0055 Max(Angles) 0.69 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3013 0.007259 -0.0055 1.2958 + 2. B(O 2,O 1) 1.3111 0.002320 -0.0018 1.3093 + 3. B(H 3,N 0) 1.0376 0.001291 -0.0017 1.0359 + 4. A(O 1,N 0,H 3) 108.61 0.004289 -0.69 107.92 + 5. A(N 0,O 1,O 2) 120.82 -0.000656 0.09 120.90 + 6. D(O 2,O 1,N 0,H 3) -60.00 -0.070073 0.00 -60.00 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (11.166 %) +Internal coordinates : 0.000 s ( 3.722 %) +B/P matrices and projection : 0.000 s (14.392 %) +Hessian update/contruction : 0.000 s (28.040 %) +Making the step : 0.000 s ( 6.576 %) +Converting the step to Cartesian: 0.000 s ( 4.963 %) +Storing new data : 0.000 s ( 3.474 %) +Checking convergence : 0.000 s ( 0.124 %) +Final printing : 0.000 s (27.419 %) +Total time : 0.001 s + +Time for energy+gradient : 5.549 s +Time for complete geometry iter : 6.393 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.492355 -0.586273 -0.358399 + O 0.301769 0.423712 -0.526631 + O 0.380626 1.373857 0.370677 + H -0.208749 -1.073452 0.510644 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.930415 -1.107896 -0.677276 + 1 O 8.0000 0 15.999 0.570261 0.800700 -0.995188 + 2 O 8.0000 0 15.999 0.719279 2.596214 0.700478 + 3 H 1.0000 0 1.008 -0.394478 -2.028530 0.964978 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.295764223509 0.00000000 0.00000000 + O 2 1 0 1.309257516629 120.90322193 0.00000000 + H 1 2 3 1.035862749239 107.92159285 300.00000007 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.448639516564 0.00000000 0.00000000 + O 2 1 0 2.474138145207 120.90322193 0.00000000 + H 1 2 3 1.957496908392 107.92159285 300.00000007 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1676 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.306977405462 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.833e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22317 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5579 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5336614753924778 0.00e+00 1.50e-04 9.95e-04 2.47e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5336921199881886 -3.06e-05 1.62e-04 2.11e-03 6.02e-04 0.0 + 3 -205.5336480791485769 4.40e-05 1.32e-04 1.58e-03 2.75e-03 0.0 + 4 -205.5336941304631182 -4.61e-05 1.25e-04 1.83e-03 6.41e-04 0.0 + 5 -205.5336697407347515 2.44e-05 8.92e-05 1.35e-03 1.95e-03 0.0 + 6 -205.5336979370550239 -2.82e-05 1.87e-05 2.05e-04 7.71e-05 0.0 + 7 -205.5336979252867309 1.18e-08 9.49e-06 1.06e-04 8.09e-05 0.0 + 8 -205.5336980482596800 -1.23e-07 4.66e-07 4.68e-06 1.47e-06 0.0 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.53369804825968 Eh -5592.85626 eV + +Components: +Nuclear Repulsion : 69.30697740546225 Eh 1885.93873 eV +Electronic Energy : -274.84067545372193 Eh -7478.79499 eV +One Electron Energy: -418.30287711603080 Eh -11382.59997 eV +Two Electron Energy: 143.46220166230887 Eh 3903.80497 eV + +Virial components: +Potential Energy : -410.36107927533874 Eh -11166.49266 eV +Kinetic Energy : 204.82738122707903 Eh 5573.63640 eV +Virial Ratio : 2.00344835156779 + +DFT components: +N(Alpha) : 11.999996050380 electrons +N(Beta) : 11.999996050380 electrons +N(Total) : 23.999992100759 electrons +E(X) : -23.330027940001 Eh +E(C) : -0.803779616221 Eh +E(XC) : -24.133807556223 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.2297e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.6804e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.6645e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.1457e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.4662e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.3668e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.3 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 20.8 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000362890 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006961651 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.527099286424 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.0 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001002 -0.000005980 0.000001693 + 2 O : 0.000000421 0.000000481 -0.000000811 + 3 O : 0.000002373 0.000006803 0.000001690 + 4 H : -0.000001793 -0.000001305 -0.000002572 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000103436 +RMS gradient ... 0.0000029859 +MAX gradient ... 0.0000068030 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.042918934 0.034589558 0.017757400 + 2 O : 0.044018043 -0.029264165 0.017823732 + 3 O : -0.024453049 0.016774075 -0.015282790 + 4 H : 0.023353940 -0.022099468 -0.020298342 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000245224 0.0000118700 -0.0000233029 + +Norm of the Cartesian gradient ... 0.0949955953 +RMS gradient ... 0.0274228663 +MAX gradient ... 0.0440180431 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.102 sec + +Densities .... 0.000 sec ( 0.4%) +One electron gradient .... 0.005 sec ( 4.7%) +RI-J Coulomb gradient .... 0.047 sec ( 46.4%) +XC gradient .... 0.015 sec ( 14.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.527099286 Eh +Current gradient norm .... 0.094995595 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999989332 +Lowest eigenvalues of augmented Hessian: + -0.000009262 0.327517486 0.401532402 0.436562132 0.582060394 +Length of the computed step .... 0.004619068 +The final length of the internal step .... 0.004619068 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0018857267 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0017457061 RMS(Int)= 0.0018857128 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000004 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000004631 +Previously predicted energy change .... -0.000070349 +Actually observed energy change .... -0.000085113 +Ratio of predicted to observed change .... 1.209879733 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000851132 0.0000050000 NO + RMS gradient 0.0008519689 0.0001000000 NO + MAX gradient 0.0019234925 0.0003000000 NO + RMS step 0.0018857267 0.0020000000 YES + MAX step 0.0036181040 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0019 Max(Angles) 0.15 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2958 0.001923 -0.0019 1.2938 + 2. B(O 2,O 1) 1.3093 0.000229 -0.0003 1.3090 + 3. B(H 3,N 0) 1.0359 -0.000243 0.0004 1.0363 + 4. A(O 1,N 0,H 3) 107.92 0.000724 -0.15 107.77 + 5. A(N 0,O 1,O 2) 120.90 -0.000140 0.02 120.93 + 6. D(O 2,O 1,N 0,H 3) -60.00 -0.070823 0.00 -60.00 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 7.212 %) +Internal coordinates : 0.000 s ( 3.606 %) +B/P matrices and projection : 0.000 s (12.205 %) +Hessian update/contruction : 0.000 s (42.857 %) +Making the step : 0.000 s ( 4.577 %) +Converting the step to Cartesian: 0.000 s ( 3.606 %) +Storing new data : 0.000 s ( 2.913 %) +Checking convergence : 0.000 s ( 1.248 %) +Final printing : 0.000 s (21.637 %) +Total time : 0.001 s + +Time for energy+gradient : 5.087 s +Time for complete geometry iter : 5.924 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.492434 -0.585587 -0.359189 + O 0.301306 0.422450 -0.526180 + O 0.380239 1.372430 0.370931 + H -0.207819 -1.071449 0.510729 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.930565 -1.106599 -0.678768 + 1 O 8.0000 0 15.999 0.569385 0.798315 -0.994335 + 2 O 8.0000 0 15.999 0.718548 2.593517 0.700958 + 3 H 1.0000 0 1.008 -0.392721 -2.024746 0.965139 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.293849605352 0.00000000 0.00000000 + O 2 1 0 1.309007157451 120.92739692 0.00000000 + H 1 2 3 1.036255673027 107.76687386 300.00000007 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.445021412597 0.00000000 0.00000000 + O 2 1 0 2.473665034926 120.92739692 0.00000000 + H 1 2 3 1.958239426743 107.76687386 300.00000007 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.359885405218 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.828e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22317 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5579 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5337049379302528 0.00e+00 4.49e-05 3.26e-04 9.84e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5337081853122925 -3.25e-06 4.45e-05 5.10e-04 1.78e-04 0.0 + 3 -205.5337055006006892 2.68e-06 3.40e-05 4.19e-04 6.23e-04 0.0 + 4 -205.5337082151967536 -2.71e-06 5.00e-05 6.66e-04 2.26e-04 0.0 + 5 -205.5337041125086728 4.10e-06 3.68e-05 5.24e-04 7.85e-04 0.0 + 6 -205.5337087437667094 -4.63e-06 5.22e-06 5.69e-05 2.11e-05 0.0 + 7 -205.5337087438047377 -3.80e-11 2.60e-06 2.92e-05 2.08e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.53370874380474 Eh -5592.85655 eV + +Components: +Nuclear Repulsion : 69.35988540521825 Eh 1887.37843 eV +Electronic Energy : -274.89359414902299 Eh -7480.23498 eV +One Electron Energy: -418.40337040040231 Eh -11385.33453 eV +Two Electron Energy: 143.50977625137929 Eh 3905.09954 eV + +Virial components: +Potential Energy : -410.36615978308259 Eh -11166.63091 eV +Kinetic Energy : 204.83245103927786 Eh 5573.77436 eV +Virial Ratio : 2.00342356741312 + +DFT components: +N(Alpha) : 11.999996025454 electrons +N(Beta) : 11.999996025454 electrons +N(Total) : 23.999992050907 electrons +E(X) : -23.331227599664 Eh +E(C) : -0.803876896706 Eh +E(XC) : -24.135104496370 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.8028e-11 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.9184e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.5968e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.9579e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.0753e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.4482e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.1 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 21.0 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000362930 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006967613 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.527104060388 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000000994 -0.000005963 0.000001696 + 2 O : 0.000000419 0.000000475 -0.000000808 + 3 O : 0.000002365 0.000006774 0.000001690 + 4 H : -0.000001790 -0.000001287 -0.000002578 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000103110 +RMS gradient ... 0.0000029765 +MAX gradient ... 0.0000067742 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.042525170 0.035865684 0.016887184 + 2 O : 0.043244582 -0.030424852 0.018920459 + 3 O : -0.024519900 0.016499813 -0.015730256 + 4 H : 0.023800489 -0.021940646 -0.020077387 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000258483 0.0000082134 -0.0000247451 + +Norm of the Cartesian gradient ... 0.0954229039 +RMS gradient ... 0.0275462196 +MAX gradient ... 0.0432445816 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.117 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 4.0%) +RI-J Coulomb gradient .... 0.055 sec ( 47.6%) +XC gradient .... 0.016 sec ( 13.9%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.527104060 Eh +Current gradient norm .... 0.095422904 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999713 +Lowest eigenvalues of augmented Hessian: + -0.000000303 0.358666724 0.399934281 0.432710892 0.506506444 +Length of the computed step .... 0.000757669 +The final length of the internal step .... 0.000757669 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0003093172 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001881231 RMS(Int)= 0.0003093247 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000151 +Previously predicted energy change .... -0.000004631 +Actually observed energy change .... -0.000004774 +Ratio of predicted to observed change .... 1.030812263 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000047740 0.0000050000 YES + RMS gradient 0.0001666203 0.0001000000 NO + MAX gradient 0.0002819770 0.0003000000 YES + RMS step 0.0003093172 0.0020000000 YES + MAX step 0.0004594236 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0002 Max(Angles) 0.02 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2938 0.000224 -0.0002 1.2936 + 2. B(O 2,O 1) 1.3090 -0.000282 0.0002 1.3092 + 3. B(H 3,N 0) 1.0363 -0.000031 0.0000 1.0363 + 4. A(O 1,N 0,H 3) 107.77 -0.000184 0.02 107.79 + 5. A(N 0,O 1,O 2) 120.93 -0.000044 0.01 120.93 + 6. D(O 2,O 1,N 0,H 3) -60.00 -0.071044 -0.00 -60.00 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.913 %) +Internal coordinates : 0.000 s ( 3.353 %) +B/P matrices and projection : 0.000 s (12.828 %) +Hessian update/contruction : 0.000 s (31.778 %) +Making the step : 0.000 s ( 6.560 %) +Converting the step to Cartesian: 0.000 s ( 4.082 %) +Storing new data : 0.000 s ( 3.499 %) +Checking convergence : 0.000 s ( 1.458 %) +Final printing : 0.000 s (26.385 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.492310 -0.585506 -0.359161 + O 0.301215 0.422379 -0.526208 + O 0.380290 1.372615 0.370934 + H -0.207903 -1.071644 0.510728 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.930331 -1.106446 -0.678717 + 1 O 8.0000 0 15.999 0.569213 0.798181 -0.994389 + 2 O 8.0000 0 15.999 0.718645 2.593867 0.700963 + 3 H 1.0000 0 1.008 -0.392880 -2.025115 0.965136 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.293606488859 0.00000000 0.00000000 + O 2 1 0 1.309222855753 120.93427361 0.00000000 + H 1 2 3 1.036303522597 107.79079204 300.00000007 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.444561989007 0.00000000 0.00000000 + O 2 1 0 2.474072645643 120.93427361 0.00000000 + H 1 2 3 1.958329849326 107.79079204 300.00000007 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.359051324096 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.829e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22317 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5579 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.3590513241 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5337080366913938 0.00e+00 8.07e-06 7.23e-05 1.37e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5337081581172356 -1.21e-07 7.39e-06 6.95e-05 2.78e-05 0.1 + 3 -205.5337080769664908 8.12e-08 5.65e-06 7.56e-05 1.25e-04 0.0 + 4 -205.5337081690859691 -9.21e-08 3.25e-06 4.96e-05 2.04e-05 0.0 + 5 -205.5337081533592709 1.57e-08 2.19e-06 3.61e-05 5.11e-05 0.0 + 6 -205.5337081723063193 -1.89e-08 3.43e-07 3.33e-06 1.05e-06 0.0 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 6 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.53370817230632 Eh -5592.85653 eV + +Components: +Nuclear Repulsion : 69.35905132409596 Eh 1887.35574 eV +Electronic Energy : -274.89275949640228 Eh -7480.21227 eV +One Electron Energy: -418.40299112127167 Eh -11385.32421 eV +Two Electron Energy: 143.51023162486942 Eh 3905.11193 eV + +Virial components: +Potential Energy : -410.36606640968802 Eh -11166.62837 eV +Kinetic Energy : 204.83235823738170 Eh 5573.77183 eV +Virial Ratio : 2.00342401923680 + +DFT components: +N(Alpha) : 11.999996025594 electrons +N(Beta) : 11.999996025594 electrons +N(Total) : 23.999992051188 electrons +E(X) : -23.331350031230 Eh +E(C) : -0.803878303884 Eh +E(XC) : -24.135228335113 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.8947e-08 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.3311e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.4291e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.1759e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.0472e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 4.9272e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.187463 -522.1174 + 1 2.0000 -19.035430 -517.9804 + 2 2.0000 -14.260979 -388.0610 + 3 2.0000 -1.245406 -33.8892 + 4 2.0000 -0.966651 -26.3039 + 5 2.0000 -0.715527 -19.4705 + 6 2.0000 -0.566806 -15.4236 + 7 2.0000 -0.517869 -14.0919 + 8 2.0000 -0.495064 -13.4714 + 9 2.0000 -0.334483 -9.1017 + 10 2.0000 -0.273498 -7.4423 + 11 2.0000 -0.264600 -7.2001 + 12 0.0000 -0.209333 -5.6962 + 13 0.0000 0.036714 0.9991 + 14 0.0000 0.092878 2.5274 + 15 0.0000 0.134361 3.6561 + 16 0.0000 0.229261 6.2385 + 17 0.0000 0.259793 7.0693 + 18 0.0000 0.313536 8.5317 + 19 0.0000 0.325859 8.8671 + 20 0.0000 0.362882 9.8745 + 21 0.0000 0.381883 10.3916 + 22 0.0000 0.395675 10.7669 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.300388 + 1 O : 0.200439 + 2 O : -0.174287 + 3 H : 0.274236 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.837199 s : 3.837199 + pz : 1.429678 p : 3.408682 + px : 0.993611 + py : 0.985392 + dz2 : 0.013193 d : 0.054507 + dxz : 0.006201 + dyz : 0.006006 + dx2y2 : 0.014811 + dxy : 0.014296 + + 1 O s : 3.743310 s : 3.743310 + pz : 1.480290 p : 3.925930 + px : 1.302705 + py : 1.142935 + dz2 : 0.032225 d : 0.130321 + dxz : 0.021700 + dyz : 0.020188 + dx2y2 : 0.033296 + dxy : 0.022912 + + 2 O s : 3.943089 s : 3.943089 + pz : 1.474517 p : 4.217056 + px : 1.592611 + py : 1.149928 + dz2 : 0.002120 d : 0.014142 + dxz : 0.002511 + dyz : 0.005345 + dx2y2 : 0.003235 + dxy : 0.000931 + + 3 H s : 0.695767 s : 0.695767 + pz : 0.015071 p : 0.029997 + px : 0.006188 + py : 0.008738 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.079663 + 1 O : -0.180722 + 2 O : -0.018663 + 3 H : 0.279047 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.339173 s : 3.339173 + pz : 1.375565 p : 3.432975 + px : 1.017318 + py : 1.040093 + dz2 : 0.044155 d : 0.307514 + dxz : 0.031894 + dyz : 0.081467 + dx2y2 : 0.063308 + dxy : 0.086690 + + 1 O s : 3.371224 s : 3.371224 + pz : 1.481187 p : 4.045995 + px : 1.283797 + py : 1.281012 + dz2 : 0.135453 d : 0.763502 + dxz : 0.066217 + dyz : 0.201098 + dx2y2 : 0.178131 + dxy : 0.182603 + + 2 O s : 3.608972 s : 3.608972 + pz : 1.446259 p : 4.161421 + px : 1.508972 + py : 1.206190 + dz2 : 0.060328 d : 0.248270 + dxz : 0.026601 + dyz : 0.080484 + dx2y2 : 0.037114 + dxy : 0.043743 + + 3 H s : 0.644135 s : 0.644135 + pz : 0.041615 p : 0.076818 + px : 0.015357 + py : 0.019846 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3004 7.0000 -0.3004 2.7639 2.7639 -0.0000 + 1 O 7.7996 8.0000 0.2004 2.5779 2.5779 0.0000 + 2 O 8.1743 8.0000 -0.1743 1.6788 1.6788 -0.0000 + 3 H 0.7258 1.0000 0.2742 0.9146 0.9146 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3971 B( 0-N , 2-O ) : 0.4985 B( 0-N , 3-H ) : 0.8683 +B( 1-O , 2-O ) : 1.1574 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.251 sec +Sum of individual times .... 1.236 sec ( 98.7%) + +SCF preparation .... 0.590 sec ( 47.2%) +Fock matrix formation .... 0.173 sec ( 13.8%) + Startup .... 0.008 sec ( 4.8% of F) + Split-RI-J .... 0.023 sec ( 13.2% of F) + XC integration .... 0.118 sec ( 68.3% of F) + Basis function eval. .... 0.008 sec ( 6.9% of XC) + Density eval. .... 0.008 sec ( 7.2% of XC) + XC-Functional eval. .... 0.006 sec ( 5.0% of XC) + XC-Potential eval. .... 0.009 sec ( 7.7% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.010 sec ( 0.8%) +Total Energy calculation .... 0.013 sec ( 1.0%) +Population analysis .... 0.400 sec ( 32.0%) +Orbital Transformation .... 0.007 sec ( 0.5%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.010 sec ( 0.8%) +SOSCF solution .... 0.034 sec ( 2.7%) +Finished LeanSCF after 1.7 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 21.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000362927 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006966779 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.527104320865 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.014.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.014.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.152666 0.781275 -0.281379 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5337081723063193 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.303759851 0.811684436 -0.324581302 +Nuclear contribution : -0.266308983 -1.384447352 0.619796457 + ----------------------------------------- +Total Dipole Moment : 0.037450868 -0.572762916 0.295215154 + ----------------------------------------- +Magnitude (a.u.) : 0.645454811 +Magnitude (Debye) : 1.640615748 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.995598 0.416858 0.375559 +Rotational constants in MHz : 89805.777329 12497.094803 11258.960889 + +Dipole components along the rotational axes: +x,y,z [a.u.] : -0.400341 0.314610 -0.396686 +x,y,z [Debye]: -1.017585 0.799676 -1.008295 + + + +Dipole moment calculation done in 0.2 sec + +Maximum memory used throughout the entire PROP-calculation: 11.6 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 15 * + * * + * Dihedral ( 2, 1, 0, 3) : -50.76923077 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2948 0.714171 + 2. B(O 2,O 1) 1.3110 0.674353 + 3. B(H 3,N 0) 1.0389 0.392852 + 4. A(O 1,N 0,H 3) 107.6011 0.359129 + 5. A(N 0,O 1,O 2) 120.7377 0.440208 + 6. D(O 2,O 1,N 0,H 3) -50.7692 0.040033 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.472577 -0.605722 -0.378222 + O 0.277547 0.435775 -0.548639 + O 0.388749 1.342587 0.391664 + H -0.212426 -1.034796 0.531488 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.893042 -1.144648 -0.714735 + 1 O 8.0000 0 15.999 0.524487 0.823495 -1.036777 + 2 O 8.0000 0 15.999 0.734629 2.537122 0.740138 + 3 H 1.0000 0 1.008 -0.401427 -1.955481 1.004367 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.293606488859 0.00000000 0.00000000 + O 2 1 0 1.309222855753 120.93427361 0.00000000 + H 1 2 3 1.036303522597 107.79079204 300.00000007 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.444561989007 0.00000000 0.00000000 + O 2 1 0 2.474072645643 120.93427361 0.00000000 + H 1 2 3 1.958329849326 107.79079204 300.00000007 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1676 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.332445806093 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.896e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22317 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5579 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.3324458061 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5405058327979191 0.00e+00 4.41e-04 3.12e-03 1.93e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.069) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5415750737108169 -1.07e-03 5.09e-04 3.62e-03 1.49e-02 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.5424598612019622 -8.85e-04 3.78e-04 2.51e-03 1.05e-02 0.700 0.0 + 4 -205.5430714122794029 -6.12e-04 9.31e-04 6.47e-03 7.44e-03 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5445152996691718 -1.44e-03 1.07e-04 1.83e-03 1.55e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -205.5445166606902490 -1.36e-06 4.31e-04 4.96e-03 1.29e-03 0.0 + 7 -205.5441460696477520 3.71e-04 3.44e-04 4.63e-03 7.87e-03 0.0 + 8 -205.5445352156493755 -3.89e-04 3.41e-05 4.35e-04 2.29e-04 0.0 + 9 -205.5445336992875127 1.52e-06 2.17e-05 3.81e-04 5.65e-04 0.0 + 10 -205.5445357149521328 -2.02e-06 5.01e-06 4.35e-05 1.62e-05 0.0 + 11 -205.5445357223626388 -7.41e-09 1.64e-06 1.45e-05 1.44e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.54453572236264 Eh -5593.15117 eV + +Components: +Nuclear Repulsion : 69.33244580609333 Eh 1886.63176 eV +Electronic Energy : -274.87698152845599 Eh -7479.78293 eV +One Electron Energy: -418.36136660769171 Eh -11384.19155 eV +Two Electron Energy: 143.48438507923572 Eh 3904.40861 eV + +Virial components: +Potential Energy : -410.35905311264702 Eh -11166.43753 eV +Kinetic Energy : 204.81451739028438 Eh 5573.28636 eV +Virial Ratio : 2.00356428997993 + +DFT components: +N(Alpha) : 11.999997147719 electrons +N(Beta) : 11.999997147719 electrons +N(Total) : 23.999994295437 electrons +E(X) : -23.329966471767 Eh +E(C) : -0.803640559712 Eh +E(XC) : -24.133607031479 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 7.4105e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.4524e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.6407e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.5542e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.4368e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.9711e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.188394 -522.1427 + 1 2.0000 -19.031277 -517.8674 + 2 2.0000 -14.266449 -388.2098 + 3 2.0000 -1.244620 -33.8678 + 4 2.0000 -0.965158 -26.2633 + 5 2.0000 -0.717785 -19.5319 + 6 2.0000 -0.564985 -15.3740 + 7 2.0000 -0.517039 -14.0694 + 8 2.0000 -0.494845 -13.4654 + 9 2.0000 -0.333992 -9.0884 + 10 2.0000 -0.273246 -7.4354 + 11 2.0000 -0.271329 -7.3832 + 12 0.0000 -0.203490 -5.5372 + 13 0.0000 0.034225 0.9313 + 14 0.0000 0.092216 2.5093 + 15 0.0000 0.132263 3.5991 + 16 0.0000 0.226054 6.1512 + 17 0.0000 0.262738 7.1495 + 18 0.0000 0.310945 8.4612 + 19 0.0000 0.326268 8.8782 + 20 0.0000 0.360702 9.8152 + 21 0.0000 0.384693 10.4680 + 22 0.0000 0.395805 10.7704 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.281792 + 1 O : 0.201872 + 2 O : -0.190531 + 3 H : 0.270451 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.841917 s : 3.841917 + pz : 1.401887 p : 3.385680 + px : 1.011304 + py : 0.972489 + dz2 : 0.013549 d : 0.054195 + dxz : 0.005349 + dyz : 0.005595 + dx2y2 : 0.015428 + dxy : 0.014274 + + 1 O s : 3.744412 s : 3.744412 + pz : 1.468581 p : 3.920635 + px : 1.308802 + py : 1.143252 + dz2 : 0.033921 d : 0.133080 + dxz : 0.020874 + dyz : 0.020546 + dx2y2 : 0.034378 + dxy : 0.023361 + + 2 O s : 3.943370 s : 3.943370 + pz : 1.444145 p : 4.232032 + px : 1.578223 + py : 1.209664 + dz2 : 0.001177 d : 0.015128 + dxz : 0.003363 + dyz : 0.006520 + dx2y2 : 0.002625 + dxy : 0.001444 + + 3 H s : 0.700210 s : 0.700210 + pz : 0.015647 p : 0.029339 + px : 0.005939 + py : 0.007753 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.067672 + 1 O : -0.180163 + 2 O : -0.030271 + 3 H : 0.278106 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.346931 s : 3.346931 + pz : 1.354974 p : 3.413893 + px : 1.021127 + py : 1.037792 + dz2 : 0.047714 d : 0.306848 + dxz : 0.028029 + dyz : 0.082168 + dx2y2 : 0.063679 + dxy : 0.085258 + + 1 O s : 3.372918 s : 3.372918 + pz : 1.476917 p : 4.044770 + px : 1.282095 + py : 1.285757 + dz2 : 0.144385 d : 0.762476 + dxz : 0.064600 + dyz : 0.202128 + dx2y2 : 0.172028 + dxy : 0.179335 + + 2 O s : 3.609057 s : 3.609057 + pz : 1.426708 p : 4.173065 + px : 1.495348 + py : 1.251009 + dz2 : 0.065830 d : 0.248149 + dxz : 0.029247 + dyz : 0.078529 + dx2y2 : 0.034358 + dxy : 0.040186 + + 3 H s : 0.646327 s : 0.646327 + pz : 0.043459 p : 0.075567 + px : 0.014702 + py : 0.017406 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2818 7.0000 -0.2818 2.7786 2.7786 -0.0000 + 1 O 7.7981 8.0000 0.2019 2.5941 2.5941 0.0000 + 2 O 8.1905 8.0000 -0.1905 1.6815 1.6815 -0.0000 + 3 H 0.7295 1.0000 0.2705 0.9184 0.9184 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4075 B( 0-N , 2-O ) : 0.4978 B( 0-N , 3-H ) : 0.8732 +B( 1-O , 2-O ) : 1.1625 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.381 sec +Sum of individual times .... 1.368 sec ( 99.0%) + +SCF preparation .... 0.531 sec ( 38.4%) +Fock matrix formation .... 0.298 sec ( 21.6%) + Startup .... 0.013 sec ( 4.4% of F) + Split-RI-J .... 0.041 sec ( 13.7% of F) + XC integration .... 0.197 sec ( 66.3% of F) + Basis function eval. .... 0.011 sec ( 5.6% of XC) + Density eval. .... 0.013 sec ( 6.7% of XC) + XC-Functional eval. .... 0.009 sec ( 4.8% of XC) + XC-Potential eval. .... 0.013 sec ( 6.6% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.022 sec ( 1.6%) +Total Energy calculation .... 0.024 sec ( 1.7%) +Population analysis .... 0.369 sec ( 26.7%) +Orbital Transformation .... 0.014 sec ( 1.0%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.070 sec ( 5.1%) +SOSCF solution .... 0.039 sec ( 2.8%) +Finished LeanSCF after 1.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 21.7 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000363218 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007013541 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.537885399281 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001041 -0.000005759 0.000001761 + 2 O : 0.000000380 0.000000492 -0.000000851 + 3 O : 0.000002315 0.000006447 0.000001810 + 4 H : -0.000001654 -0.000001180 -0.000002720 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000100096 +RMS gradient ... 0.0000028895 +MAX gradient ... 0.0000064471 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.043463326 0.026595867 0.014701770 + 2 O : 0.044211188 -0.022098303 0.009084907 + 3 O : -0.022868196 0.016209266 -0.009368400 + 4 H : 0.022120334 -0.020706829 -0.014418278 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000229382 -0.0000222973 -0.0000040018 + +Norm of the Cartesian gradient ... 0.0856590498 +RMS gradient ... 0.0247276377 +MAX gradient ... 0.0442111880 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.108 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.3%) +RI-J Coulomb gradient .... 0.052 sec ( 47.8%) +XC gradient .... 0.017 sec ( 15.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.537885399 Eh +Current gradient norm .... 0.085659050 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999888856 +Lowest eigenvalues of augmented Hessian: + -0.000125895 0.358306583 0.389099469 0.439336545 0.669857805 +Length of the computed step .... 0.014910548 +The final length of the internal step .... 0.014910548 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0060872059 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0060018096 RMS(Int)= 0.0060864354 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0035959879 0.0001000000 NO + MAX gradient 0.0076643560 0.0003000000 NO + RMS step 0.0060872059 0.0020000000 NO + MAX step 0.0107760864 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0057 Max(Angles) 0.49 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2948 0.007664 -0.0057 1.2891 + 2. B(O 2,O 1) 1.3110 0.002554 -0.0020 1.3090 + 3. B(H 3,N 0) 1.0389 0.001466 -0.0020 1.0369 + 4. A(O 1,N 0,H 3) 107.60 0.003085 -0.49 107.11 + 5. A(N 0,O 1,O 2) 120.74 -0.000812 0.11 120.84 + 6. D(O 2,O 1,N 0,H 3) -50.77 -0.062683 0.00 -50.77 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.013 %) +Internal coordinates : 0.000 s ( 3.504 %) +B/P matrices and projection : 0.000 s (13.642 %) +Hessian update/contruction : 0.000 s (26.533 %) +Making the step : 0.000 s ( 6.884 %) +Converting the step to Cartesian: 0.000 s ( 5.257 %) +Storing new data : 0.000 s ( 4.506 %) +Checking convergence : 0.000 s ( 0.125 %) +Final printing : 0.000 s (29.161 %) +Total time : 0.001 s + +Time for energy+gradient : 5.598 s +Time for complete geometry iter : 6.450 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.472509 -0.604294 -0.379474 + O 0.276118 0.431761 -0.546377 + O 0.387372 1.337584 0.392062 + H -0.209689 -1.027208 0.530080 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.892912 -1.141950 -0.717101 + 1 O 8.0000 0 15.999 0.521787 0.815910 -1.032502 + 2 O 8.0000 0 15.999 0.732027 2.527668 0.740890 + 3 H 1.0000 0 1.008 -0.396255 -1.941141 1.001706 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.289072582707 0.00000000 0.00000000 + O 2 1 0 1.309030362373 120.84361857 0.00000000 + H 1 2 3 1.036927400741 107.10802564 309.23076898 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.435994148063 0.00000000 0.00000000 + O 2 1 0 2.473708885873 120.84361857 0.00000000 + H 1 2 3 1.959508808160 107.10802564 309.23076898 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.536240716329 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.868e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22315 +Total number of batches ... 349 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5579 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5445963432847520 0.00e+00 1.39e-04 1.03e-03 1.94e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5446241095772848 -2.78e-05 1.50e-04 1.83e-03 5.12e-04 0.0 + 3 -205.5445858552955087 3.83e-05 1.22e-04 1.62e-03 2.31e-03 0.0 + 4 -205.5446245621088224 -3.87e-05 1.32e-04 1.95e-03 6.85e-04 0.0 + 5 -205.5445972996611772 2.73e-05 9.37e-05 1.47e-03 2.20e-03 0.0 + 6 -205.5446285375219304 -3.12e-05 1.98e-05 2.17e-04 8.25e-05 0.0 + 7 -205.5446285115910428 2.59e-08 1.04e-05 1.15e-04 8.95e-05 0.0 + 8 -205.5446286590546947 -1.47e-07 2.22e-07 2.26e-06 1.04e-06 0.0 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.54462865905469 Eh -5593.15370 eV + +Components: +Nuclear Repulsion : 69.53624071632902 Eh 1892.17731 eV +Electronic Energy : -275.08086937538371 Eh -7485.33100 eV +One Electron Energy: -418.75011944954610 Eh -11394.77005 eV +Two Electron Energy: 143.66925007416239 Eh 3909.43905 eV + +Virial components: +Potential Energy : -410.38141913226713 Eh -11167.04614 eV +Kinetic Energy : 204.83679047321243 Eh 5573.89244 eV +Virial Ratio : 2.00345562037077 + +DFT components: +N(Alpha) : 11.999997371733 electrons +N(Beta) : 11.999997371733 electrons +N(Total) : 23.999994743465 electrons +E(X) : -23.335968291432 Eh +E(C) : -0.804033775011 Eh +E(XC) : -24.140002066443 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.4746e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.2562e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.2230e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.2866e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.0371e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.0366e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 21.8 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000363329 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007030186 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.537961802670 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001017 -0.000005703 0.000001771 + 2 O : 0.000000374 0.000000475 -0.000000834 + 3 O : 0.000002285 0.000006347 0.000001805 + 4 H : -0.000001642 -0.000001119 -0.000002741 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000098979 +RMS gradient ... 0.0000028573 +MAX gradient ... 0.0000063466 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.041811964 0.029594207 0.013888566 + 2 O : 0.042015872 -0.025455317 0.013182358 + 3 O : -0.023178084 0.014985098 -0.011290242 + 4 H : 0.022974176 -0.019123988 -0.015780681 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000161913 -0.0000226229 -0.0000055392 + +Norm of the Cartesian gradient ... 0.0862313559 +RMS gradient ... 0.0248928483 +MAX gradient ... 0.0420158717 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.122 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.9%) +RI-J Coulomb gradient .... 0.057 sec ( 46.7%) +XC gradient .... 0.017 sec ( 14.1%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.537961803 Eh +Current gradient norm .... 0.086231356 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999989384 +Lowest eigenvalues of augmented Hessian: + -0.000010670 0.361744983 0.405535702 0.432828215 0.536465653 +Length of the computed step .... 0.004607817 +The final length of the internal step .... 0.004607817 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0018811335 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0012002844 RMS(Int)= 0.0018810877 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000005335 +Previously predicted energy change .... -0.000062961 +Actually observed energy change .... -0.000076403 +Ratio of predicted to observed change .... 1.213494931 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000764034 0.0000050000 NO + RMS gradient 0.0009528313 0.0001000000 NO + MAX gradient 0.0022789874 0.0003000000 NO + RMS step 0.0018811335 0.0020000000 YES + MAX step 0.0043693091 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0023 Max(Angles) 0.06 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2891 0.002279 -0.0023 1.2868 + 2. B(O 2,O 1) 1.3090 0.000306 -0.0004 1.3087 + 3. B(H 3,N 0) 1.0369 -0.000219 0.0003 1.0372 + 4. A(O 1,N 0,H 3) 107.11 0.000096 -0.03 107.07 + 5. A(N 0,O 1,O 2) 120.84 -0.000320 0.06 120.90 + 6. D(O 2,O 1,N 0,H 3) -50.77 -0.063319 0.00 -50.77 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 7.250 %) +Internal coordinates : 0.000 s ( 3.000 %) +B/P matrices and projection : 0.000 s (12.750 %) +Hessian update/contruction : 0.000 s (42.500 %) +Making the step : 0.000 s ( 5.375 %) +Converting the step to Cartesian: 0.000 s ( 4.000 %) +Storing new data : 0.000 s ( 3.000 %) +Checking convergence : 0.000 s ( 1.375 %) +Final printing : 0.000 s (20.625 %) +Total time : 0.001 s + +Time for energy+gradient : 5.091 s +Time for complete geometry iter : 5.845 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.472060 -0.603365 -0.379885 + O 0.275479 0.430756 -0.545810 + O 0.387157 1.336717 0.391937 + H -0.209284 -1.026264 0.530050 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.892063 -1.140195 -0.717879 + 1 O 8.0000 0 15.999 0.520580 0.814012 -1.031431 + 2 O 8.0000 0 15.999 0.731620 2.526028 0.740653 + 3 H 1.0000 0 1.008 -0.395490 -1.939358 1.001650 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.286760443918 0.00000000 0.00000000 + O 2 1 0 1.308665238798 120.89957371 0.00000000 + H 1 2 3 1.037245218222 107.07410068 309.23076898 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.431624838968 0.00000000 0.00000000 + O 2 1 0 2.473018902310 120.89957371 0.00000000 + H 1 2 3 1.960109396159 107.07410068 309.23076898 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.597444939556 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.861e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22315 +Total number of batches ... 349 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5579 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5446314589140968 0.00e+00 4.90e-05 4.27e-04 7.63e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5446355605011206 -4.10e-06 4.73e-05 4.70e-04 1.98e-04 0.1 + 3 -205.5446326741494261 2.89e-06 3.52e-05 5.02e-04 5.78e-04 0.0 + 4 -205.5446354580661534 -2.78e-06 5.76e-05 7.92e-04 2.64e-04 0.0 + 5 -205.5446299353424990 5.52e-06 4.24e-05 6.34e-04 9.63e-04 0.0 + 6 -205.5446361297640863 -6.19e-06 6.70e-06 7.28e-05 2.66e-05 0.0 + 7 -205.5446361280936856 1.67e-09 3.46e-06 3.83e-05 2.82e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.54463612809369 Eh -5593.15390 eV + +Components: +Nuclear Repulsion : 69.59744493955620 Eh 1893.84276 eV +Electronic Energy : -275.14208106764988 Eh -7486.99666 eV +One Electron Energy: -418.86610935681034 Eh -11397.92629 eV +Two Electron Energy: 143.72402828916046 Eh 3910.92964 eV + +Virial components: +Potential Energy : -410.38743257166897 Eh -11167.20977 eV +Kinetic Energy : 204.84279644357528 Eh 5574.05587 eV +Virial Ratio : 2.00342623561435 + +DFT components: +N(Alpha) : 11.999997283985 electrons +N(Beta) : 11.999997283985 electrons +N(Total) : 23.999994567971 electrons +E(X) : -23.337440385710 Eh +E(C) : -0.804149111553 Eh +E(XC) : -24.141589497263 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.6704e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.8321e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.4596e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.9494e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.8163e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.9245e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.3 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 22.0 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000363359 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007031672 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.537967814317 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001012 -0.000005691 0.000001773 + 2 O : 0.000000372 0.000000471 -0.000000831 + 3 O : 0.000002278 0.000006327 0.000001802 + 4 H : -0.000001638 -0.000001107 -0.000002744 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000098749 +RMS gradient ... 0.0000028506 +MAX gradient ... 0.0000063271 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.041161829 0.031139425 0.013192017 + 2 O : 0.041168065 -0.026729713 0.014295054 + 3 O : -0.023268193 0.014639432 -0.011855841 + 4 H : 0.023261957 -0.019049144 -0.015631230 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000164346 -0.0000277480 -0.0000034514 + +Norm of the Cartesian gradient ... 0.0865807809 +RMS gradient ... 0.0249937186 +MAX gradient ... 0.0411680649 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.131 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.0%) +RI-J Coulomb gradient .... 0.063 sec ( 47.8%) +XC gradient .... 0.021 sec ( 15.7%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.537967814 Eh +Current gradient norm .... 0.086580781 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999998484 +Lowest eigenvalues of augmented Hessian: + -0.000001134 0.341909026 0.394544079 0.421253590 0.499410019 +Length of the computed step .... 0.001741086 +The final length of the internal step .... 0.001741086 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0007107956 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0005150046 RMS(Int)= 0.0007108380 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000567 +Previously predicted energy change .... -0.000005335 +Actually observed energy change .... -0.000006012 +Ratio of predicted to observed change .... 1.126794848 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000060116 0.0000050000 NO + RMS gradient 0.0002756143 0.0001000000 NO + MAX gradient 0.0004265360 0.0003000000 NO + RMS step 0.0007107956 0.0020000000 YES + MAX step 0.0011818465 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0006 Max(Angles) 0.07 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2868 0.000367 -0.0006 1.2862 + 2. B(O 2,O 1) 1.3087 -0.000346 0.0003 1.3089 + 3. B(H 3,N 0) 1.0372 -0.000052 0.0001 1.0373 + 4. A(O 1,N 0,H 3) 107.07 -0.000427 0.07 107.14 + 5. A(N 0,O 1,O 2) 120.90 -0.000129 0.03 120.92 + 6. D(O 2,O 1,N 0,H 3) -50.77 -0.063511 -0.00 -50.77 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.303 %) +Internal coordinates : 0.000 s ( 2.909 %) +B/P matrices and projection : 0.000 s (11.273 %) +Hessian update/contruction : 0.000 s (34.303 %) +Making the step : 0.000 s ( 5.939 %) +Converting the step to Cartesian: 0.000 s ( 3.879 %) +Storing new data : 0.000 s ( 3.030 %) +Checking convergence : 0.000 s ( 1.818 %) +Final printing : 0.000 s (26.182 %) +Total time : 0.001 s + +Time for energy+gradient : 4.839 s +Time for complete geometry iter : 5.690 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 4 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.471724 -0.603117 -0.379775 + O 0.275257 0.430678 -0.545762 + O 0.387299 1.337146 0.391803 + H -0.209540 -1.026863 0.530026 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.891429 -1.139726 -0.717671 + 1 O 8.0000 0 15.999 0.520160 0.813864 -1.031341 + 2 O 8.0000 0 15.999 0.731888 2.526840 0.740400 + 3 H 1.0000 0 1.008 -0.395972 -1.940490 1.001605 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.286182278185 0.00000000 0.00000000 + O 2 1 0 1.308917647900 120.92464281 0.00000000 + H 1 2 3 1.037323613760 107.14181550 309.23076898 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.430532264072 0.00000000 0.00000000 + O 2 1 0 2.473495886387 120.92464281 0.00000000 + H 1 2 3 1.960257542255 107.14181550 309.23076898 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.601316851688 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.863e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22316 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5579 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5446335126576685 0.00e+00 1.77e-05 1.56e-04 3.23e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5446340790718125 -5.66e-07 1.52e-05 1.24e-04 5.02e-05 0.1 + 3 -205.5446338137259374 2.65e-07 1.17e-05 1.74e-04 2.11e-04 0.0 + 4 -205.5446341117542204 -2.98e-07 1.12e-05 1.68e-04 6.52e-05 0.0 + 5 -205.5446339622083372 1.50e-07 6.88e-06 1.17e-04 1.70e-04 0.0 + 6 -205.5446341467512923 -1.85e-07 2.01e-06 2.08e-05 5.84e-06 0.0 + 7 -205.5446341464865156 2.65e-10 9.30e-07 9.72e-06 6.23e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.54463414648652 Eh -5593.15385 eV + +Components: +Nuclear Repulsion : 69.60131685168844 Eh 1893.94812 eV +Electronic Energy : -275.14595099817495 Eh -7487.10196 eV +One Electron Energy: -418.87476147662278 Eh -11398.16173 eV +Two Electron Energy: 143.72881047844785 Eh 3911.05977 eV + +Virial components: +Potential Energy : -410.38792395612518 Eh -11167.22314 eV +Kinetic Energy : 204.84328980963863 Eh 5574.06930 eV +Virial Ratio : 2.00342380918359 + +DFT components: +N(Alpha) : 11.999997210792 electrons +N(Beta) : 11.999997210792 electrons +N(Total) : 23.999994421585 electrons +E(X) : -23.337723495611 Eh +E(C) : -0.804160524149 Eh +E(XC) : -24.141884019759 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -2.6478e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 9.7177e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 9.3000e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.4835e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 6.2251e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 5.7239e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.5 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 22.2 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000363354 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007028830 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.537968671391 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001014 -0.000005693 0.000001773 + 2 O : 0.000000372 0.000000471 -0.000000832 + 3 O : 0.000002279 0.000006333 0.000001802 + 4 H : -0.000001637 -0.000001110 -0.000002743 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000098805 +RMS gradient ... 0.0000028523 +MAX gradient ... 0.0000063331 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.040973455 0.031467630 0.013174155 + 2 O : 0.040996351 -0.027030713 0.014265410 + 3 O : -0.023251519 0.014706025 -0.011829630 + 4 H : 0.023228623 -0.019142941 -0.015609935 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000146406 -0.0000249026 -0.0000044019 + +Norm of the Cartesian gradient ... 0.0866255615 +RMS gradient ... 0.0250066456 +MAX gradient ... 0.0409963511 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.113 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.3%) +RI-J Coulomb gradient .... 0.053 sec ( 46.8%) +XC gradient .... 0.019 sec ( 16.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.537968671 Eh +Current gradient norm .... 0.086625561 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.675 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999998444 +Lowest eigenvalues of augmented Hessian: + -0.000000630 0.187763302 0.399972442 0.424801614 0.504019886 +Length of the computed step .... 0.001763974 +The final length of the internal step .... 0.001763974 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0007201392 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0005907850 RMS(Int)= 0.0007201778 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000315 +Previously predicted energy change .... -0.000000567 +Actually observed energy change .... -0.000000857 +Ratio of predicted to observed change .... 1.511301433 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000008571 0.0000050000 YES + RMS gradient 0.0001572416 0.0001000000 NO + MAX gradient 0.0002790578 0.0003000000 YES + RMS step 0.0007201392 0.0020000000 YES + MAX step 0.0013596332 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0004 Max(Angles) 0.08 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2862 0.000084 -0.0004 1.2858 + 2. B(O 2,O 1) 1.3089 -0.000279 0.0004 1.3093 + 3. B(H 3,N 0) 1.0373 0.000001 0.0000 1.0373 + 4. A(O 1,N 0,H 3) 107.14 -0.000249 0.08 107.22 + 5. A(N 0,O 1,O 2) 120.92 -0.000036 0.02 120.94 + 6. D(O 2,O 1,N 0,H 3) -50.77 -0.063530 -0.00 -50.77 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.291 %) +Internal coordinates : 0.000 s ( 2.732 %) +B/P matrices and projection : 0.000 s (10.565 %) +Hessian update/contruction : 0.000 s (31.876 %) +Making the step : 0.000 s ( 5.373 %) +Converting the step to Cartesian: 0.000 s ( 3.552 %) +Storing new data : 0.000 s ( 3.188 %) +Checking convergence : 0.000 s ( 1.275 %) +Final printing : 0.000 s (30.874 %) +Total time : 0.001 s + +Time for energy+gradient : 5.324 s +Time for complete geometry iter : 6.162 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 5 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.471407 -0.602952 -0.379593 + O 0.275084 0.430661 -0.545815 + O 0.387470 1.337716 0.391714 + H -0.209856 -1.027581 0.529987 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.890830 -1.139415 -0.717328 + 1 O 8.0000 0 15.999 0.519834 0.813831 -1.031441 + 2 O 8.0000 0 15.999 0.732213 2.527917 0.740232 + 3 H 1.0000 0 1.008 -0.396570 -1.941847 1.001530 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.285781868960 0.00000000 0.00000000 + O 2 1 0 1.309328319690 120.94164244 0.00000000 + H 1 2 3 1.037330406588 107.21971674 309.23076898 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.429775600296 0.00000000 0.00000000 + O 2 1 0 2.474271943601 120.94164244 0.00000000 + H 1 2 3 1.960270378840 107.21971674 309.23076898 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.597506559797 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.867e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22316 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5579 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5446307648691118 0.00e+00 1.75e-05 1.70e-04 3.13e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5446312882323809 -5.23e-07 1.56e-05 1.53e-04 4.83e-05 0.0 + 3 -205.5446309537810521 3.34e-07 1.17e-05 1.69e-04 2.32e-04 0.0 + 4 -205.5446313424653226 -3.89e-07 4.74e-06 6.42e-05 2.67e-05 0.0 + 5 -205.5446313259458861 1.65e-08 2.51e-06 4.36e-05 6.16e-05 0.0 + 6 -205.5446313496716471 -2.37e-08 1.44e-06 9.66e-06 6.97e-06 0.0 + 7 -205.5446313493935691 2.78e-10 5.86e-07 4.50e-06 2.77e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.54463134939357 Eh -5593.15377 eV + +Components: +Nuclear Repulsion : 69.59750655979651 Eh 1893.84443 eV +Electronic Energy : -275.14213790919007 Eh -7486.99820 eV +One Electron Energy: -418.86787787064037 Eh -11397.97442 eV +Two Electron Energy: 143.72573996145030 Eh 3910.97621 eV + +Virial components: +Potential Energy : -410.38771239027449 Eh -11167.21738 eV +Kinetic Energy : 204.84308104088095 Eh 5574.06362 eV +Virial Ratio : 2.00342481818252 + +DFT components: +N(Alpha) : 11.999997149675 electrons +N(Beta) : 11.999997149675 electrons +N(Total) : 23.999994299350 electrons +E(X) : -23.337722574278 Eh +E(C) : -0.804154767488 Eh +E(XC) : -24.141877341766 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -2.7808e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.4986e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 5.8605e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.3283e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.7741e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 7.8047e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.3 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 22.4 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000363346 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007025690 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.537969005165 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001016 -0.000005698 0.000001772 + 2 O : 0.000000371 0.000000470 -0.000000834 + 3 O : 0.000002281 0.000006342 0.000001802 + 4 H : -0.000001637 -0.000001115 -0.000002741 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000098893 +RMS gradient ... 0.0000028548 +MAX gradient ... 0.0000063420 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.040822660 0.031654280 0.013255018 + 2 O : 0.040886591 -0.027262510 0.014071120 + 3 O : -0.023217753 0.014847990 -0.011698944 + 4 H : 0.023153823 -0.019239761 -0.015627194 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000147499 -0.0000240121 -0.0000037564 + +Norm of the Cartesian gradient ... 0.0866256426 +RMS gradient ... 0.0250066690 +MAX gradient ... 0.0408865906 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.105 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.5%) +RI-J Coulomb gradient .... 0.054 sec ( 50.9%) +XC gradient .... 0.018 sec ( 16.7%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.537969005 Eh +Current gradient norm .... 0.086625643 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999982 +Lowest eigenvalues of augmented Hessian: + -0.000000017 0.187196456 0.400337616 0.424827667 0.503151077 +Length of the computed step .... 0.000188393 +The final length of the internal step .... 0.000188393 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0000769110 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0000391506 RMS(Int)= 0.0000769110 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000008 +Previously predicted energy change .... -0.000000315 +Actually observed energy change .... -0.000000334 +Ratio of predicted to observed change .... 1.059942623 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000003338 0.0000050000 YES + RMS gradient 0.0000393007 0.0001000000 YES + MAX gradient 0.0000833229 0.0003000000 YES + RMS step 0.0000769110 0.0020000000 YES + MAX step 0.0001568755 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2858 -0.000029 0.0000 1.2858 + 2. B(O 2,O 1) 1.3093 -0.000083 0.0001 1.3094 + 3. B(H 3,N 0) 1.0373 0.000012 -0.0000 1.0373 + 4. A(O 1,N 0,H 3) 107.22 -0.000005 0.00 107.22 + 5. A(N 0,O 1,O 2) 120.94 0.000036 -0.00 120.94 + 6. D(O 2,O 1,N 0,H 3) -50.77 -0.063525 -0.00 -50.77 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (12.173 %) +Internal coordinates : 0.000 s ( 3.390 %) +B/P matrices and projection : 0.000 s (12.789 %) +Hessian update/contruction : 0.000 s (25.578 %) +Making the step : 0.000 s ( 5.085 %) +Converting the step to Cartesian: 0.000 s ( 4.006 %) +Storing new data : 0.000 s ( 3.544 %) +Checking convergence : 0.000 s ( 1.387 %) +Final printing : 0.000 s (29.430 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 5 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.471405 -0.602957 -0.379575 + O 0.275092 0.430653 -0.545865 + O 0.387471 1.337744 0.391745 + H -0.209866 -1.027596 0.529986 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.890827 -1.139423 -0.717292 + 1 O 8.0000 0 15.999 0.519849 0.813816 -1.031536 + 2 O 8.0000 0 15.999 0.732214 2.527971 0.740291 + 3 H 1.0000 0 1.008 -0.396590 -1.941875 1.001529 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.285791436762 0.00000000 0.00000000 + O 2 1 0 1.309411334646 120.93726779 0.00000000 + H 1 2 3 1.037315062616 107.22328778 309.23076898 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.429793680822 0.00000000 0.00000000 + O 2 1 0 2.474428819133 120.93726779 0.00000000 + H 1 2 3 1.960241382935 107.22328778 309.23076898 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.595485273521 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.868e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22316 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5579 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.5954852735 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5446313690038096 0.00e+00 2.47e-06 2.73e-05 3.86e-06 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5446313760944577 -7.09e-09 2.31e-06 3.13e-05 7.31e-06 0.0 + 3 -205.5446313670481118 9.05e-09 1.74e-06 2.15e-05 3.57e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 3 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.54463136704811 Eh -5593.15377 eV + +Components: +Nuclear Repulsion : 69.59548527352092 Eh 1893.78943 eV +Electronic Energy : -275.14011664056898 Eh -7486.94320 eV +One Electron Energy: -418.86441818183977 Eh -11397.88028 eV +Two Electron Energy: 143.72430154127076 Eh 3910.93707 eV + +Virial components: +Potential Energy : -410.38760456094349 Eh -11167.21445 eV +Kinetic Energy : 204.84297319389538 Eh 5574.06068 eV +Virial Ratio : 2.00342534655796 + +DFT components: +N(Alpha) : 11.999997153936 electrons +N(Beta) : 11.999997153936 electrons +N(Total) : 23.999994307872 electrons +E(X) : -23.337718722177 Eh +E(C) : -0.804150515615 Eh +E(XC) : -24.141869237792 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -9.0463e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.1454e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.7402e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.5885e-05 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.5697e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 5.0306e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.188627 -522.1491 + 1 2.0000 -19.030139 -517.8364 + 2 2.0000 -14.266290 -388.2055 + 3 2.0000 -1.248563 -33.9751 + 4 2.0000 -0.968390 -26.3512 + 5 2.0000 -0.716962 -19.5095 + 6 2.0000 -0.566395 -15.4124 + 7 2.0000 -0.519012 -14.1230 + 8 2.0000 -0.496100 -13.4996 + 9 2.0000 -0.333820 -9.0837 + 10 2.0000 -0.273325 -7.4376 + 11 2.0000 -0.270657 -7.3650 + 12 0.0000 -0.202190 -5.5019 + 13 0.0000 0.036746 0.9999 + 14 0.0000 0.093680 2.5492 + 15 0.0000 0.135914 3.6984 + 16 0.0000 0.228487 6.2174 + 17 0.0000 0.262195 7.1347 + 18 0.0000 0.310605 8.4520 + 19 0.0000 0.326490 8.8842 + 20 0.0000 0.360101 9.7988 + 21 0.0000 0.384912 10.4740 + 22 0.0000 0.396787 10.7971 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.279409 + 1 O : 0.203557 + 2 O : -0.193925 + 3 H : 0.269777 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.838586 s : 3.838586 + pz : 1.401651 p : 3.385828 + px : 1.010287 + py : 0.973890 + dz2 : 0.013622 d : 0.054995 + dxz : 0.005442 + dyz : 0.005682 + dx2y2 : 0.015775 + dxy : 0.014475 + + 1 O s : 3.740292 s : 3.740292 + pz : 1.470566 p : 3.922044 + px : 1.307293 + py : 1.144185 + dz2 : 0.034083 d : 0.134108 + dxz : 0.021019 + dyz : 0.020732 + dx2y2 : 0.034696 + dxy : 0.023577 + + 2 O s : 3.942594 s : 3.942594 + pz : 1.446524 p : 4.236030 + px : 1.581221 + py : 1.208285 + dz2 : 0.001198 d : 0.015300 + dxz : 0.003371 + dyz : 0.006581 + dx2y2 : 0.002658 + dxy : 0.001493 + + 3 H s : 0.700752 s : 0.700752 + pz : 0.015723 p : 0.029471 + px : 0.005987 + py : 0.007761 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.065411 + 1 O : -0.182711 + 2 O : -0.029966 + 3 H : 0.278088 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.341417 s : 3.341417 + pz : 1.352407 p : 3.413982 + px : 1.020957 + py : 1.040619 + dz2 : 0.048124 d : 0.310012 + dxz : 0.028423 + dyz : 0.083041 + dx2y2 : 0.064467 + dxy : 0.085956 + + 1 O s : 3.367573 s : 3.367573 + pz : 1.478213 p : 4.046767 + px : 1.281479 + py : 1.287075 + dz2 : 0.144703 d : 0.768371 + dxz : 0.065639 + dyz : 0.204070 + dx2y2 : 0.173706 + dxy : 0.180252 + + 2 O s : 3.607540 s : 3.607540 + pz : 1.427588 p : 4.174601 + px : 1.497323 + py : 1.249690 + dz2 : 0.065636 d : 0.247825 + dxz : 0.029123 + dyz : 0.078429 + dx2y2 : 0.034421 + dxy : 0.040215 + + 3 H s : 0.646201 s : 0.646201 + pz : 0.043593 p : 0.075711 + px : 0.014817 + py : 0.017302 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2794 7.0000 -0.2794 2.7811 2.7811 -0.0000 + 1 O 7.7964 8.0000 0.2036 2.5968 2.5968 -0.0000 + 2 O 8.1939 8.0000 -0.1939 1.6784 1.6784 -0.0000 + 3 H 0.7302 1.0000 0.2698 0.9192 0.9192 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4117 B( 0-N , 2-O ) : 0.4954 B( 0-N , 3-H ) : 0.8740 +B( 1-O , 2-O ) : 1.1614 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.194 sec +Sum of individual times .... 1.181 sec ( 98.9%) + +SCF preparation .... 0.575 sec ( 48.1%) +Fock matrix formation .... 0.089 sec ( 7.5%) + Startup .... 0.006 sec ( 6.5% of F) + Split-RI-J .... 0.016 sec ( 17.6% of F) + XC integration .... 0.057 sec ( 63.6% of F) + Basis function eval. .... 0.004 sec ( 6.9% of XC) + Density eval. .... 0.006 sec ( 10.5% of XC) + XC-Functional eval. .... 0.003 sec ( 5.9% of XC) + XC-Potential eval. .... 0.006 sec ( 11.3% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.005 sec ( 0.4%) +Total Energy calculation .... 0.006 sec ( 0.5%) +Population analysis .... 0.471 sec ( 39.5%) +Orbital Transformation .... 0.006 sec ( 0.5%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.011 sec ( 0.9%) +SOSCF solution .... 0.018 sec ( 1.5%) +Finished LeanSCF after 1.7 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 22.7 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000363346 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007025705 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.537969007121 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.015.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.015.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.152175 0.756130 -0.291349 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5446313670481118 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.268588886 0.749511867 -0.367783076 +Nuclear contribution : -0.268062676 -1.330661343 0.642904074 + ----------------------------------------- +Total Dipole Moment : 0.000526209 -0.581149476 0.275120997 + ----------------------------------------- +Magnitude (a.u.) : 0.642982545 +Magnitude (Debye) : 1.634331748 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.979962 0.422464 0.377647 +Rotational constants in MHz : 89337.021865 12665.156362 11321.560025 + +Dipole components along the rotational axes: +x,y,z [a.u.] : -0.417904 0.351367 -0.339595 +x,y,z [Debye]: -1.062227 0.893103 -0.863181 + + + +Dipole moment calculation done in 0.2 sec + +Maximum memory used throughout the entire PROP-calculation: 12.3 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 16 * + * * + * Dihedral ( 2, 1, 0, 3) : -41.53846154 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2872 0.734971 + 2. B(O 2,O 1) 1.3111 0.673886 + 3. B(H 3,N 0) 1.0398 0.391395 + 4. A(O 1,N 0,H 3) 107.0167 0.360661 + 5. A(N 0,O 1,O 2) 120.7263 0.442442 + 6. D(O 2,O 1,N 0,H 3) -41.5385 0.042675 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.448736 -0.623455 -0.396124 + O 0.249320 0.444737 -0.564917 + O 0.397254 1.309274 0.409602 + H -0.216547 -0.992713 0.547731 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.847988 -1.178159 -0.748566 + 1 O 8.0000 0 15.999 0.471147 0.840432 -1.067538 + 2 O 8.0000 0 15.999 0.750702 2.474170 0.774035 + 3 H 1.0000 0 1.008 -0.409214 -1.875956 1.035062 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.285791436762 0.00000000 0.00000000 + O 2 1 0 1.309411334646 120.93726779 0.00000000 + H 1 2 3 1.037315062616 107.22328778 309.23076898 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.429793680822 0.00000000 0.00000000 + O 2 1 0 2.474428819133 120.93726779 0.00000000 + H 1 2 3 1.960241382935 107.22328778 309.23076898 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.567889614714 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.933e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.001 sec +Total time needed ... 0.003 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22312 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.5678896147 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5500476438679129 0.00e+00 4.07e-04 3.18e-03 2.16e-02 0.700 0.1 +Warning: op=0 Small HOMO/LUMO gap ( 0.074) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5511325455138945 -1.08e-03 4.77e-04 3.68e-03 1.67e-02 0.700 0.1 + ***Turning on AO-DIIS*** + 3 -205.5520273890153931 -8.95e-04 3.57e-04 2.44e-03 1.18e-02 0.700 0.0 + 4 -205.5526481836685093 -6.21e-04 8.83e-04 6.46e-03 8.34e-03 0.000 0.1 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5541100984582954 -1.46e-03 1.11e-04 1.98e-03 1.66e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -205.5541105887351137 -4.90e-07 4.38e-04 5.33e-03 1.56e-03 0.0 + 7 -205.5537076678180028 4.03e-04 3.55e-04 5.09e-03 9.17e-03 0.0 + 8 -205.5541305876534466 -4.23e-04 4.18e-05 6.46e-04 3.25e-04 0.0 + 9 -205.5541275318005319 3.06e-06 2.89e-05 5.14e-04 8.24e-04 0.0 + 10 -205.5541312689414895 -3.74e-06 4.33e-06 3.92e-05 1.46e-05 0.0 + 11 -205.5541312747017173 -5.76e-09 1.28e-06 1.02e-05 1.20e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.55413127470172 Eh -5593.41228 eV + +Components: +Nuclear Repulsion : 69.56788961471399 Eh 1893.03852 eV +Electronic Energy : -275.12202088941569 Eh -7486.45079 eV +One Electron Energy: -418.81821888624438 Eh -11396.62313 eV +Two Electron Energy: 143.69619799682869 Eh 3910.17234 eV + +Virial components: +Potential Energy : -410.37831564617932 Eh -11166.96169 eV +Kinetic Energy : 204.82418437147760 Eh 5573.54941 eV +Virial Ratio : 2.00356377302546 + +DFT components: +N(Alpha) : 12.000000526096 electrons +N(Beta) : 12.000000526096 electrons +N(Total) : 24.000001052193 electrons +E(X) : -23.335899130255 Eh +E(C) : -0.803943148715 Eh +E(XC) : -24.139842278970 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 5.7602e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.0154e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.2781e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.6594e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.2014e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.4471e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.189946 -522.1850 + 1 2.0000 -19.027002 -517.7511 + 2 2.0000 -14.270452 -388.3187 + 3 2.0000 -1.247988 -33.9595 + 4 2.0000 -0.966932 -26.3116 + 5 2.0000 -0.719038 -19.5660 + 6 2.0000 -0.564378 -15.3575 + 7 2.0000 -0.518623 -14.1125 + 8 2.0000 -0.496079 -13.4990 + 9 2.0000 -0.333617 -9.0782 + 10 2.0000 -0.279734 -7.6120 + 11 2.0000 -0.269958 -7.3459 + 12 0.0000 -0.196896 -5.3578 + 13 0.0000 0.033183 0.9029 + 14 0.0000 0.094316 2.5665 + 15 0.0000 0.134048 3.6476 + 16 0.0000 0.225082 6.1248 + 17 0.0000 0.265650 7.2287 + 18 0.0000 0.307766 8.3747 + 19 0.0000 0.327340 8.9074 + 20 0.0000 0.358461 9.7542 + 21 0.0000 0.384242 10.4558 + 22 0.0000 0.396431 10.7874 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.265772 + 1 O : 0.206658 + 2 O : -0.207138 + 3 H : 0.266251 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.844413 s : 3.844413 + pz : 1.380891 p : 3.367227 + px : 1.025124 + py : 0.961212 + dz2 : 0.013646 d : 0.054132 + dxz : 0.004387 + dyz : 0.005423 + dx2y2 : 0.016109 + dxy : 0.014567 + + 1 O s : 3.741990 s : 3.741990 + pz : 1.458610 p : 3.914601 + px : 1.313085 + py : 1.142906 + dz2 : 0.035675 d : 0.136750 + dxz : 0.020279 + dyz : 0.021510 + dx2y2 : 0.034856 + dxy : 0.024430 + + 2 O s : 3.942391 s : 3.942391 + pz : 1.413186 p : 4.248130 + px : 1.562422 + py : 1.272522 + dz2 : 0.000463 d : 0.016617 + dxz : 0.004414 + dyz : 0.007519 + dx2y2 : 0.002244 + dxy : 0.001977 + + 3 H s : 0.704835 s : 0.704835 + pz : 0.016323 p : 0.028913 + px : 0.005707 + py : 0.006883 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.056246 + 1 O : -0.181281 + 2 O : -0.040119 + 3 H : 0.277645 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.347708 s : 3.347708 + pz : 1.337645 p : 3.399638 + px : 1.022502 + py : 1.039490 + dz2 : 0.051607 d : 0.308900 + dxz : 0.024446 + dyz : 0.083351 + dx2y2 : 0.065457 + dxy : 0.084038 + + 1 O s : 3.369368 s : 3.369368 + pz : 1.473503 p : 4.044528 + px : 1.279260 + py : 1.291764 + dz2 : 0.152497 d : 0.767385 + dxz : 0.064594 + dyz : 0.204773 + dx2y2 : 0.168574 + dxy : 0.176946 + + 2 O s : 3.607641 s : 3.607641 + pz : 1.404123 p : 4.184543 + px : 1.480365 + py : 1.300055 + dz2 : 0.070655 d : 0.247935 + dxz : 0.031725 + dyz : 0.076333 + dx2y2 : 0.032226 + dxy : 0.036997 + + 3 H s : 0.647759 s : 0.647759 + pz : 0.045418 p : 0.074595 + px : 0.014072 + py : 0.015105 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2658 7.0000 -0.2658 2.7880 2.7880 0.0000 + 1 O 7.7933 8.0000 0.2067 2.6131 2.6131 0.0000 + 2 O 8.2071 8.0000 -0.2071 1.6815 1.6815 -0.0000 + 3 H 0.7337 1.0000 0.2663 0.9227 0.9227 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4209 B( 0-N , 2-O ) : 0.4912 B( 0-N , 3-H ) : 0.8760 +B( 1-O , 2-O ) : 1.1679 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.527 sec +Sum of individual times .... 1.496 sec ( 98.0%) + +SCF preparation .... 0.568 sec ( 37.2%) +Fock matrix formation .... 0.290 sec ( 19.0%) + Startup .... 0.015 sec ( 5.3% of F) + Split-RI-J .... 0.046 sec ( 15.9% of F) + XC integration .... 0.181 sec ( 62.6% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.012 sec ( 6.8% of XC) + Density eval. .... 0.018 sec ( 9.8% of XC) + XC-Functional eval. .... 0.010 sec ( 5.5% of XC) + XC-Potential eval. .... 0.017 sec ( 9.6% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.026 sec ( 1.7%) +Total Energy calculation .... 0.026 sec ( 1.7%) +Population analysis .... 0.445 sec ( 29.1%) +Orbital Transformation .... 0.014 sec ( 0.9%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.090 sec ( 5.9%) +SOSCF solution .... 0.037 sec ( 2.4%) +Finished LeanSCF after 2.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 23.1 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000363578 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007078642 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.547416210406 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001077 -0.000005500 0.000001826 + 2 O : 0.000000330 0.000000489 -0.000000871 + 3 O : 0.000002234 0.000006052 0.000001907 + 4 H : -0.000001487 -0.000001040 -0.000002861 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000096221 +RMS gradient ... 0.0000027777 +MAX gradient ... 0.0000060519 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.039938466 0.021152459 0.011094418 + 2 O : 0.039852191 -0.017953599 0.004533283 + 3 O : -0.020531598 0.013916058 -0.005440831 + 4 H : 0.020617873 -0.017114919 -0.010186870 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000011337 -0.0000106099 -0.0000153716 + +Norm of the Cartesian gradient ... 0.0745873210 +RMS gradient ... 0.0215315049 +MAX gradient ... 0.0399384659 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.121 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 4.1%) +RI-J Coulomb gradient .... 0.057 sec ( 47.0%) +XC gradient .... 0.019 sec ( 15.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.547416210 Eh +Current gradient norm .... 0.074587321 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999907157 +Lowest eigenvalues of augmented Hessian: + -0.000109492 0.359814807 0.387882813 0.441542208 0.669718940 +Length of the computed step .... 0.013627615 +The final length of the internal step .... 0.013627615 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0055634506 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0053040687 RMS(Int)= 0.0055631184 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0034165000 0.0001000000 NO + MAX gradient 0.0072453261 0.0003000000 NO + RMS step 0.0055634506 0.0020000000 NO + MAX step 0.0099065615 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0052 Max(Angles) 0.41 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2872 0.007245 -0.0052 1.2819 + 2. B(O 2,O 1) 1.3111 0.002816 -0.0022 1.3089 + 3. B(H 3,N 0) 1.0398 0.001436 -0.0020 1.0378 + 4. A(O 1,N 0,H 3) 107.02 0.002597 -0.41 106.60 + 5. A(N 0,O 1,O 2) 120.73 -0.000897 0.12 120.84 + 6. D(O 2,O 1,N 0,H 3) -41.54 -0.053745 0.00 -41.54 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.399 %) +Internal coordinates : 0.000 s ( 3.640 %) +B/P matrices and projection : 0.000 s (14.558 %) +Hessian update/contruction : 0.000 s (28.769 %) +Making the step : 0.000 s ( 5.893 %) +Converting the step to Cartesian: 0.000 s ( 4.853 %) +Storing new data : 0.000 s ( 3.813 %) +Checking convergence : 0.000 s ( 0.000 %) +Final printing : 0.000 s (27.383 %) +Total time : 0.001 s + +Time for energy+gradient : 5.533 s +Time for complete geometry iter : 6.242 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.448470 -0.622119 -0.397020 + O 0.248046 0.441256 -0.562666 + O 0.395974 1.304797 0.409744 + H -0.214259 -0.986090 0.546234 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.847485 -1.175635 -0.750258 + 1 O 8.0000 0 15.999 0.468739 0.833854 -1.063286 + 2 O 8.0000 0 15.999 0.748283 2.465709 0.774304 + 3 H 1.0000 0 1.008 -0.404890 -1.863440 1.032233 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.281928367813 0.00000000 0.00000000 + O 2 1 0 1.308880264094 120.84271226 0.00000000 + H 1 2 3 1.037813786050 106.60325914 318.46153846 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.422493538471 0.00000000 0.00000000 + O 2 1 0 2.473425241233 120.84271226 0.00000000 + H 1 2 3 1.961183833643 106.60325914 318.46153846 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.764702613407 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.903e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22309 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5541849878325706 0.00e+00 1.28e-04 9.95e-04 1.94e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5542088639473945 -2.39e-05 1.27e-04 1.45e-03 4.15e-04 0.0 + 3 -205.5541838348732995 2.50e-05 1.01e-04 1.43e-03 1.90e-03 0.0 + 4 -205.5542087335580845 -2.49e-05 1.22e-04 1.81e-03 6.36e-04 0.0 + 5 -205.5541860160026886 2.27e-05 8.55e-05 1.38e-03 2.14e-03 0.0 + 6 -205.5542121420805302 -2.61e-05 2.02e-05 2.17e-04 8.63e-05 0.0 + 7 -205.5542121076453554 3.44e-08 1.08e-05 1.18e-04 9.71e-05 0.0 + 8 -205.5542122661356075 -1.58e-07 2.05e-07 2.40e-06 1.07e-06 0.0 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.55421226613561 Eh -5593.41448 eV + +Components: +Nuclear Repulsion : 69.76470261340718 Eh 1898.39407 eV +Electronic Energy : -275.31891487954277 Eh -7491.80855 eV +One Electron Energy: -419.19322657899681 Eh -11406.82761 eV +Two Electron Energy: 143.87431169945404 Eh 3915.01906 eV + +Virial components: +Potential Energy : -410.40009376731348 Eh -11167.55430 eV +Kinetic Energy : 204.84588150117790 Eh 5574.13982 eV +Virial Ratio : 2.00345787164363 + +DFT components: +N(Alpha) : 12.000000764088 electrons +N(Beta) : 12.000000764088 electrons +N(Total) : 24.000001528176 electrons +E(X) : -23.341728592723 Eh +E(C) : -0.804324162886 Eh +E(XC) : -24.146052755609 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.5849e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.4028e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.0494e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.2489e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.0671e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.7481e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.3 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 23.2 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000363669 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007093607 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.547482328607 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001057 -0.000005450 0.000001834 + 2 O : 0.000000325 0.000000475 -0.000000854 + 3 O : 0.000002207 0.000005965 0.000001900 + 4 H : -0.000001476 -0.000000990 -0.000002879 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000095259 +RMS gradient ... 0.0000027499 +MAX gradient ... 0.0000059649 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.038356323 0.024135953 0.010468931 + 2 O : 0.037942194 -0.021190710 0.008506698 + 3 O : -0.020900373 0.012709820 -0.007400414 + 4 H : 0.021314501 -0.015655063 -0.011575215 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000029901 -0.0000121790 -0.0000173623 + +Norm of the Cartesian gradient ... 0.0749057822 +RMS gradient ... 0.0216234367 +MAX gradient ... 0.0383563226 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.117 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.1%) +RI-J Coulomb gradient .... 0.056 sec ( 47.5%) +XC gradient .... 0.017 sec ( 14.6%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.547482329 Eh +Current gradient norm .... 0.074905782 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999991040 +Lowest eigenvalues of augmented Hessian: + -0.000009202 0.368710546 0.408419888 0.431095784 0.545267961 +Length of the computed step .... 0.004233212 +The final length of the internal step .... 0.004233212 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0017282017 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0009806097 RMS(Int)= 0.0017281558 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000004601 +Previously predicted energy change .... -0.000054756 +Actually observed energy change .... -0.000066118 +Ratio of predicted to observed change .... 1.207504436 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000661182 0.0000050000 NO + RMS gradient 0.0008931645 0.0001000000 NO + MAX gradient 0.0020804394 0.0003000000 NO + RMS step 0.0017282017 0.0020000000 YES + MAX step 0.0038888860 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0021 Max(Angles) 0.06 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2819 0.002080 -0.0021 1.2799 + 2. B(O 2,O 1) 1.3089 0.000525 -0.0006 1.3083 + 3. B(H 3,N 0) 1.0378 -0.000218 0.0003 1.0381 + 4. A(O 1,N 0,H 3) 106.60 -0.000062 -0.00 106.60 + 5. A(N 0,O 1,O 2) 120.84 -0.000362 0.06 120.91 + 6. D(O 2,O 1,N 0,H 3) -41.54 -0.054263 0.00 -41.54 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 7.662 %) +Internal coordinates : 0.000 s ( 3.247 %) +B/P matrices and projection : 0.000 s (13.247 %) +Hessian update/contruction : 0.000 s (40.000 %) +Making the step : 0.000 s ( 4.805 %) +Converting the step to Cartesian: 0.000 s ( 4.026 %) +Storing new data : 0.000 s ( 2.857 %) +Checking convergence : 0.000 s ( 1.429 %) +Final printing : 0.000 s (22.597 %) +Total time : 0.001 s + +Time for energy+gradient : 4.917 s +Time for complete geometry iter : 5.732 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.447975 -0.621206 -0.397296 + O 0.247503 0.440509 -0.562046 + O 0.395816 1.304143 0.409426 + H -0.214051 -0.985602 0.546208 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.846550 -1.173908 -0.750780 + 1 O 8.0000 0 15.999 0.467712 0.832441 -1.062113 + 2 O 8.0000 0 15.999 0.747983 2.464472 0.773703 + 3 H 1.0000 0 1.008 -0.404499 -1.862517 1.032184 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.279870457972 0.00000000 0.00000000 + O 2 1 0 1.308288419999 120.90545003 0.00000000 + H 1 2 3 1.038125323859 106.60243657 318.46153846 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.418604652464 0.00000000 0.00000000 + O 2 1 0 2.472306817979 120.90545003 0.00000000 + H 1 2 3 1.961772554783 106.60243657 318.46153846 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1679 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.824589382987 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.895e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22309 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5542135343152381 0.00e+00 4.69e-05 3.97e-04 8.22e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5542170059296723 -3.47e-06 4.02e-05 4.51e-04 1.89e-04 0.0 + 3 -205.5542153964387921 1.61e-06 2.62e-05 3.98e-04 4.41e-04 0.0 + 4 -205.5542170144829015 -1.62e-06 4.92e-05 6.30e-04 2.69e-04 0.0 + 5 -205.5542127590896939 4.26e-06 3.70e-05 5.25e-04 8.34e-04 0.0 + 6 -205.5542174410980465 -4.68e-06 6.87e-06 7.33e-05 2.79e-05 0.0 + 7 -205.5542174385812473 2.52e-09 3.59e-06 3.90e-05 3.03e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.55421743858125 Eh -5593.41462 eV + +Components: +Nuclear Repulsion : 69.82458938298663 Eh 1900.02367 eV +Electronic Energy : -275.37880682156788 Eh -7493.43829 eV +One Electron Energy: -419.30649878546552 Eh -11409.90990 eV +Two Electron Energy: 143.92769196389762 Eh 3916.47161 eV + +Virial components: +Potential Energy : -410.40600323252892 Eh -11167.71510 eV +Kinetic Energy : 204.85178579394767 Eh 5574.30048 eV +Virial Ratio : 2.00342897496310 + +DFT components: +N(Alpha) : 12.000000652982 electrons +N(Beta) : 12.000000652982 electrons +N(Total) : 24.000001305964 electrons +E(X) : -23.343171813283 Eh +E(C) : -0.804437285231 Eh +E(XC) : -24.147609098514 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -2.5168e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.8957e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.5855e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.5101e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.0266e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.9813e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 23.4 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000363693 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007093635 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.547487497117 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001053 -0.000005440 0.000001836 + 2 O : 0.000000324 0.000000473 -0.000000851 + 3 O : 0.000002202 0.000005950 0.000001895 + 4 H : -0.000001472 -0.000000982 -0.000002880 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000095079 +RMS gradient ... 0.0000027447 +MAX gradient ... 0.0000059496 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.037716385 0.025634705 0.009855984 + 2 O : 0.037213286 -0.022336870 0.009615712 + 3 O : -0.021011183 0.012321425 -0.008044374 + 4 H : 0.021514283 -0.015619261 -0.011427322 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000034977 -0.0000168112 -0.0000153189 + +Norm of the Cartesian gradient ... 0.0751560986 +RMS gradient ... 0.0216956969 +MAX gradient ... 0.0377163853 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.128 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.0%) +RI-J Coulomb gradient .... 0.056 sec ( 43.7%) +XC gradient .... 0.018 sec ( 14.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.547487497 Eh +Current gradient norm .... 0.075156099 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999998866 +Lowest eigenvalues of augmented Hessian: + -0.000000813 0.333041783 0.394351179 0.425253583 0.543155932 +Length of the computed step .... 0.001506053 +The final length of the internal step .... 0.001506053 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0006148436 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0005210433 RMS(Int)= 0.0006148780 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000406 +Previously predicted energy change .... -0.000004601 +Actually observed energy change .... -0.000005169 +Ratio of predicted to observed change .... 1.123331729 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000051685 0.0000050000 NO + RMS gradient 0.0002272632 0.0001000000 NO + MAX gradient 0.0003929178 0.0003000000 NO + RMS step 0.0006148436 0.0020000000 YES + MAX step 0.0011372527 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0004 Max(Angles) 0.07 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2799 0.000293 -0.0004 1.2794 + 2. B(O 2,O 1) 1.3083 -0.000222 0.0001 1.3084 + 3. B(H 3,N 0) 1.0381 -0.000053 0.0001 1.0382 + 4. A(O 1,N 0,H 3) 106.60 -0.000393 0.07 106.67 + 5. A(N 0,O 1,O 2) 120.91 -0.000133 0.03 120.93 + 6. D(O 2,O 1,N 0,H 3) -41.54 -0.054412 -0.00 -41.54 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.104 %) +Internal coordinates : 0.000 s ( 4.160 %) +B/P matrices and projection : 0.000 s (13.224 %) +Hessian update/contruction : 0.000 s (28.975 %) +Making the step : 0.000 s ( 6.241 %) +Converting the step to Cartesian: 0.000 s ( 4.458 %) +Storing new data : 0.000 s ( 3.715 %) +Checking convergence : 0.000 s ( 1.634 %) +Final printing : 0.000 s (27.192 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.447693 -0.620972 -0.397182 + O 0.247336 0.440497 -0.561966 + O 0.395962 1.304571 0.409242 + H -0.214314 -0.986252 0.546199 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.846016 -1.173467 -0.750566 + 1 O 8.0000 0 15.999 0.467397 0.832418 -1.061962 + 2 O 8.0000 0 15.999 0.748261 2.465282 0.773355 + 3 H 1.0000 0 1.008 -0.404995 -1.863746 1.032166 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.279427360620 0.00000000 0.00000000 + O 2 1 0 1.308418691525 120.93056721 0.00000000 + H 1 2 3 1.038201913920 106.66759636 318.46153846 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.417767319818 0.00000000 0.00000000 + O 2 1 0 2.472552995486 120.93056721 0.00000000 + H 1 2 3 1.961917289023 106.66759636 318.46153846 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.828285643391 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.896e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22309 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.8282856434 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5542145337230124 0.00e+00 1.52e-05 1.35e-04 3.02e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5542149228204210 -3.89e-07 1.15e-05 8.79e-05 3.18e-05 0.0 + 3 -205.5542148108464460 1.12e-07 9.08e-06 1.40e-04 1.53e-04 0.0 + 4 -205.5542149343571907 -1.24e-07 9.73e-06 1.39e-04 5.55e-05 0.0 + 5 -205.5542148525806567 8.18e-08 5.28e-06 9.35e-05 1.42e-04 0.0 + 6 -205.5542149639216234 -1.11e-07 2.78e-06 2.90e-05 7.80e-06 0.0 + 7 -205.5542149635857356 3.36e-10 1.26e-06 1.35e-05 7.59e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.55421496358574 Eh -5593.41455 eV + +Components: +Nuclear Repulsion : 69.82828564339084 Eh 1900.12425 eV +Electronic Energy : -275.38250060697658 Eh -7493.53881 eV +One Electron Energy: -419.31473145120913 Eh -11410.13392 eV +Two Electron Energy: 143.93223084423255 Eh 3916.59512 eV + +Virial components: +Potential Energy : -410.40648487346022 Eh -11167.72821 eV +Kinetic Energy : 204.85226990987448 Eh 5574.31366 eV +Virial Ratio : 2.00342659153360 + +DFT components: +N(Alpha) : 12.000000569253 electrons +N(Beta) : 12.000000569253 electrons +N(Total) : 24.000001138507 electrons +E(X) : -23.343444120006 Eh +E(C) : -0.804448062684 Eh +E(XC) : -24.147892182690 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -3.3589e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.3510e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.2594e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.9639e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 7.5928e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.4873e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.190281 -522.1941 + 1 2.0000 -19.026237 -517.7302 + 2 2.0000 -14.270098 -388.3091 + 3 2.0000 -1.252144 -34.0726 + 4 2.0000 -0.970074 -26.3971 + 5 2.0000 -0.718267 -19.5450 + 6 2.0000 -0.565591 -15.3905 + 7 2.0000 -0.520741 -14.1701 + 8 2.0000 -0.497399 -13.5349 + 9 2.0000 -0.333439 -9.0733 + 10 2.0000 -0.279663 -7.6100 + 11 2.0000 -0.269655 -7.3377 + 12 0.0000 -0.195525 -5.3205 + 13 0.0000 0.035811 0.9745 + 14 0.0000 0.096090 2.6148 + 15 0.0000 0.137277 3.7355 + 16 0.0000 0.227236 6.1834 + 17 0.0000 0.265296 7.2191 + 18 0.0000 0.307317 8.3625 + 19 0.0000 0.327856 8.9214 + 20 0.0000 0.357877 9.7383 + 21 0.0000 0.384449 10.4614 + 22 0.0000 0.397297 10.8110 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.263923 + 1 O : 0.208559 + 2 O : -0.209986 + 3 H : 0.265350 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.841580 s : 3.841580 + pz : 1.380838 p : 3.367547 + px : 1.024320 + py : 0.962389 + dz2 : 0.013693 d : 0.054796 + dxz : 0.004452 + dyz : 0.005499 + dx2y2 : 0.016398 + dxy : 0.014755 + + 1 O s : 3.737966 s : 3.737966 + pz : 1.460300 p : 3.915621 + px : 1.311597 + py : 1.143723 + dz2 : 0.035902 d : 0.137854 + dxz : 0.020430 + dyz : 0.021661 + dx2y2 : 0.035185 + dxy : 0.024677 + + 2 O s : 3.941530 s : 3.941530 + pz : 1.415254 p : 4.251607 + px : 1.564383 + py : 1.271970 + dz2 : 0.000484 d : 0.016850 + dxz : 0.004432 + dyz : 0.007620 + dx2y2 : 0.002282 + dxy : 0.002032 + + 3 H s : 0.705609 s : 0.705609 + pz : 0.016395 p : 0.029040 + px : 0.005747 + py : 0.006899 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.054267 + 1 O : -0.183726 + 2 O : -0.039456 + 3 H : 0.277449 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.342935 s : 3.342935 + pz : 1.335545 p : 3.399865 + px : 1.022149 + py : 1.042171 + dz2 : 0.051950 d : 0.311467 + dxz : 0.024718 + dyz : 0.084088 + dx2y2 : 0.066080 + dxy : 0.084630 + + 1 O s : 3.364152 s : 3.364152 + pz : 1.474885 p : 4.046344 + px : 1.278325 + py : 1.293133 + dz2 : 0.153050 d : 0.773230 + dxz : 0.065499 + dyz : 0.206669 + dx2y2 : 0.170077 + dxy : 0.177934 + + 2 O s : 3.605497 s : 3.605497 + pz : 1.404952 p : 4.185841 + px : 1.481378 + py : 1.299511 + dz2 : 0.070643 d : 0.248118 + dxz : 0.031666 + dyz : 0.076335 + dx2y2 : 0.032357 + dxy : 0.037117 + + 3 H s : 0.647794 s : 0.647794 + pz : 0.045551 p : 0.074757 + px : 0.014170 + py : 0.015036 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2639 7.0000 -0.2639 2.7898 2.7898 -0.0000 + 1 O 7.7914 8.0000 0.2086 2.6156 2.6156 -0.0000 + 2 O 8.2100 8.0000 -0.2100 1.6791 1.6791 -0.0000 + 3 H 0.7346 1.0000 0.2654 0.9236 0.9236 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4241 B( 0-N , 2-O ) : 0.4888 B( 0-N , 3-H ) : 0.8768 +B( 1-O , 2-O ) : 1.1675 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.407 sec +Sum of individual times .... 1.390 sec ( 98.8%) + +SCF preparation .... 0.570 sec ( 40.5%) +Fock matrix formation .... 0.171 sec ( 12.1%) + Startup .... 0.009 sec ( 5.3% of F) + Split-RI-J .... 0.024 sec ( 13.9% of F) + XC integration .... 0.112 sec ( 65.3% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.007 sec ( 6.7% of XC) + Density eval. .... 0.010 sec ( 9.3% of XC) + XC-Functional eval. .... 0.006 sec ( 5.6% of XC) + XC-Potential eval. .... 0.010 sec ( 8.7% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.011 sec ( 0.8%) +Total Energy calculation .... 0.015 sec ( 1.0%) +Population analysis .... 0.570 sec ( 40.5%) +Orbital Transformation .... 0.006 sec ( 0.4%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.010 sec ( 0.7%) +SOSCF solution .... 0.037 sec ( 2.7%) +Finished LeanSCF after 2.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 23.7 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000363689 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007090565 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.547488088373 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.016.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.016.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.152956 0.732659 -0.299708 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5542149635857356 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.239405458 0.699409944 -0.406653845 +Nuclear contribution : -0.272792225 -1.280229306 0.662343098 + ----------------------------------------- +Total Dipole Moment : -0.033386767 -0.580819362 0.255689254 + ----------------------------------------- +Magnitude (a.u.) : 0.635486272 +Magnitude (Debye) : 1.615277735 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.972017 0.427869 0.379588 +Rotational constants in MHz : 89098.832725 12827.193917 11379.749230 + +Dipole components along the rotational axes: +x,y,z [a.u.] : -0.428233 0.377036 -0.279827 +x,y,z [Debye]: -1.088481 0.958350 -0.711264 + + + +Dipole moment calculation done in 0.2 sec + +Maximum memory used throughout the entire PROP-calculation: 12.8 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 17 * + * * + * Dihedral ( 2, 1, 0, 3) : -32.30769231 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2810 0.752357 + 2. B(O 2,O 1) 1.3100 0.676348 + 3. B(H 3,N 0) 1.0405 0.390122 + 4. A(O 1,N 0,H 3) 106.4456 0.361901 + 5. A(N 0,O 1,O 2) 120.7058 0.444611 + 6. D(O 2,O 1,N 0,H 3) -32.3077 0.044965 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.422054 -0.641274 -0.411236 + O 0.219459 0.455026 -0.577372 + O 0.407284 1.278488 0.423969 + H -0.223397 -0.954396 0.560931 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.797567 -1.211832 -0.777123 + 1 O 8.0000 0 15.999 0.414717 0.859874 -1.091075 + 2 O 8.0000 0 15.999 0.769656 2.415993 0.801186 + 3 H 1.0000 0 1.008 -0.422158 -1.803548 1.060005 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.279427360620 0.00000000 0.00000000 + O 2 1 0 1.308418691525 120.93056721 0.00000000 + H 1 2 3 1.038201913920 106.66759636 318.46153846 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.417767319818 0.00000000 0.00000000 + O 2 1 0 2.472552995486 120.93056721 0.00000000 + H 1 2 3 1.961917289023 106.66759636 318.46153846 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1679 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.797499820117 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.937e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22314 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.7974998201 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5579671609824004 0.00e+00 3.84e-04 3.33e-03 2.37e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.079) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5590797593631009 -1.11e-03 4.55e-04 3.81e-03 1.83e-02 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.5599970406491366 -9.17e-04 3.44e-04 2.56e-03 1.30e-02 0.700 0.0 + 4 -205.5606358920297794 -6.39e-04 8.55e-04 6.69e-03 9.19e-03 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5621364649966267 -1.50e-03 1.14e-04 2.06e-03 1.68e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -205.5621359602031362 5.05e-07 4.50e-04 5.72e-03 1.75e-03 0.1 + 7 -205.5616992640917147 4.37e-04 3.69e-04 5.53e-03 1.03e-02 0.0 + 8 -205.5621573170585634 -4.58e-04 4.56e-05 7.53e-04 3.81e-04 0.0 + 9 -205.5621534693758008 3.85e-06 3.19e-05 5.77e-04 9.79e-04 0.0 + 10 -205.5621580926511456 -4.62e-06 4.10e-06 3.69e-05 1.69e-05 0.0 + 11 -205.5621580979899932 -5.34e-09 1.29e-06 1.14e-05 1.27e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56215809798999 Eh -5593.63070 eV + +Components: +Nuclear Repulsion : 69.79749982011710 Eh 1899.28653 eV +Electronic Energy : -275.35965791810708 Eh -7492.91722 eV +One Electron Energy: -419.26129844825118 Eh -11408.67994 eV +Two Electron Energy: 143.90164053014411 Eh 3915.76271 eV + +Virial components: +Potential Energy : -410.39630554183867 Eh -11167.45122 eV +Kinetic Energy : 204.83414744384868 Eh 5573.82052 eV +Virial Ratio : 2.00355414691948 + +DFT components: +N(Alpha) : 12.000002569248 electrons +N(Beta) : 12.000002569248 electrons +N(Total) : 24.000005138496 electrons +E(X) : -23.341414505153 Eh +E(C) : -0.804273200638 Eh +E(XC) : -24.145687705791 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 5.3388e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.1431e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.2932e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.6769e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.2662e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.4309e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.191590 -522.2297 + 1 2.0000 -19.023782 -517.6634 + 2 2.0000 -14.273301 -388.3963 + 3 2.0000 -1.251579 -34.0572 + 4 2.0000 -0.968631 -26.3578 + 5 2.0000 -0.720094 -19.5948 + 6 2.0000 -0.563453 -15.3323 + 7 2.0000 -0.520613 -14.1666 + 8 2.0000 -0.497393 -13.5347 + 9 2.0000 -0.333594 -9.0776 + 10 2.0000 -0.285040 -7.7563 + 11 2.0000 -0.268939 -7.3182 + 12 0.0000 -0.190956 -5.1962 + 13 0.0000 0.031761 0.8643 + 14 0.0000 0.097463 2.6521 + 15 0.0000 0.135675 3.6919 + 16 0.0000 0.223977 6.0947 + 17 0.0000 0.268922 7.3177 + 18 0.0000 0.304345 8.2816 + 19 0.0000 0.328812 8.9474 + 20 0.0000 0.357002 9.7145 + 21 0.0000 0.381363 10.3774 + 22 0.0000 0.396403 10.7867 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.254500 + 1 O : 0.213437 + 2 O : -0.221193 + 3 H : 0.262256 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.848581 s : 3.848581 + pz : 1.365781 p : 3.352312 + px : 1.036491 + py : 0.950040 + dz2 : 0.013449 d : 0.053607 + dxz : 0.003253 + dyz : 0.005466 + dx2y2 : 0.016458 + dxy : 0.014981 + + 1 O s : 3.739917 s : 3.739917 + pz : 1.448819 p : 3.906520 + px : 1.316917 + py : 1.140784 + dz2 : 0.037427 d : 0.140126 + dxz : 0.019763 + dyz : 0.022572 + dx2y2 : 0.034518 + dxy : 0.025846 + + 2 O s : 3.941556 s : 3.941556 + pz : 1.382950 p : 4.261409 + px : 1.541665 + py : 1.336793 + dz2 : -0.000069 d : 0.018228 + dxz : 0.005550 + dyz : 0.008316 + dx2y2 : 0.002069 + dxy : 0.002361 + + 3 H s : 0.709171 s : 0.709171 + pz : 0.016969 p : 0.028573 + px : 0.005458 + py : 0.006147 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.047491 + 1 O : -0.181802 + 2 O : -0.048077 + 3 H : 0.277370 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.348143 s : 3.348143 + pz : 1.325494 p : 3.389174 + px : 1.021964 + py : 1.041716 + dz2 : 0.055167 d : 0.310173 + dxz : 0.020738 + dyz : 0.084341 + dx2y2 : 0.067739 + dxy : 0.082187 + + 1 O s : 3.365996 s : 3.365996 + pz : 1.470188 p : 4.043764 + px : 1.275816 + py : 1.297760 + dz2 : 0.159368 d : 0.772043 + dxz : 0.064932 + dyz : 0.207069 + dx2y2 : 0.166127 + dxy : 0.174546 + + 2 O s : 3.605609 s : 3.605609 + pz : 1.380622 p : 4.194017 + px : 1.461506 + py : 1.351889 + dz2 : 0.074922 d : 0.248451 + dxz : 0.034240 + dyz : 0.074172 + dx2y2 : 0.030765 + dxy : 0.034353 + + 3 H s : 0.648837 s : 0.648837 + pz : 0.047250 p : 0.073793 + px : 0.013393 + py : 0.013149 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2545 7.0000 -0.2545 2.7909 2.7909 -0.0000 + 1 O 7.7866 8.0000 0.2134 2.6296 2.6296 0.0000 + 2 O 8.2212 8.0000 -0.2212 1.6815 1.6815 -0.0000 + 3 H 0.7377 1.0000 0.2623 0.9266 0.9266 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4317 B( 0-N , 2-O ) : 0.4828 B( 0-N , 3-H ) : 0.8764 +B( 1-O , 2-O ) : 1.1732 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.638 sec +Sum of individual times .... 1.620 sec ( 98.9%) + +SCF preparation .... 0.587 sec ( 35.8%) +Fock matrix formation .... 0.297 sec ( 18.1%) + Startup .... 0.013 sec ( 4.4% of F) + Split-RI-J .... 0.042 sec ( 14.1% of F) + XC integration .... 0.196 sec ( 66.2% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.009 sec ( 4.8% of XC) + Density eval. .... 0.016 sec ( 7.9% of XC) + XC-Functional eval. .... 0.010 sec ( 5.2% of XC) + XC-Potential eval. .... 0.016 sec ( 7.9% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.020 sec ( 1.2%) +Total Energy calculation .... 0.023 sec ( 1.4%) +Population analysis .... 0.571 sec ( 34.9%) +Orbital Transformation .... 0.014 sec ( 0.9%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.069 sec ( 4.2%) +SOSCF solution .... 0.038 sec ( 2.3%) +Finished LeanSCF after 2.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 24.1 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000363866 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007147102 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.555374862107 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001133 -0.000005260 0.000001878 + 2 O : 0.000000281 0.000000493 -0.000000883 + 3 O : 0.000002161 0.000005711 0.000001982 + 4 H : -0.000001308 -0.000000944 -0.000002978 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000092879 +RMS gradient ... 0.0000026812 +MAX gradient ... 0.0000057114 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.034487915 0.015018026 0.007854445 + 2 O : 0.033820076 -0.012854644 0.001073191 + 3 O : -0.017326969 0.010860397 -0.002433116 + 4 H : 0.017994808 -0.013023778 -0.006494519 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000111289 0.0000438934 -0.0000102955 + +Norm of the Cartesian gradient ... 0.0612090161 +RMS gradient ... 0.0176695210 +MAX gradient ... 0.0344879148 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.128 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 4.0%) +RI-J Coulomb gradient .... 0.059 sec ( 46.4%) +XC gradient .... 0.019 sec ( 15.0%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.555374862 Eh +Current gradient norm .... 0.061209016 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999930803 +Lowest eigenvalues of augmented Hessian: + -0.000086229 0.361032412 0.386862100 0.443680857 0.672483479 +Length of the computed step .... 0.011764731 +The final length of the internal step .... 0.011764731 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0048029315 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0042734972 RMS(Int)= 0.0048029732 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0031012754 0.0001000000 NO + MAX gradient 0.0067289408 0.0003000000 NO + RMS step 0.0048029315 0.0020000000 NO + MAX step 0.0089952713 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0048 Max(Angles) 0.30 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2810 0.006729 -0.0048 1.2763 + 2. B(O 2,O 1) 1.3100 0.002485 -0.0020 1.3080 + 3. B(H 3,N 0) 1.0405 0.001284 -0.0018 1.0387 + 4. A(O 1,N 0,H 3) 106.45 0.001910 -0.30 106.14 + 5. A(N 0,O 1,O 2) 120.71 -0.000978 0.13 120.83 + 6. D(O 2,O 1,N 0,H 3) -32.31 -0.043523 0.00 -32.31 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.789 %) +Internal coordinates : 0.000 s ( 3.464 %) +B/P matrices and projection : 0.000 s (14.608 %) +Hessian update/contruction : 0.000 s (26.506 %) +Making the step : 0.000 s ( 8.283 %) +Converting the step to Cartesian: 0.000 s ( 4.669 %) +Storing new data : 0.000 s ( 3.614 %) +Checking convergence : 0.000 s ( 0.151 %) +Final printing : 0.000 s (28.313 %) +Total time : 0.001 s + +Time for energy+gradient : 5.861 s +Time for complete geometry iter : 6.623 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.421599 -0.639997 -0.411795 + O 0.218326 0.452068 -0.575292 + O 0.406252 1.275008 0.423900 + H -0.221687 -0.949235 0.559479 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.796707 -1.209419 -0.778179 + 1 O 8.0000 0 15.999 0.412576 0.854284 -1.087145 + 2 O 8.0000 0 15.999 0.767706 2.409417 0.801056 + 3 H 1.0000 0 1.008 -0.418927 -1.793795 1.057262 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.276260306527 0.00000000 0.00000000 + O 2 1 0 1.308026829602 120.83205933 0.00000000 + H 1 2 3 1.038732994537 106.14256771 327.69230795 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.411782454931 0.00000000 0.00000000 + O 2 1 0 2.471812483769 120.83205933 0.00000000 + H 1 2 3 1.962920885943 106.14256771 327.69230795 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1680 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.972469860224 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.912e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22311 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5622002543988742 0.00e+00 1.13e-04 9.32e-04 1.81e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5622194164038206 -1.92e-05 1.10e-04 1.21e-03 3.91e-04 0.0 + 3 -205.5622015334436128 1.79e-05 8.55e-05 1.30e-03 1.76e-03 0.0 + 4 -205.5622191741878169 -1.76e-05 1.08e-04 1.63e-03 5.76e-04 0.0 + 5 -205.5622017567981175 1.74e-05 7.49e-05 1.24e-03 1.99e-03 0.0 + 6 -205.5622218440898905 -2.01e-05 1.91e-05 2.01e-04 8.18e-05 0.0 + 7 -205.5622218094922005 3.46e-08 1.03e-05 1.10e-04 9.41e-05 0.0 + 8 -205.5622219510233322 -1.42e-07 1.86e-07 2.19e-06 8.85e-07 0.0 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56222195102333 Eh -5593.63243 eV + +Components: +Nuclear Repulsion : 69.97246986022360 Eh 1904.04770 eV +Electronic Energy : -275.53469181124694 Eh -7497.68014 eV +One Electron Energy: -419.59441253460409 Eh -11417.74443 eV +Two Electron Energy: 144.05972072335715 Eh 3920.06429 eV + +Virial components: +Potential Energy : -410.41594084579731 Eh -11167.98552 eV +Kinetic Energy : 204.85371889477400 Eh 5574.35309 eV +Virial Ratio : 2.00345858039616 + +DFT components: +N(Alpha) : 12.000002655037 electrons +N(Beta) : 12.000002655037 electrons +N(Total) : 24.000005310075 electrons +E(X) : -23.346664840545 Eh +E(C) : -0.804613016012 Eh +E(XC) : -24.151277856557 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.4153e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.1950e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.8647e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.1086e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 8.8548e-07 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.4095e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 1.6 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 24.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000363935 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007158448 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.555427438040 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001117 -0.000005219 0.000001884 + 2 O : 0.000000277 0.000000482 -0.000000868 + 3 O : 0.000002139 0.000005645 0.000001974 + 4 H : -0.000001299 -0.000000907 -0.000002990 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000092135 +RMS gradient ... 0.0000026597 +MAX gradient ... 0.0000056446 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.033034691 0.017905599 0.007390406 + 2 O : 0.032210300 -0.015966903 0.004605548 + 3 O : -0.017681579 0.009864767 -0.004205167 + 4 H : 0.018505970 -0.011803463 -0.007790787 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000080201 0.0000437853 -0.0000063544 + +Norm of the Cartesian gradient ... 0.0612396949 +RMS gradient ... 0.0176783772 +MAX gradient ... 0.0330346914 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.148 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.009 sec ( 6.1%) +RI-J Coulomb gradient .... 0.064 sec ( 43.5%) +XC gradient .... 0.022 sec ( 15.0%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.555427438 Eh +Current gradient norm .... 0.061239695 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999991256 +Lowest eigenvalues of augmented Hessian: + -0.000008790 0.373452321 0.413208652 0.427316415 0.542606820 +Length of the computed step .... 0.004181948 +The final length of the internal step .... 0.004181948 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0017072731 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0008880604 RMS(Int)= 0.0017072394 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000004395 +Previously predicted energy change .... -0.000043120 +Actually observed energy change .... -0.000052576 +Ratio of predicted to observed change .... 1.219284479 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000525759 0.0000050000 NO + RMS gradient 0.0008642217 0.0001000000 NO + MAX gradient 0.0020120599 0.0003000000 NO + RMS step 0.0017072731 0.0020000000 YES + MAX step 0.0038126637 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0020 Max(Angles) 0.06 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2763 0.002012 -0.0020 1.2742 + 2. B(O 2,O 1) 1.3080 0.000456 -0.0005 1.3075 + 3. B(H 3,N 0) 1.0387 -0.000212 0.0003 1.0390 + 4. A(O 1,N 0,H 3) 106.14 -0.000235 0.03 106.18 + 5. A(N 0,O 1,O 2) 120.83 -0.000353 0.06 120.90 + 6. D(O 2,O 1,N 0,H 3) -32.31 -0.043897 0.00 -32.31 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 6.590 %) +Internal coordinates : 0.000 s ( 2.775 %) +B/P matrices and projection : 0.000 s (10.751 %) +Hessian update/contruction : 0.000 s (44.509 %) +Making the step : 0.000 s ( 5.434 %) +Converting the step to Cartesian: 0.000 s ( 3.699 %) +Storing new data : 0.000 s ( 2.890 %) +Checking convergence : 0.000 s ( 1.272 %) +Final printing : 0.000 s (21.850 %) +Total time : 0.001 s + +Time for energy+gradient : 5.124 s +Time for complete geometry iter : 5.921 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.421051 -0.639019 -0.411951 + O 0.217842 0.451403 -0.574708 + O 0.406147 1.274604 0.423491 + H -0.221646 -0.949144 0.559460 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.795671 -1.207571 -0.778474 + 1 O 8.0000 0 15.999 0.411661 0.853028 -1.086042 + 2 O 8.0000 0 15.999 0.767508 2.408652 0.800282 + 3 H 1.0000 0 1.008 -0.418850 -1.793621 1.057227 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.274242731784 0.00000000 0.00000000 + O 2 1 0 1.307486270679 120.89562166 0.00000000 + H 1 2 3 1.039028205711 106.17727219 327.69230795 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.407969791212 0.00000000 0.00000000 + O 2 1 0 2.470790975446 120.89562166 0.00000000 + H 1 2 3 1.963478754212 106.17727219 327.69230795 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1680 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.029505799618 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.904e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22312 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5622216539007354 0.00e+00 4.69e-05 4.00e-04 9.06e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5622251064016268 -3.45e-06 3.99e-05 4.43e-04 1.93e-04 0.0 + 3 -205.5622234984716101 1.61e-06 2.66e-05 4.23e-04 4.64e-04 0.0 + 4 -205.5622250836362923 -1.59e-06 4.79e-05 6.49e-04 2.87e-04 0.0 + 5 -205.5622210691959708 4.01e-06 3.54e-05 5.34e-04 8.76e-04 0.0 + 6 -205.5622255228676636 -4.45e-06 6.85e-06 7.19e-05 2.78e-05 0.0 + 7 -205.5622255202964652 2.57e-09 3.58e-06 3.84e-05 3.06e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56222552029647 Eh -5593.63253 eV + +Components: +Nuclear Repulsion : 70.02950579961765 Eh 1905.59973 eV +Electronic Energy : -275.59173131991412 Eh -7499.23226 eV +One Electron Energy: -419.70222272877089 Eh -11420.67810 eV +Two Electron Energy: 144.11049140885677 Eh 3921.44583 eV + +Virial components: +Potential Energy : -410.42167193168791 Eh -11168.14147 eV +Kinetic Energy : 204.85944641139142 Eh 5574.50894 eV +Virial Ratio : 2.00343054284885 + +DFT components: +N(Alpha) : 12.000002604666 electrons +N(Beta) : 12.000002604666 electrons +N(Total) : 24.000005209333 electrons +E(X) : -23.348063721138 Eh +E(C) : -0.804719766058 Eh +E(XC) : -24.152783487196 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -2.5712e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.8425e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.5788e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.6303e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.0576e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.0045e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 24.4 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000363955 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007157063 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.555432411893 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.0 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001115 -0.000005213 0.000001887 + 2 O : 0.000000276 0.000000480 -0.000000866 + 3 O : 0.000002135 0.000005633 0.000001970 + 4 H : -0.000001296 -0.000000901 -0.000002991 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000092001 +RMS gradient ... 0.0000026558 +MAX gradient ... 0.0000056335 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.032370983 0.019455228 0.006862040 + 2 O : 0.031541910 -0.017160212 0.005609682 + 3 O : -0.017799205 0.009518431 -0.004820089 + 4 H : 0.018628278 -0.011813447 -0.007651633 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000062078 0.0000392929 -0.0000028668 + +Norm of the Cartesian gradient ... 0.0614009027 +RMS gradient ... 0.0177249139 +MAX gradient ... 0.0323709834 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.093 sec + +Densities .... 0.000 sec ( 0.4%) +One electron gradient .... 0.005 sec ( 5.2%) +RI-J Coulomb gradient .... 0.045 sec ( 48.1%) +XC gradient .... 0.013 sec ( 14.0%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.555432412 Eh +Current gradient norm .... 0.061400903 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999998884 +Lowest eigenvalues of augmented Hessian: + -0.000000773 0.317040288 0.394613054 0.432065862 0.559574707 +Length of the computed step .... 0.001493839 +The final length of the internal step .... 0.001493839 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0006098572 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0005413174 RMS(Int)= 0.0006098949 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000386 +Previously predicted energy change .... -0.000004395 +Actually observed energy change .... -0.000004974 +Ratio of predicted to observed change .... 1.131731922 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000049739 0.0000050000 YES + RMS gradient 0.0002199668 0.0001000000 NO + MAX gradient 0.0003880015 0.0003000000 NO + RMS step 0.0006098572 0.0020000000 YES + MAX step 0.0011731577 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0004 Max(Angles) 0.07 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2742 0.000250 -0.0004 1.2738 + 2. B(O 2,O 1) 1.3075 -0.000249 0.0002 1.3076 + 3. B(H 3,N 0) 1.0390 -0.000055 0.0001 1.0391 + 4. A(O 1,N 0,H 3) 106.18 -0.000388 0.07 106.24 + 5. A(N 0,O 1,O 2) 120.90 -0.000111 0.02 120.92 + 6. D(O 2,O 1,N 0,H 3) -32.31 -0.044010 -0.00 -32.31 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 8.617 %) +Internal coordinates : 0.000 s ( 2.608 %) +B/P matrices and projection : 0.000 s (17.687 %) +Hessian update/contruction : 0.000 s (36.395 %) +Making the step : 0.000 s ( 4.762 %) +Converting the step to Cartesian: 0.000 s ( 3.288 %) +Storing new data : 0.000 s ( 2.721 %) +Checking convergence : 0.000 s ( 1.134 %) +Final printing : 0.000 s (22.449 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.420801 -0.638770 -0.411830 + O 0.217709 0.451389 -0.574651 + O 0.406301 1.275063 0.423308 + H -0.221917 -0.949838 0.559465 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.795199 -1.207101 -0.778247 + 1 O 8.0000 0 15.999 0.411411 0.853002 -1.085934 + 2 O 8.0000 0 15.999 0.767797 2.409520 0.799937 + 3 H 1.0000 0 1.008 -0.419362 -1.794934 1.057236 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.273834286542 0.00000000 0.00000000 + O 2 1 0 1.307642673839 120.91800208 0.00000000 + H 1 2 3 1.039102235757 106.24448918 327.69230795 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.407197941564 0.00000000 0.00000000 + O 2 1 0 2.471086534584 120.91800208 0.00000000 + H 1 2 3 1.963618650725 106.24448918 327.69230795 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1680 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.031816981431 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.905e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22313 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.0318169814 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5622223689570376 0.00e+00 1.47e-05 1.30e-04 3.27e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5622227302246472 -3.61e-07 1.16e-05 1.03e-04 3.15e-05 0.1 + 3 -205.5622225701232253 1.60e-07 8.78e-06 1.38e-04 1.97e-04 0.0 + 4 -205.5622227489522800 -1.79e-07 7.85e-06 1.19e-04 4.85e-05 0.0 + 5 -205.5622226803665455 6.86e-08 4.64e-06 8.27e-05 1.33e-04 0.0 + 6 -205.5622227660408328 -8.57e-08 1.66e-06 1.76e-05 4.53e-06 0.0 + 7 -205.5622227657077872 3.33e-10 7.58e-07 8.10e-06 4.90e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56222276570779 Eh -5593.63246 eV + +Components: +Nuclear Repulsion : 70.03181698143121 Eh 1905.66262 eV +Electronic Energy : -275.59403974713899 Eh -7499.29508 eV +One Electron Energy: -419.70791802137296 Eh -11420.83307 eV +Two Electron Energy: 144.11387827423397 Eh 3921.53799 eV + +Virial components: +Potential Energy : -410.42202715601945 Eh -11168.15114 eV +Kinetic Energy : 204.85980439031167 Eh 5574.51868 eV +Virial Ratio : 2.00342877597431 + +DFT components: +N(Alpha) : 12.000002565176 electrons +N(Beta) : 12.000002565176 electrons +N(Total) : 24.000005130352 electrons +E(X) : -23.348317379015 Eh +E(C) : -0.804727288979 Eh +E(XC) : -24.153044667994 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -3.3305e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.1002e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 7.5819e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.9203e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.9013e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 6.4820e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.191895 -522.2380 + 1 2.0000 -19.023040 -517.6432 + 2 2.0000 -14.272984 -388.3876 + 3 2.0000 -1.255384 -34.1607 + 4 2.0000 -0.971493 -26.4357 + 5 2.0000 -0.719452 -19.5773 + 6 2.0000 -0.564499 -15.3608 + 7 2.0000 -0.522662 -14.2224 + 8 2.0000 -0.498609 -13.5679 + 9 2.0000 -0.333195 -9.0667 + 10 2.0000 -0.285024 -7.7559 + 11 2.0000 -0.268670 -7.3109 + 12 0.0000 -0.189583 -5.1588 + 13 0.0000 0.033910 0.9227 + 14 0.0000 0.099233 2.7003 + 15 0.0000 0.138452 3.7675 + 16 0.0000 0.226036 6.1508 + 17 0.0000 0.268707 7.3119 + 18 0.0000 0.303806 8.2670 + 19 0.0000 0.329504 8.9663 + 20 0.0000 0.356514 9.7013 + 21 0.0000 0.381564 10.3829 + 22 0.0000 0.397197 10.8083 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.252716 + 1 O : 0.215213 + 2 O : -0.223830 + 3 H : 0.261334 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.845846 s : 3.845846 + pz : 1.366068 p : 3.352693 + px : 1.035657 + py : 0.950968 + dz2 : 0.013450 d : 0.054177 + dxz : 0.003282 + dyz : 0.005561 + dx2y2 : 0.016713 + dxy : 0.015171 + + 1 O s : 3.736150 s : 3.736150 + pz : 1.450578 p : 3.907463 + px : 1.315405 + py : 1.141480 + dz2 : 0.037666 d : 0.141175 + dxz : 0.019879 + dyz : 0.022664 + dx2y2 : 0.034847 + dxy : 0.026119 + + 2 O s : 3.940733 s : 3.940733 + pz : 1.385313 p : 4.264660 + px : 1.543163 + py : 1.336184 + dz2 : -0.000052 d : 0.018437 + dxz : 0.005560 + dyz : 0.008413 + dx2y2 : 0.002106 + dxy : 0.002410 + + 3 H s : 0.709985 s : 0.709985 + pz : 0.017027 p : 0.028681 + px : 0.005477 + py : 0.006177 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.045722 + 1 O : -0.183946 + 2 O : -0.047478 + 3 H : 0.277146 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.343543 s : 3.343543 + pz : 1.323859 p : 3.389568 + px : 1.021353 + py : 1.044355 + dz2 : 0.055447 d : 0.312611 + dxz : 0.020928 + dyz : 0.085210 + dx2y2 : 0.068311 + dxy : 0.082714 + + 1 O s : 3.361210 s : 3.361210 + pz : 1.471568 p : 4.045386 + px : 1.274678 + py : 1.299140 + dz2 : 0.159879 d : 0.777350 + dxz : 0.065620 + dyz : 0.208851 + dx2y2 : 0.167454 + dxy : 0.175546 + + 2 O s : 3.603713 s : 3.603713 + pz : 1.381712 p : 4.195237 + px : 1.462212 + py : 1.351313 + dz2 : 0.074844 d : 0.248528 + dxz : 0.034138 + dyz : 0.074176 + dx2y2 : 0.030904 + dxy : 0.034467 + + 3 H s : 0.648913 s : 0.648913 + pz : 0.047356 p : 0.073941 + px : 0.013443 + py : 0.013143 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2527 7.0000 -0.2527 2.7926 2.7926 -0.0000 + 1 O 7.7848 8.0000 0.2152 2.6321 2.6321 -0.0000 + 2 O 8.2238 8.0000 -0.2238 1.6794 1.6794 0.0000 + 3 H 0.7387 1.0000 0.2613 0.9275 0.9275 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4349 B( 0-N , 2-O ) : 0.4806 B( 0-N , 3-H ) : 0.8771 +B( 1-O , 2-O ) : 1.1728 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.356 sec +Sum of individual times .... 1.342 sec ( 98.9%) + +SCF preparation .... 0.559 sec ( 41.2%) +Fock matrix formation .... 0.179 sec ( 13.2%) + Startup .... 0.008 sec ( 4.7% of F) + Split-RI-J .... 0.023 sec ( 12.7% of F) + XC integration .... 0.122 sec ( 68.3% of F) + Basis function eval. .... 0.006 sec ( 5.3% of XC) + Density eval. .... 0.009 sec ( 7.4% of XC) + XC-Functional eval. .... 0.006 sec ( 4.8% of XC) + XC-Potential eval. .... 0.009 sec ( 7.0% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.011 sec ( 0.8%) +Total Energy calculation .... 0.013 sec ( 1.0%) +Population analysis .... 0.531 sec ( 39.1%) +Orbital Transformation .... 0.006 sec ( 0.4%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.009 sec ( 0.7%) +SOSCF solution .... 0.035 sec ( 2.6%) +Finished LeanSCF after 1.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 24.7 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000363951 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007153761 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.555432955872 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.017.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.017.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.155384 0.712142 -0.306529 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5622227657077872 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.215122120 0.659423188 -0.440054438 +Nuclear contribution : -0.281313125 -1.235873605 0.678242241 + ----------------------------------------- +Total Dipole Moment : -0.066191004 -0.576450417 0.238187803 + ----------------------------------------- +Magnitude (a.u.) : 0.627223853 +Magnitude (Debye) : 1.594276336 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.968794 0.432614 0.381188 +Rotational constants in MHz : 89002.218676 12969.435440 11427.714188 + +Dipole components along the rotational axes: +x,y,z [a.u.] : 0.435788 0.394660 0.218501 +x,y,z [Debye]: 1.107684 1.003146 0.555384 + + + +Dipole moment calculation done in 0.2 sec + +Maximum memory used throughout the entire PROP-calculation: 13.3 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 18 * + * * + * Dihedral ( 2, 1, 0, 3) : -23.07692308 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2756 0.767975 + 2. B(O 2,O 1) 1.3091 0.678279 + 3. B(H 3,N 0) 1.0412 0.388834 + 4. A(O 1,N 0,H 3) 106.0090 0.362968 + 5. A(N 0,O 1,O 2) 120.6811 0.446499 + 6. D(O 2,O 1,N 0,H 3) -23.0769 0.047086 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.392281 -0.658330 -0.423445 + O 0.187863 0.466030 -0.586165 + O 0.419294 1.252192 0.434659 + H -0.233584 -0.922049 0.571243 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.741303 -1.244063 -0.800195 + 1 O 8.0000 0 15.999 0.355009 0.880670 -1.107692 + 2 O 8.0000 0 15.999 0.792351 2.366301 0.821387 + 3 H 1.0000 0 1.008 -0.441410 -1.742420 1.079493 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.273834286542 0.00000000 0.00000000 + O 2 1 0 1.307642673839 120.91800208 0.00000000 + H 1 2 3 1.039102235757 106.24448918 327.69230795 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.407197941564 0.00000000 0.00000000 + O 2 1 0 2.471086534584 120.91800208 0.00000000 + H 1 2 3 1.963618650725 106.24448918 327.69230795 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1680 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.995471389757 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.916e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22315 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5579 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.9954713898 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5641013724389836 0.00e+00 3.73e-04 3.36e-03 2.57e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.083) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5652443512042851 -1.14e-03 4.44e-04 3.79e-03 1.99e-02 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.5661871034309343 -9.43e-04 3.37e-04 2.61e-03 1.41e-02 0.700 0.0 + 4 -205.5668462792013997 -6.59e-04 8.42e-04 6.85e-03 9.96e-03 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5683902231898514 -1.54e-03 1.15e-04 2.06e-03 1.60e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -205.5683882628581500 1.96e-06 4.61e-04 6.06e-03 1.90e-03 0.0 + 7 -205.5679264496877749 4.62e-04 3.80e-04 5.89e-03 1.13e-02 0.0 + 8 -205.5684104067306635 -4.84e-04 4.84e-05 8.24e-04 4.23e-04 0.0 + 9 -205.5684060735901539 4.33e-06 3.37e-05 6.16e-04 1.10e-03 0.0 + 10 -205.5684112540228625 -5.18e-06 4.23e-06 3.75e-05 2.12e-05 0.0 + 11 -205.5684112594495332 -5.43e-09 1.42e-06 1.34e-05 1.44e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56841125944953 Eh -5593.80085 eV + +Components: +Nuclear Repulsion : 69.99547138975724 Eh 1904.67361 eV +Electronic Energy : -275.56388264920679 Eh -7498.47446 eV +One Electron Energy: -419.64237522842933 Eh -11419.04956 eV +Two Electron Energy: 144.07849257922257 Eh 3920.57510 eV + +Virial components: +Potential Energy : -410.41153705878571 Eh -11167.86569 eV +Kinetic Energy : 204.84312579933618 Eh 5574.06483 eV +Virial Ratio : 2.00354068732980 + +DFT components: +N(Alpha) : 12.000001475074 electrons +N(Beta) : 12.000001475074 electrons +N(Total) : 24.000002950147 electrons +E(X) : -23.346062414553 Eh +E(C) : -0.804575561339 Eh +E(XC) : -24.150637975892 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 5.4267e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.3372e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.4221e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.6002e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.4396e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.5370e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.193045 -522.2693 + 1 2.0000 -19.021370 -517.5978 + 2 2.0000 -14.275313 -388.4510 + 3 2.0000 -1.254766 -34.1439 + 4 2.0000 -0.970112 -26.3981 + 5 2.0000 -0.720946 -19.6179 + 6 2.0000 -0.562445 -15.3049 + 7 2.0000 -0.522671 -14.2226 + 8 2.0000 -0.498549 -13.5662 + 9 2.0000 -0.333699 -9.0804 + 10 2.0000 -0.288927 -7.8621 + 11 2.0000 -0.268316 -7.3013 + 12 0.0000 -0.185980 -5.0608 + 13 0.0000 0.029943 0.8148 + 14 0.0000 0.100762 2.7419 + 15 0.0000 0.137112 3.7310 + 16 0.0000 0.223154 6.0723 + 17 0.0000 0.272228 7.4077 + 18 0.0000 0.300879 8.1873 + 19 0.0000 0.330222 8.9858 + 20 0.0000 0.356786 9.7086 + 21 0.0000 0.377014 10.2591 + 22 0.0000 0.396056 10.7772 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.246648 + 1 O : 0.221037 + 2 O : -0.233409 + 3 H : 0.259019 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.853047 s : 3.853047 + pz : 1.355823 p : 3.340654 + px : 1.045656 + py : 0.939175 + dz2 : 0.013093 d : 0.052946 + dxz : 0.002049 + dyz : 0.005768 + dx2y2 : 0.016526 + dxy : 0.015510 + + 1 O s : 3.738129 s : 3.738129 + pz : 1.440337 p : 3.897931 + px : 1.320271 + py : 1.137323 + dz2 : 0.039010 d : 0.142902 + dxz : 0.019256 + dyz : 0.023515 + dx2y2 : 0.033520 + dxy : 0.027601 + + 2 O s : 3.941343 s : 3.941343 + pz : 1.357377 p : 4.272432 + px : 1.516748 + py : 1.398308 + dz2 : -0.000418 d : 0.019634 + dxz : 0.006577 + dyz : 0.008879 + dx2y2 : 0.002066 + dxy : 0.002530 + + 3 H s : 0.712676 s : 0.712676 + pz : 0.017529 p : 0.028304 + px : 0.005212 + py : 0.005563 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.041048 + 1 O : -0.181873 + 2 O : -0.054426 + 3 H : 0.277347 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.347898 s : 3.347898 + pz : 1.317576 p : 3.381832 + px : 1.019989 + py : 1.044267 + dz2 : 0.058232 d : 0.311318 + dxz : 0.017095 + dyz : 0.085613 + dx2y2 : 0.070595 + dxy : 0.079783 + + 1 O s : 3.363070 s : 3.363070 + pz : 1.467155 p : 4.042930 + px : 1.272140 + py : 1.303635 + dz2 : 0.164367 d : 0.775872 + dxz : 0.065507 + dyz : 0.209005 + dx2y2 : 0.164846 + dxy : 0.172147 + + 2 O s : 3.603879 s : 3.603879 + pz : 1.359450 p : 4.201548 + px : 1.439659 + py : 1.402438 + dz2 : 0.078108 d : 0.249000 + dxz : 0.036715 + dyz : 0.071987 + dx2y2 : 0.029936 + dxy : 0.032253 + + 3 H s : 0.649507 s : 0.649507 + pz : 0.048829 p : 0.073146 + px : 0.012715 + py : 0.011602 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2466 7.0000 -0.2466 2.7903 2.7903 0.0000 + 1 O 7.7790 8.0000 0.2210 2.6425 2.6425 0.0000 + 2 O 8.2334 8.0000 -0.2334 1.6808 1.6808 -0.0000 + 3 H 0.7410 1.0000 0.2590 0.9297 0.9297 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4408 B( 0-N , 2-O ) : 0.4743 B( 0-N , 3-H ) : 0.8753 +B( 1-O , 2-O ) : 1.1769 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.624 sec +Sum of individual times .... 1.610 sec ( 99.1%) + +SCF preparation .... 0.580 sec ( 35.7%) +Fock matrix formation .... 0.296 sec ( 18.2%) + Startup .... 0.013 sec ( 4.2% of F) + Split-RI-J .... 0.057 sec ( 19.2% of F) + XC integration .... 0.184 sec ( 62.0% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.012 sec ( 6.5% of XC) + Density eval. .... 0.018 sec ( 9.5% of XC) + XC-Functional eval. .... 0.010 sec ( 5.2% of XC) + XC-Potential eval. .... 0.018 sec ( 10.0% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.026 sec ( 1.6%) +Total Energy calculation .... 0.022 sec ( 1.4%) +Population analysis .... 0.568 sec ( 35.0%) +Orbital Transformation .... 0.014 sec ( 0.8%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.067 sec ( 4.1%) +SOSCF solution .... 0.038 sec ( 2.3%) +Finished LeanSCF after 2.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 25.1 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000364080 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007209435 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.561565904475 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001211 -0.000005053 0.000001920 + 2 O : 0.000000230 0.000000500 -0.000000890 + 3 O : 0.000002101 0.000005447 0.000002039 + 4 H : -0.000001120 -0.000000894 -0.000003068 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000090270 +RMS gradient ... 0.0000026059 +MAX gradient ... 0.0000054467 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.026896931 0.009145831 0.005058874 + 2 O : 0.025971075 -0.007883286 -0.001535494 + 3 O : -0.013213167 0.007697488 -0.000114851 + 4 H : 0.014139022 -0.008960033 -0.003408530 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000426227 0.0000464170 0.0000447117 + +Norm of the Cartesian gradient ... 0.0457968175 +RMS gradient ... 0.0132204025 +MAX gradient ... 0.0268969307 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.144 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.007 sec ( 5.1%) +RI-J Coulomb gradient .... 0.062 sec ( 43.1%) +XC gradient .... 0.025 sec ( 17.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.561565904 Eh +Current gradient norm .... 0.045796817 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999950163 +Lowest eigenvalues of augmented Hessian: + -0.000063602 0.362084542 0.385825091 0.445541137 0.674710051 +Length of the computed step .... 0.009984086 +The final length of the internal step .... 0.009984086 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0040759860 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0034455007 RMS(Int)= 0.0040761204 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0026931183 0.0001000000 NO + MAX gradient 0.0058500897 0.0003000000 NO + RMS step 0.0040759860 0.0020000000 NO + MAX step 0.0076673066 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0041 Max(Angles) 0.23 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2756 0.005850 -0.0041 1.2716 + 2. B(O 2,O 1) 1.3091 0.002202 -0.0017 1.3074 + 3. B(H 3,N 0) 1.0412 0.001161 -0.0016 1.0396 + 4. A(O 1,N 0,H 3) 106.01 0.001470 -0.23 105.78 + 5. A(N 0,O 1,O 2) 120.68 -0.000969 0.12 120.81 + 6. D(O 2,O 1,N 0,H 3) -23.08 -0.032179 0.00 -23.08 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.479 %) +Internal coordinates : 0.000 s ( 3.593 %) +B/P matrices and projection : 0.000 s (14.072 %) +Hessian update/contruction : 0.000 s (30.389 %) +Making the step : 0.000 s ( 5.838 %) +Converting the step to Cartesian: 0.000 s ( 4.491 %) +Storing new data : 0.000 s ( 3.593 %) +Checking convergence : 0.000 s ( 0.150 %) +Final printing : 0.000 s (27.096 %) +Total time : 0.001 s + +Time for energy+gradient : 5.865 s +Time for complete geometry iter : 6.694 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.391830 -0.657222 -0.423781 + O 0.186947 0.463560 -0.584282 + O 0.418459 1.249509 0.434474 + H -0.232283 -0.918003 0.569880 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.740452 -1.241969 -0.800829 + 1 O 8.0000 0 15.999 0.353278 0.876002 -1.104133 + 2 O 8.0000 0 15.999 0.790773 2.361229 0.821037 + 3 H 1.0000 0 1.008 -0.438952 -1.734775 1.076918 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.271571960435 0.00000000 0.00000000 + O 2 1 0 1.307354903074 120.80566328 0.00000000 + H 1 2 3 1.039627142410 105.77645749 336.92307686 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.402922764795 0.00000000 0.00000000 + O 2 1 0 2.470542726649 120.80566328 0.00000000 + H 1 2 3 1.964610580545 105.77645749 336.92307686 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1680 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.145559746121 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.894e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22313 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5684427416500739 0.00e+00 9.78e-05 8.27e-04 1.60e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5684569444830458 -1.42e-05 9.21e-05 9.96e-04 3.45e-04 0.0 + 3 -205.5684451184336012 1.18e-05 7.06e-05 1.12e-03 1.54e-03 0.0 + 4 -205.5684566989720565 -1.16e-05 9.16e-05 1.39e-03 4.97e-04 0.0 + 5 -205.5684446456461387 1.21e-05 6.27e-05 1.06e-03 1.75e-03 0.0 + 6 -205.5684586181691884 -1.40e-05 1.77e-05 1.82e-04 7.53e-05 0.0 + 7 -205.5684585852700934 3.29e-08 9.63e-06 1.01e-04 8.87e-05 0.0 + 8 -205.5684587061248294 -1.21e-07 1.76e-07 2.03e-06 8.72e-07 0.0 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56845870612483 Eh -5593.80214 eV + +Components: +Nuclear Repulsion : 70.14555974612104 Eh 1908.75772 eV +Electronic Energy : -275.71401845224591 Eh -7502.55986 eV +One Electron Energy: -419.92780063997333 Eh -11426.81638 eV +Two Electron Energy: 144.21378218772745 Eh 3924.25652 eV + +Virial components: +Potential Energy : -410.42864462881562 Eh -11168.33121 eV +Kinetic Energy : 204.86018592269076 Eh 5574.52906 eV +Virial Ratio : 2.00345734716702 + +DFT components: +N(Alpha) : 12.000001507735 electrons +N(Beta) : 12.000001507735 electrons +N(Total) : 24.000003015470 electrons +E(X) : -23.350621364819 Eh +E(C) : -0.804868178148 Eh +E(XC) : -24.155489542968 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.2085e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.0342e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.7628e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.8745e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 8.7179e-07 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.3345e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.6 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 25.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000364132 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007218101 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.561604737063 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001199 -0.000005022 0.000001924 + 2 O : 0.000000228 0.000000492 -0.000000878 + 3 O : 0.000002084 0.000005396 0.000002031 + 4 H : -0.000001112 -0.000000866 -0.000003077 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000089696 +RMS gradient ... 0.0000025893 +MAX gradient ... 0.0000053956 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.025683921 0.011732879 0.004742621 + 2 O : 0.024720531 -0.010697395 0.001545089 + 3 O : -0.013540278 0.006896811 -0.001679830 + 4 H : 0.014503668 -0.007932296 -0.004607880 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000449341 0.0000474412 0.0000473535 + +Norm of the Cartesian gradient ... 0.0455629250 +RMS gradient ... 0.0131528835 +MAX gradient ... 0.0256839212 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.127 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.006 sec ( 4.4%) +RI-J Coulomb gradient .... 0.060 sec ( 47.1%) +XC gradient .... 0.019 sec ( 15.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.561604737 Eh +Current gradient norm .... 0.045562925 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999993176 +Lowest eigenvalues of augmented Hessian: + -0.000006834 0.373516697 0.413849356 0.430262117 0.547716733 +Length of the computed step .... 0.003694468 +The final length of the internal step .... 0.003694468 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0015082602 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0007801847 RMS(Int)= 0.0015082393 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000003417 +Previously predicted energy change .... -0.000031804 +Actually observed energy change .... -0.000038833 +Ratio of predicted to observed change .... 1.220995766 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000388326 0.0000050000 NO + RMS gradient 0.0007620583 0.0001000000 NO + MAX gradient 0.0017572393 0.0003000000 NO + RMS step 0.0015082602 0.0020000000 YES + MAX step 0.0033028556 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0017 Max(Angles) 0.05 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2716 0.001757 -0.0017 1.2698 + 2. B(O 2,O 1) 1.3074 0.000444 -0.0005 1.3068 + 3. B(H 3,N 0) 1.0396 -0.000196 0.0003 1.0399 + 4. A(O 1,N 0,H 3) 105.78 -0.000270 0.04 105.82 + 5. A(N 0,O 1,O 2) 120.81 -0.000296 0.05 120.86 + 6. D(O 2,O 1,N 0,H 3) -23.08 -0.032418 0.00 -23.08 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 6.645 %) +Internal coordinates : 0.000 s ( 2.397 %) +B/P matrices and projection : 0.000 s ( 9.804 %) +Hessian update/contruction : 0.000 s (44.662 %) +Making the step : 0.000 s ( 5.773 %) +Converting the step to Cartesian: 0.000 s ( 4.031 %) +Storing new data : 0.000 s ( 2.832 %) +Checking convergence : 0.000 s ( 1.198 %) +Final printing : 0.000 s (22.331 %) +Total time : 0.001 s + +Time for energy+gradient : 5.155 s +Time for complete geometry iter : 5.970 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.391359 -0.656300 -0.423872 + O 0.186594 0.463010 -0.583775 + O 0.418364 1.249213 0.434051 + H -0.232307 -0.918079 0.569888 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.739561 -1.240227 -0.801002 + 1 O 8.0000 0 15.999 0.352611 0.874962 -1.103175 + 2 O 8.0000 0 15.999 0.790593 2.360670 0.820237 + 3 H 1.0000 0 1.008 -0.438996 -1.734918 1.076933 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.269824164551 0.00000000 0.00000000 + O 2 1 0 1.306829004757 120.86022167 0.00000000 + H 1 2 3 1.039897145414 105.82030001 336.92307686 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.399619909237 0.00000000 0.00000000 + O 2 1 0 2.469548922855 120.86022167 0.00000000 + H 1 2 3 1.965120812280 105.82030001 336.92307686 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1680 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.196281804283 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.886e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22314 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5684578671694283 0.00e+00 4.21e-05 3.62e-04 8.41e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5684605277811841 -2.66e-06 3.48e-05 3.94e-04 1.80e-04 0.0 + 3 -205.5684593408770695 1.19e-06 2.27e-05 3.69e-04 4.49e-04 0.0 + 4 -205.5684605236231448 -1.18e-06 4.17e-05 5.59e-04 2.61e-04 0.0 + 5 -205.5684574155531266 3.11e-06 3.11e-05 4.64e-04 7.89e-04 0.0 + 6 -205.5684608405638016 -3.43e-06 6.09e-06 6.30e-05 2.48e-05 0.0 + 7 -205.5684608386137313 1.95e-09 3.19e-06 3.38e-05 2.74e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56846083861373 Eh -5593.80220 eV + +Components: +Nuclear Repulsion : 70.19628180428296 Eh 1910.13794 eV +Electronic Energy : -275.76474264289669 Eh -7503.94014 eV +One Electron Energy: -420.02367287648042 Eh -11429.42520 eV +Two Electron Energy: 144.25893023358373 Eh 3925.48506 eV + +Virial components: +Potential Energy : -410.43376683723830 Eh -11168.47059 eV +Kinetic Energy : 204.86530599862454 Eh 5574.66839 eV +Virial Ratio : 2.00343227876756 + +DFT components: +N(Alpha) : 12.000001540543 electrons +N(Beta) : 12.000001540543 electrons +N(Total) : 24.000003081087 electrons +E(X) : -23.351870176855 Eh +E(C) : -0.804962333692 Eh +E(XC) : -24.156832510548 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.9501e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.3769e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.1926e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.9210e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.7385e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.9419e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.5 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 25.5 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000364148 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007216407 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.561608579779 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001198 -0.000005017 0.000001926 + 2 O : 0.000000227 0.000000491 -0.000000875 + 3 O : 0.000002080 0.000005387 0.000002027 + 4 H : -0.000001110 -0.000000861 -0.000003077 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000089590 +RMS gradient ... 0.0000025862 +MAX gradient ... 0.0000053868 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.025104512 0.013155532 0.004304632 + 2 O : 0.024196972 -0.011777217 0.002413344 + 3 O : -0.013664456 0.006582938 -0.002244510 + 4 H : 0.014571996 -0.007961253 -0.004473465 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000451471 0.0000434742 0.0000490393 + +Norm of the Cartesian gradient ... 0.0456364075 +RMS gradient ... 0.0131740961 +MAX gradient ... 0.0251045124 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.116 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.006 sec ( 4.8%) +RI-J Coulomb gradient .... 0.054 sec ( 46.2%) +XC gradient .... 0.017 sec ( 15.0%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.561608580 Eh +Current gradient norm .... 0.045636407 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999253 +Lowest eigenvalues of augmented Hessian: + -0.000000519 0.316199803 0.394673942 0.436363305 0.575382882 +Length of the computed step .... 0.001222658 +The final length of the internal step .... 0.001222658 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0004991480 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0004656936 RMS(Int)= 0.0004991755 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000260 +Previously predicted energy change .... -0.000003417 +Actually observed energy change .... -0.000003843 +Ratio of predicted to observed change .... 1.124530182 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000038427 0.0000050000 YES + RMS gradient 0.0001809705 0.0001000000 NO + MAX gradient 0.0003242709 0.0003000000 NO + RMS step 0.0004991480 0.0020000000 YES + MAX step 0.0009860972 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0003 Max(Angles) 0.06 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2698 0.000195 -0.0003 1.2695 + 2. B(O 2,O 1) 1.3068 -0.000207 0.0001 1.3070 + 3. B(H 3,N 0) 1.0399 -0.000049 0.0001 1.0400 + 4. A(O 1,N 0,H 3) 105.82 -0.000324 0.06 105.88 + 5. A(N 0,O 1,O 2) 120.86 -0.000090 0.02 120.88 + 6. D(O 2,O 1,N 0,H 3) -23.08 -0.032489 -0.00 -23.08 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 8.614 %) +Internal coordinates : 0.000 s ( 3.096 %) +B/P matrices and projection : 0.000 s (12.248 %) +Hessian update/contruction : 0.000 s (32.840 %) +Making the step : 0.000 s ( 5.114 %) +Converting the step to Cartesian: 0.000 s ( 3.634 %) +Storing new data : 0.000 s ( 2.961 %) +Checking convergence : 0.000 s ( 1.346 %) +Final printing : 0.000 s (29.879 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.391180 -0.656082 -0.423772 + O 0.186512 0.462999 -0.583730 + O 0.418497 1.249615 0.433891 + H -0.232537 -0.918689 0.569903 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.739224 -1.239815 -0.800812 + 1 O 8.0000 0 15.999 0.352457 0.874942 -1.103090 + 2 O 8.0000 0 15.999 0.790845 2.361431 0.819934 + 3 H 1.0000 0 1.008 -0.439431 -1.736070 1.076961 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.269510736319 0.00000000 0.00000000 + O 2 1 0 1.306955796506 120.87829928 0.00000000 + H 1 2 3 1.039961381528 105.87679922 336.92307686 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.399027615715 0.00000000 0.00000000 + O 2 1 0 2.469788524536 120.87829928 0.00000000 + H 1 2 3 1.965242200942 105.87679922 336.92307686 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1681 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.197608947742 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.887e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22313 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.1976089477 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5684579973532493 0.00e+00 1.19e-05 1.01e-04 2.95e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5684582296019869 -2.32e-07 9.46e-06 1.01e-04 3.04e-05 0.0 + 3 -205.5684581104460733 1.19e-07 7.13e-06 1.13e-04 1.82e-04 0.0 + 4 -205.5684582426643203 -1.32e-07 5.56e-06 8.51e-05 3.65e-05 0.0 + 5 -205.5684582062293941 3.64e-08 3.34e-06 6.01e-05 1.02e-04 0.0 + 6 -205.5684582512202212 -4.50e-08 1.10e-06 1.19e-05 3.20e-06 0.0 + 7 -205.5684582506196136 6.01e-10 5.02e-07 5.41e-06 3.26e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56845825061961 Eh -5593.80213 eV + +Components: +Nuclear Repulsion : 70.19760894774166 Eh 1910.17405 eV +Electronic Energy : -275.76606719836127 Eh -7503.97618 eV +One Electron Energy: -420.02737491870619 Eh -11429.52594 eV +Two Electron Energy: 144.26130772034492 Eh 3925.54975 eV + +Virial components: +Potential Energy : -410.43400882366581 Eh -11168.47717 eV +Kinetic Energy : 204.86555057304619 Eh 5574.67504 eV +Virial Ratio : 2.00343106820843 + +DFT components: +N(Alpha) : 12.000001547727 electrons +N(Beta) : 12.000001547727 electrons +N(Total) : 24.000003095455 electrons +E(X) : -23.352079482973 Eh +E(C) : -0.804967297066 Eh +E(XC) : -24.157046780039 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -6.0061e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.4095e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 5.0200e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.5523e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.2603e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.1355e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.193313 -522.2766 + 1 2.0000 -19.020748 -517.5809 + 2 2.0000 -14.275017 -388.4430 + 3 2.0000 -1.258098 -34.2346 + 4 2.0000 -0.972597 -26.4657 + 5 2.0000 -0.720433 -19.6040 + 6 2.0000 -0.563266 -15.3273 + 7 2.0000 -0.524551 -14.2738 + 8 2.0000 -0.499610 -13.5951 + 9 2.0000 -0.333231 -9.0677 + 10 2.0000 -0.288986 -7.8637 + 11 2.0000 -0.268099 -7.2953 + 12 0.0000 -0.184716 -5.0264 + 13 0.0000 0.031717 0.8631 + 14 0.0000 0.102422 2.7870 + 15 0.0000 0.139376 3.7926 + 16 0.0000 0.224970 6.1217 + 17 0.0000 0.272128 7.4050 + 18 0.0000 0.300338 8.1726 + 19 0.0000 0.330890 9.0040 + 20 0.0000 0.356476 9.7002 + 21 0.0000 0.377179 10.2636 + 22 0.0000 0.396715 10.7952 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.245155 + 1 O : 0.222615 + 2 O : -0.235604 + 3 H : 0.258144 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.850716 s : 3.850716 + pz : 1.356189 p : 3.341033 + px : 1.044974 + py : 0.939870 + dz2 : 0.013064 d : 0.053406 + dxz : 0.002064 + dyz : 0.005859 + dx2y2 : 0.016733 + dxy : 0.015686 + + 1 O s : 3.734832 s : 3.734832 + pz : 1.441903 p : 3.898711 + px : 1.318892 + py : 1.137916 + dz2 : 0.039248 d : 0.143842 + dxz : 0.019354 + dyz : 0.023556 + dx2y2 : 0.033817 + dxy : 0.027867 + + 2 O s : 3.940602 s : 3.940602 + pz : 1.359637 p : 4.275184 + px : 1.517938 + py : 1.397609 + dz2 : -0.000405 d : 0.019817 + dxz : 0.006582 + dyz : 0.008971 + dx2y2 : 0.002098 + dxy : 0.002571 + + 3 H s : 0.713457 s : 0.713457 + pz : 0.017579 p : 0.028400 + px : 0.005224 + py : 0.005596 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.039544 + 1 O : -0.183710 + 2 O : -0.053824 + 3 H : 0.277078 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.343897 s : 3.343897 + pz : 1.316295 p : 3.382259 + px : 1.019339 + py : 1.046625 + dz2 : 0.058448 d : 0.313388 + dxz : 0.017226 + dyz : 0.086423 + dx2y2 : 0.071065 + dxy : 0.080225 + + 1 O s : 3.358922 s : 3.358922 + pz : 1.468388 p : 4.044312 + px : 1.270995 + py : 1.304928 + dz2 : 0.164824 d : 0.780477 + dxz : 0.066030 + dyz : 0.210588 + dx2y2 : 0.165950 + dxy : 0.173085 + + 2 O s : 3.602173 s : 3.602173 + pz : 1.360568 p : 4.202561 + px : 1.440204 + py : 1.401788 + dz2 : 0.078025 d : 0.249090 + dxz : 0.036617 + dyz : 0.072009 + dx2y2 : 0.030070 + dxy : 0.032370 + + 3 H s : 0.649629 s : 0.649629 + pz : 0.048921 p : 0.073293 + px : 0.012748 + py : 0.011624 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2452 7.0000 -0.2452 2.7917 2.7917 -0.0000 + 1 O 7.7774 8.0000 0.2226 2.6447 2.6447 0.0000 + 2 O 8.2356 8.0000 -0.2356 1.6790 1.6790 -0.0000 + 3 H 0.7419 1.0000 0.2581 0.9304 0.9304 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4436 B( 0-N , 2-O ) : 0.4724 B( 0-N , 3-H ) : 0.8758 +B( 1-O , 2-O ) : 1.1766 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.438 sec +Sum of individual times .... 1.421 sec ( 98.8%) + +SCF preparation .... 0.596 sec ( 41.5%) +Fock matrix formation .... 0.176 sec ( 12.2%) + Startup .... 0.009 sec ( 5.2% of F) + Split-RI-J .... 0.032 sec ( 18.4% of F) + XC integration .... 0.106 sec ( 60.4% of F) + Basis function eval. .... 0.007 sec ( 6.7% of XC) + Density eval. .... 0.011 sec ( 10.2% of XC) + XC-Functional eval. .... 0.006 sec ( 5.4% of XC) + XC-Potential eval. .... 0.010 sec ( 9.6% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.011 sec ( 0.8%) +Total Energy calculation .... 0.014 sec ( 1.0%) +Population analysis .... 0.570 sec ( 39.7%) +Orbital Transformation .... 0.006 sec ( 0.4%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.010 sec ( 0.7%) +SOSCF solution .... 0.037 sec ( 2.6%) +Finished LeanSCF after 2.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 25.8 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000364145 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007213455 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.561608940617 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.018.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.018.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.159412 0.694758 -0.311863 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5684582506196136 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.195756491 0.629807372 -0.466727561 +Nuclear contribution : -0.293468587 -1.197996570 0.690738225 + ----------------------------------------- +Total Dipole Moment : -0.097712095 -0.568189198 0.224010664 + ----------------------------------------- +Magnitude (a.u.) : 0.618520328 +Magnitude (Debye) : 1.572153733 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.966749 0.436552 0.382483 +Rotational constants in MHz : 88940.884121 13087.489196 11466.559049 + +Dipole components along the rotational axes: +x,y,z [a.u.] : 0.439984 0.405601 0.156426 +x,y,z [Debye]: 1.118351 1.030955 0.397604 + + + +Dipole moment calculation done in 0.2 sec + +Maximum memory used throughout the entire PROP-calculation: 13.9 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 19 * + * * + * Dihedral ( 2, 1, 0, 3) : -13.84615385 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2715 0.780271 + 2. B(O 2,O 1) 1.3083 0.679992 + 3. B(H 3,N 0) 1.0419 0.387609 + 4. A(O 1,N 0,H 3) 105.6306 0.363759 + 5. A(N 0,O 1,O 2) 120.6315 0.447992 + 6. D(O 2,O 1,N 0,H 3) -13.8462 0.048799 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.359991 -0.674347 -0.433003 + O 0.154958 0.477380 -0.591163 + O 0.433258 1.230682 0.441651 + H -0.246932 -0.895872 0.578806 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.680285 -1.274331 -0.818257 + 1 O 8.0000 0 15.999 0.292829 0.902118 -1.117135 + 2 O 8.0000 0 15.999 0.818738 2.325653 0.834600 + 3 H 1.0000 0 1.008 -0.466635 -1.692953 1.093786 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.269510736319 0.00000000 0.00000000 + O 2 1 0 1.306955796506 120.87829928 0.00000000 + H 1 2 3 1.039961381528 105.87679922 336.92307686 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.399027615715 0.00000000 0.00000000 + O 2 1 0 2.469788524536 120.87829928 0.00000000 + H 1 2 3 1.965242200942 105.87679922 336.92307686 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1680 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.153337631611 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.881e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22310 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.1533376316 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.1 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.8 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5682954144540986 0.00e+00 3.68e-04 3.23e-03 2.73e-02 0.700 0.4 +Warning: op=0 Small HOMO/LUMO gap ( 0.086) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5694675735242072 -1.17e-03 4.39e-04 3.60e-03 2.11e-02 0.700 0.3 + ***Turning on AO-DIIS*** + 3 -205.5704349094575605 -9.67e-04 3.35e-04 2.66e-03 1.50e-02 0.700 0.2 + 4 -205.5711136563937771 -6.79e-04 8.39e-04 6.91e-03 1.06e-02 0.000 0.1 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5726997649115333 -1.59e-03 1.08e-04 1.89e-03 1.42e-03 0.3 + *** Restarting incremental Fock matrix formation *** + 6 -205.5726975642746766 2.20e-06 4.39e-04 5.90e-03 1.86e-03 0.3 + 7 -205.5722832364729129 4.14e-04 3.61e-04 5.76e-03 1.12e-02 0.1 + 8 -205.5727179901710997 -4.35e-04 5.18e-05 8.89e-04 4.61e-04 0.1 + 9 -205.5727131503611531 4.84e-06 3.56e-05 6.57e-04 1.21e-03 0.1 + 10 -205.5727189278136962 -5.78e-06 4.67e-06 4.12e-05 2.43e-05 0.2 + 11 -205.5727189337152367 -5.90e-09 1.62e-06 1.59e-05 1.70e-05 0.2 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57271893371524 Eh -5593.91807 eV + +Components: +Nuclear Repulsion : 70.15333763161078 Eh 1908.96937 eV +Electronic Energy : -275.72605656532602 Eh -7502.88744 eV +One Electron Energy: -419.94573089570031 Eh -11427.30429 eV +Two Electron Energy: 144.21967433037429 Eh 3924.41685 eV + +Virial components: +Potential Energy : -410.42362740887052 Eh -11168.19468 eV +Kinetic Energy : 204.85090847515528 Eh 5574.27661 eV +Virial Ratio : 2.00352358924807 + +DFT components: +N(Alpha) : 11.999999280858 electrons +N(Beta) : 11.999999280858 electrons +N(Total) : 23.999998561716 electrons +E(X) : -23.349671148928 Eh +E(C) : -0.804828092607 Eh +E(XC) : -24.154499241535 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 5.9015e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.5867e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.6238e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.4180e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.6955e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.7014e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.194151 -522.2994 + 1 2.0000 -19.019764 -517.5541 + 2 2.0000 -14.276576 -388.4854 + 3 2.0000 -1.257346 -34.2141 + 4 2.0000 -0.971275 -26.4297 + 5 2.0000 -0.721511 -19.6333 + 6 2.0000 -0.561518 -15.2797 + 7 2.0000 -0.524498 -14.2723 + 8 2.0000 -0.499433 -13.5903 + 9 2.0000 -0.333960 -9.0875 + 10 2.0000 -0.291419 -7.9299 + 11 2.0000 -0.268017 -7.2931 + 12 0.0000 -0.182322 -4.9612 + 13 0.0000 0.028387 0.7724 + 14 0.0000 0.103590 2.8188 + 15 0.0000 0.138263 3.7623 + 16 0.0000 0.222617 6.0577 + 17 0.0000 0.275169 7.4877 + 18 0.0000 0.297774 8.1029 + 19 0.0000 0.331117 9.0102 + 20 0.0000 0.358300 9.7498 + 21 0.0000 0.371920 10.1205 + 22 0.0000 0.395637 10.7658 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.241662 + 1 O : 0.227723 + 2 O : -0.242922 + 3 H : 0.256861 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.856866 s : 3.856866 + pz : 1.350019 p : 3.332389 + px : 1.053517 + py : 0.928853 + dz2 : 0.012791 d : 0.052407 + dxz : 0.000926 + dyz : 0.006268 + dx2y2 : 0.016344 + dxy : 0.016078 + + 1 O s : 3.736794 s : 3.736794 + pz : 1.433705 p : 3.890590 + px : 1.323427 + py : 1.133459 + dz2 : 0.040189 d : 0.144892 + dxz : 0.018734 + dyz : 0.024333 + dx2y2 : 0.031994 + dxy : 0.029642 + + 2 O s : 3.941584 s : 3.941584 + pz : 1.338487 p : 4.280667 + px : 1.487634 + py : 1.454546 + dz2 : -0.000549 d : 0.020670 + dxz : 0.007318 + dyz : 0.009195 + dx2y2 : 0.002193 + dxy : 0.002513 + + 3 H s : 0.715026 s : 0.715026 + pz : 0.017973 p : 0.028113 + px : 0.005018 + py : 0.005122 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.036765 + 1 O : -0.181797 + 2 O : -0.058950 + 3 H : 0.277512 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.347546 s : 3.347546 + pz : 1.312923 p : 3.376991 + px : 1.017399 + py : 1.046669 + dz2 : 0.060662 d : 0.312228 + dxz : 0.013720 + dyz : 0.087072 + dx2y2 : 0.073840 + dxy : 0.076936 + + 1 O s : 3.360782 s : 3.360782 + pz : 1.464463 p : 4.042315 + px : 1.268670 + py : 1.309182 + dz2 : 0.167229 d : 0.778700 + dxz : 0.066362 + dyz : 0.210539 + dx2y2 : 0.164701 + dxy : 0.169870 + + 2 O s : 3.602470 s : 3.602470 + pz : 1.343029 p : 4.206899 + px : 1.414902 + py : 1.448968 + dz2 : 0.080046 d : 0.249580 + dxz : 0.039234 + dyz : 0.069802 + dx2y2 : 0.029734 + dxy : 0.030763 + + 3 H s : 0.649818 s : 0.649818 + pz : 0.050078 p : 0.072669 + px : 0.012155 + py : 0.010437 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2417 7.0000 -0.2417 2.7883 2.7883 -0.0000 + 1 O 7.7723 8.0000 0.2277 2.6511 2.6511 -0.0000 + 2 O 8.2429 8.0000 -0.2429 1.6795 1.6795 0.0000 + 3 H 0.7431 1.0000 0.2569 0.9316 0.9316 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4474 B( 0-N , 2-O ) : 0.4674 B( 0-N , 3-H ) : 0.8735 +B( 1-O , 2-O ) : 1.1788 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 4 sec + +Total time .... 4.038 sec +Sum of individual times .... 3.862 sec ( 95.7%) + +SCF preparation .... 0.579 sec ( 14.4%) +Fock matrix formation .... 1.635 sec ( 40.5%) + Startup .... 0.238 sec ( 14.6% of F) + Split-RI-J .... 0.041 sec ( 2.5% of F) + XC integration .... 0.277 sec ( 17.0% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.012 sec ( 4.3% of XC) + Density eval. .... 0.016 sec ( 5.8% of XC) + XC-Functional eval. .... 0.010 sec ( 3.6% of XC) + XC-Potential eval. .... 0.018 sec ( 6.6% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.286 sec ( 7.1%) +Total Energy calculation .... 0.024 sec ( 0.6%) +Population analysis .... 0.743 sec ( 18.4%) +Orbital Transformation .... 0.213 sec ( 5.3%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.246 sec ( 6.1%) +SOSCF solution .... 0.137 sec ( 3.4%) +Finished LeanSCF after 4.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 26.1 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000364233 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007263117 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.565820049023 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001311 -0.000004883 0.000001951 + 2 O : 0.000000180 0.000000510 -0.000000892 + 3 O : 0.000002056 0.000005253 0.000002077 + 4 H : -0.000000926 -0.000000880 -0.000003136 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000088349 +RMS gradient ... 0.0000025504 +MAX gradient ... 0.0000052529 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.017553847 0.003775897 0.002593288 + 2 O : 0.016656950 -0.003222982 -0.002884029 + 3 O : -0.008299495 0.004499525 0.001263628 + 4 H : 0.009196392 -0.005052440 -0.000972887 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000605001 0.0000077537 0.0000039642 + +Norm of the Cartesian gradient ... 0.0287584890 +RMS gradient ... 0.0083018607 +MAX gradient ... 0.0175538472 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.296 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.005 sec ( 1.7%) +RI-J Coulomb gradient .... 0.057 sec ( 19.2%) +XC gradient .... 0.017 sec ( 5.9%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.565820049 Eh +Current gradient norm .... 0.028758489 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999967460 +Lowest eigenvalues of augmented Hessian: + -0.000042022 0.362862875 0.384821496 0.447009628 0.676676051 +Length of the computed step .... 0.008067431 +The final length of the internal step .... 0.008067431 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0032935149 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0024068357 RMS(Int)= 0.0032936136 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000016 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0022002600 0.0001000000 NO + MAX gradient 0.0047421110 0.0003000000 NO + RMS step 0.0032935149 0.0020000000 NO + MAX step 0.0061213307 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0032 Max(Angles) 0.14 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2715 0.004742 -0.0032 1.2682 + 2. B(O 2,O 1) 1.3083 0.001828 -0.0014 1.3069 + 3. B(H 3,N 0) 1.0419 0.001121 -0.0015 1.0404 + 4. A(O 1,N 0,H 3) 105.63 0.000883 -0.14 105.49 + 5. A(N 0,O 1,O 2) 120.63 -0.001086 0.14 120.77 + 6. D(O 2,O 1,N 0,H 3) -13.85 -0.019859 0.00 -13.85 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.200 %) +Internal coordinates : 0.000 s ( 0.059 %) +B/P matrices and projection : 0.000 s ( 0.223 %) +Hessian update/contruction : 0.027 s (68.523 %) +Making the step : 0.000 s ( 0.151 %) +Converting the step to Cartesian: 0.000 s ( 0.105 %) +Storing new data : 0.000 s ( 0.085 %) +Checking convergence : 0.000 s ( 0.000 %) +Final printing : 0.012 s (30.643 %) +Total time : 0.039 s + +Time for energy+gradient : 9.373 s +Time for complete geometry iter : 10.377 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.359561 -0.673442 -0.433044 + O 0.154272 0.475456 -0.589391 + O 0.432770 1.229200 0.441235 + H -0.246189 -0.893370 0.577492 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.679471 -1.272621 -0.818334 + 1 O 8.0000 0 15.999 0.291533 0.898482 -1.113788 + 2 O 8.0000 0 15.999 0.817816 2.322851 0.833814 + 3 H 1.0000 0 1.008 -0.465230 -1.688225 1.091301 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.268241456550 0.00000000 0.00000000 + O 2 1 0 1.306859138512 120.77075873 0.00000000 + H 1 2 3 1.040386107223 105.49123527 346.15384635 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.396629024565 0.00000000 0.00000000 + O 2 1 0 2.469605867400 120.77075873 0.00000000 + H 1 2 3 1.966044816187 105.49123527 346.15384635 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1681 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.271697643538 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.863e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22310 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.9 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5727366892141674 0.00e+00 8.29e-05 6.99e-04 1.51e-04 0.5 + *** Restarting incremental Fock matrix formation *** + 2 -205.5727465539391403 -9.86e-06 7.51e-05 8.17e-04 2.54e-04 0.5 + 3 -205.5727388254255459 7.73e-06 5.73e-05 9.27e-04 1.38e-03 0.3 + 4 -205.5727465232663178 -7.70e-06 6.93e-05 1.03e-03 3.88e-04 0.3 + 5 -205.5727405218392221 6.00e-06 4.54e-05 7.73e-04 1.30e-03 0.1 + 6 -205.5727475909872908 -7.07e-06 1.61e-05 1.72e-04 6.71e-05 0.3 + 7 -205.5727475582745285 3.27e-08 8.97e-06 9.44e-05 8.23e-05 0.3 + 8 -205.5727476588993738 -1.01e-07 1.67e-07 1.76e-06 8.65e-07 0.2 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57274765889937 Eh -5593.91885 eV + +Components: +Nuclear Repulsion : 70.27169764353803 Eh 1912.19011 eV +Electronic Energy : -275.84444530243741 Eh -7506.10896 eV +One Electron Energy: -420.17032628660257 Eh -11433.41584 eV +Two Electron Energy: 144.32588098416517 Eh 3927.30688 eV + +Virial components: +Potential Energy : -410.43765229876959 Eh -11168.57632 eV +Kinetic Energy : 204.86490463987022 Eh 5574.65747 eV +Virial Ratio : 2.00345516973868 + +DFT components: +N(Alpha) : 11.999999314003 electrons +N(Beta) : 11.999999314003 electrons +N(Total) : 23.999998628006 electrons +E(X) : -23.353408213648 Eh +E(C) : -0.805062030631 Eh +E(XC) : -24.158470244279 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.0062e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.7612e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.6673e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.5413e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 8.6473e-07 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.3372e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 3 sec +Finished LeanSCF after 4.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 26.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000364263 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007266087 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.565845835010 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001304 -0.000004863 0.000001953 + 2 O : 0.000000178 0.000000504 -0.000000882 + 3 O : 0.000002045 0.000005222 0.000002070 + 4 H : -0.000000920 -0.000000862 -0.000003141 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000087988 +RMS gradient ... 0.0000025400 +MAX gradient ... 0.0000052217 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.016605652 0.005911134 0.002504335 + 2 O : 0.015758405 -0.005612792 -0.000304484 + 3 O : -0.008549251 0.003964532 -0.000061379 + 4 H : 0.009396498 -0.004262873 -0.002138473 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000607751 0.0000090776 0.0000034131 + +Norm of the Cartesian gradient ... 0.0282264879 +RMS gradient ... 0.0081482852 +MAX gradient ... 0.0166056517 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.244 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.004 sec ( 1.8%) +RI-J Coulomb gradient .... 0.054 sec ( 22.0%) +XC gradient .... 0.019 sec ( 7.8%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.565845835 Eh +Current gradient norm .... 0.028226488 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999994650 +Lowest eigenvalues of augmented Hessian: + -0.000005139 0.368337604 0.410706033 0.439132978 0.551122460 +Length of the computed step .... 0.003271100 +The final length of the internal step .... 0.003271100 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0013354210 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0007120580 RMS(Int)= 0.0013354042 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000006 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000002569 +Previously predicted energy change .... -0.000021012 +Actually observed energy change .... -0.000025786 +Ratio of predicted to observed change .... 1.227174745 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000257860 0.0000050000 NO + RMS gradient 0.0006507214 0.0001000000 NO + MAX gradient 0.0014722281 0.0003000000 NO + RMS step 0.0013354210 0.0020000000 YES + MAX step 0.0028006367 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0015 Max(Angles) 0.06 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2682 0.001472 -0.0015 1.2668 + 2. B(O 2,O 1) 1.3069 0.000422 -0.0005 1.3064 + 3. B(H 3,N 0) 1.0404 -0.000158 0.0002 1.0406 + 4. A(O 1,N 0,H 3) 105.49 -0.000334 0.06 105.55 + 5. A(N 0,O 1,O 2) 120.77 -0.000243 0.05 120.82 + 6. D(O 2,O 1,N 0,H 3) -13.85 -0.019969 0.00 -13.85 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.037 %) +Internal coordinates : 0.000 s ( 0.013 %) +B/P matrices and projection : 0.000 s ( 0.056 %) +Hessian update/contruction : 0.133 s (89.416 %) +Making the step : 0.000 s ( 0.039 %) +Converting the step to Cartesian: 0.000 s ( 0.023 %) +Storing new data : 0.000 s ( 0.019 %) +Checking convergence : 0.000 s ( 0.007 %) +Final printing : 0.015 s (10.388 %) +Total time : 0.149 s + +Time for energy+gradient : 9.087 s +Time for complete geometry iter : 10.144 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.359152 -0.672573 -0.433034 + O 0.154042 0.475034 -0.588945 + O 0.432711 1.229078 0.440773 + H -0.246309 -0.893695 0.577498 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.678699 -1.270979 -0.818316 + 1 O 8.0000 0 15.999 0.291098 0.897684 -1.112945 + 2 O 8.0000 0 15.999 0.817704 2.322621 0.832940 + 3 H 1.0000 0 1.008 -0.465456 -1.688839 1.091314 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.266759423447 0.00000000 0.00000000 + O 2 1 0 1.306352487035 120.81882062 0.00000000 + H 1 2 3 1.040579019241 105.55141780 346.15384635 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.393828387879 0.00000000 0.00000000 + O 2 1 0 2.468648434864 120.81882062 0.00000000 + H 1 2 3 1.966409367070 105.55141780 346.15384635 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1681 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.315738301308 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.856e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22310 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 1.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5727456981711043 0.00e+00 3.78e-05 3.21e-04 7.95e-05 0.4 + *** Restarting incremental Fock matrix formation *** + 2 -205.5727477303205433 -2.03e-06 3.00e-05 3.34e-04 1.58e-04 0.4 + 3 -205.5727468567051233 8.74e-07 1.97e-05 3.29e-04 4.04e-04 0.1 + 4 -205.5727477165049777 -8.60e-07 3.59e-05 4.90e-04 2.34e-04 0.1 + 5 -205.5727454525973599 2.26e-06 2.65e-05 4.05e-04 7.07e-04 0.2 + 6 -205.5727479565119893 -2.50e-06 5.46e-06 5.62e-05 2.20e-05 0.2 + 7 -205.5727479548363021 1.68e-09 2.87e-06 2.98e-05 2.45e-05 0.2 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57274795483630 Eh -5593.91886 eV + +Components: +Nuclear Repulsion : 70.31573830130758 Eh 1913.38851 eV +Electronic Energy : -275.88848625614389 Eh -7507.30738 eV +One Electron Energy: -420.25354470222771 Eh -11435.68033 eV +Two Electron Energy: 144.36505844608379 Eh 3928.37295 eV + +Virial components: +Potential Energy : -410.44215980375145 Eh -11168.69897 eV +Kinetic Energy : 204.86941184891515 Eh 5574.78011 eV +Virial Ratio : 2.00343309476790 + +DFT components: +N(Alpha) : 11.999999366608 electrons +N(Beta) : 11.999999366608 electrons +N(Total) : 23.999998733216 electrons +E(X) : -23.354510349375 Eh +E(C) : -0.805143407704 Eh +E(XC) : -24.159653757079 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.6757e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.9801e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.8696e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.0767e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.4521e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.8601e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 2 sec +Finished LeanSCF after 3.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 26.5 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000364276 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007263522 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.565848708563 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001302 -0.000004861 0.000001956 + 2 O : 0.000000178 0.000000504 -0.000000880 + 3 O : 0.000002043 0.000005216 0.000002065 + 4 H : -0.000000918 -0.000000859 -0.000003141 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000087916 +RMS gradient ... 0.0000025379 +MAX gradient ... 0.0000052158 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.016108248 0.007187489 0.002203093 + 2 O : 0.015374336 -0.006544913 0.000419553 + 3 O : -0.008675081 0.003680907 -0.000577415 + 4 H : 0.009408994 -0.004323483 -0.002045231 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000606957 0.0000064900 0.0000035828 + +Norm of the Cartesian gradient ... 0.0282119750 +RMS gradient ... 0.0081440957 +MAX gradient ... 0.0161082484 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.307 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.005 sec ( 1.6%) +RI-J Coulomb gradient .... 0.055 sec ( 17.8%) +XC gradient .... 0.016 sec ( 5.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.565848709 Eh +Current gradient norm .... 0.028211975 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999510 +Lowest eigenvalues of augmented Hessian: + -0.000000336 0.305412605 0.395996306 0.444945859 0.594054114 +Length of the computed step .... 0.000990340 +The final length of the internal step .... 0.000990340 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0004043048 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0003960251 RMS(Int)= 0.0004043259 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000168 +Previously predicted energy change .... -0.000002569 +Actually observed energy change .... -0.000002874 +Ratio of predicted to observed change .... 1.118346166 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000028736 0.0000050000 YES + RMS gradient 0.0001455525 0.0001000000 NO + MAX gradient 0.0002646511 0.0003000000 YES + RMS step 0.0004043048 0.0020000000 YES + MAX step 0.0008236760 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0002 Max(Angles) 0.05 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2668 0.000138 -0.0002 1.2665 + 2. B(O 2,O 1) 1.3064 -0.000176 0.0001 1.3065 + 3. B(H 3,N 0) 1.0406 -0.000053 0.0001 1.0406 + 4. A(O 1,N 0,H 3) 105.55 -0.000265 0.05 105.60 + 5. A(N 0,O 1,O 2) 120.82 -0.000065 0.01 120.83 + 6. D(O 2,O 1,N 0,H 3) -13.85 -0.020004 -0.00 -13.85 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.084 %) +Internal coordinates : 0.000 s ( 0.028 %) +B/P matrices and projection : 0.000 s ( 0.141 %) +Hessian update/contruction : 0.009 s ( 9.908 %) +Making the step : 0.000 s ( 0.051 %) +Converting the step to Cartesian: 0.000 s ( 0.039 %) +Storing new data : 0.000 s ( 0.031 %) +Checking convergence : 0.000 s ( 0.012 %) +Final printing : 0.080 s (89.704 %) +Total time : 0.089 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.359033 -0.672387 -0.432952 + O 0.154003 0.475030 -0.588918 + O 0.432824 1.229425 0.440638 + H -0.246502 -0.894224 0.577524 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.678474 -1.270627 -0.818160 + 1 O 8.0000 0 15.999 0.291024 0.897677 -1.112893 + 2 O 8.0000 0 15.999 0.817919 2.323276 0.832685 + 3 H 1.0000 0 1.008 -0.465821 -1.689839 1.091362 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.266529987983 0.00000000 0.00000000 + O 2 1 0 1.306459374374 120.83278319 0.00000000 + H 1 2 3 1.040641997156 105.59861096 346.15384635 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.393394817686 0.00000000 0.00000000 + O 2 1 0 2.468850422662 120.83278319 0.00000000 + H 1 2 3 1.966528378081 105.59861096 346.15384635 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1681 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.316025198453 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.856e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22310 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.3160251985 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.1 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.7 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5727454734660284 0.00e+00 9.40e-06 7.79e-05 2.48e-05 0.5 + *** Restarting incremental Fock matrix formation *** + 2 -205.5727456167027469 -1.43e-07 7.38e-06 8.82e-05 2.59e-05 0.2 + 3 -205.5727455409110291 7.58e-08 5.56e-06 8.89e-05 1.53e-04 0.1 + 4 -205.5727456247081193 -8.38e-08 3.86e-06 5.87e-05 2.65e-05 0.1 + 5 -205.5727456072462758 1.75e-08 2.31e-06 4.19e-05 7.42e-05 0.1 + 6 -205.5727456288636006 -2.16e-08 7.47e-07 8.12e-06 2.46e-06 0.1 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 6 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57274562886360 Eh -5593.91880 eV + +Components: +Nuclear Repulsion : 70.31602519845271 Eh 1913.39632 eV +Electronic Energy : -275.88877082731631 Eh -7507.31512 eV +One Electron Energy: -420.25533064323344 Eh -11435.72893 eV +Two Electron Energy: 144.36655981591713 Eh 3928.41381 eV + +Virial components: +Potential Energy : -410.44217141139552 Eh -11168.69929 eV +Kinetic Energy : 204.86942578253192 Eh 5574.78049 eV +Virial Ratio : 2.00343301516878 + +DFT components: +N(Alpha) : 11.999999387003 electrons +N(Beta) : 11.999999387003 electrons +N(Total) : 23.999998774007 electrons +E(X) : -23.354692739437 Eh +E(C) : -0.805146289205 Eh +E(XC) : -24.159839028642 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.1617e-08 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.1248e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 7.4689e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.2264e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.4621e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 5.1905e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.194356 -522.3050 + 1 2.0000 -19.019268 -517.5406 + 2 2.0000 -14.276278 -388.4773 + 3 2.0000 -1.260059 -34.2879 + 4 2.0000 -0.973352 -26.4863 + 5 2.0000 -0.721134 -19.6230 + 6 2.0000 -0.562167 -15.2973 + 7 2.0000 -0.526095 -14.3158 + 8 2.0000 -0.500314 -13.6142 + 9 2.0000 -0.333428 -9.0730 + 10 2.0000 -0.291526 -7.9328 + 11 2.0000 -0.267828 -7.2880 + 12 0.0000 -0.181220 -4.9312 + 13 0.0000 0.029840 0.8120 + 14 0.0000 0.104994 2.8570 + 15 0.0000 0.140038 3.8106 + 16 0.0000 0.224185 6.1004 + 17 0.0000 0.275165 7.4876 + 18 0.0000 0.297284 8.0895 + 19 0.0000 0.331649 9.0246 + 20 0.0000 0.358206 9.7473 + 21 0.0000 0.372002 10.1227 + 22 0.0000 0.396206 10.7813 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.240482 + 1 O : 0.229075 + 2 O : -0.244608 + 3 H : 0.256015 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.854822 s : 3.854822 + pz : 1.350540 p : 3.332921 + px : 1.053081 + py : 0.929299 + dz2 : 0.012732 d : 0.052738 + dxz : 0.000931 + dyz : 0.006346 + dx2y2 : 0.016499 + dxy : 0.016231 + + 1 O s : 3.733953 s : 3.733953 + pz : 1.435282 p : 3.891270 + px : 1.322230 + py : 1.133759 + dz2 : 0.040407 d : 0.145701 + dxz : 0.018804 + dyz : 0.024315 + dx2y2 : 0.032265 + dxy : 0.029911 + + 2 O s : 3.940984 s : 3.940984 + pz : 1.341304 p : 4.282816 + px : 1.488329 + py : 1.453184 + dz2 : -0.000548 d : 0.020808 + dxz : 0.007314 + dyz : 0.009268 + dx2y2 : 0.002225 + dxy : 0.002550 + + 3 H s : 0.715779 s : 0.715779 + pz : 0.018017 p : 0.028207 + px : 0.005029 + py : 0.005161 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.035528 + 1 O : -0.183332 + 2 O : -0.058262 + 3 H : 0.277122 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.344077 s : 3.344077 + pz : 1.312146 p : 3.377564 + px : 1.016831 + py : 1.048587 + dz2 : 0.060792 d : 0.313887 + dxz : 0.013802 + dyz : 0.087814 + dx2y2 : 0.074200 + dxy : 0.077279 + + 1 O s : 3.357342 s : 3.357342 + pz : 1.465605 p : 4.043434 + px : 1.267603 + py : 1.310225 + dz2 : 0.167561 d : 0.782555 + dxz : 0.066697 + dyz : 0.211862 + dx2y2 : 0.165651 + dxy : 0.170785 + + 2 O s : 3.601037 s : 3.601037 + pz : 1.344653 p : 4.207606 + px : 1.415138 + py : 1.447815 + dz2 : 0.079908 d : 0.249619 + dxz : 0.039121 + dyz : 0.069840 + dx2y2 : 0.029864 + dxy : 0.030887 + + 3 H s : 0.650028 s : 0.650028 + pz : 0.050162 p : 0.072849 + px : 0.012190 + py : 0.010498 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2405 7.0000 -0.2405 2.7896 2.7896 0.0000 + 1 O 7.7709 8.0000 0.2291 2.6529 2.6529 -0.0000 + 2 O 8.2446 8.0000 -0.2446 1.6782 1.6782 -0.0000 + 3 H 0.7440 1.0000 0.2560 0.9323 0.9323 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4497 B( 0-N , 2-O ) : 0.4659 B( 0-N , 3-H ) : 0.8740 +B( 1-O , 2-O ) : 1.1786 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.938 sec +Sum of individual times .... 2.767 sec ( 94.2%) + +SCF preparation .... 0.602 sec ( 20.5%) +Fock matrix formation .... 0.774 sec ( 26.3%) + Startup .... 0.190 sec ( 24.5% of F) + Split-RI-J .... 0.027 sec ( 3.5% of F) + XC integration .... 0.190 sec ( 24.6% of F) + Basis function eval. .... 0.009 sec ( 4.5% of XC) + Density eval. .... 0.011 sec ( 6.0% of XC) + XC-Functional eval. .... 0.007 sec ( 3.9% of XC) + XC-Potential eval. .... 0.013 sec ( 6.8% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.030 sec ( 1.0%) +Total Energy calculation .... 0.013 sec ( 0.5%) +Population analysis .... 0.926 sec ( 31.5%) +Orbital Transformation .... 0.072 sec ( 2.5%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.090 sec ( 3.1%) +SOSCF solution .... 0.259 sec ( 8.8%) +Finished LeanSCF after 3.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 26.8 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000364273 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007260963 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.565848939277 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.019.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.019.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.165253 0.681322 -0.315720 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5727456288636006 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.181227800 0.610598416 -0.485309533 +Nuclear contribution : -0.309670392 -1.168334798 0.699846540 + ----------------------------------------- +Total Dipole Moment : -0.128442592 -0.557736382 0.214537007 + ----------------------------------------- +Magnitude (a.u.) : 0.611222954 +Magnitude (Debye) : 1.553605281 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.965517 0.439397 0.383413 +Rotational constants in MHz : 88903.972704 13172.801713 11494.424149 + +Dipole components along the rotational axes: +x,y,z [a.u.] : -0.441920 0.411667 -0.093969 +x,y,z [Debye]: -1.123271 1.046375 -0.238849 + + + +Dipole moment calculation done in 0.2 sec + +Maximum memory used throughout the entire PROP-calculation: 14.4 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 20 * + * * + * Dihedral ( 2, 1, 0, 3) : -4.61538462 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2686 0.788862 + 2. B(O 2,O 1) 1.3077 0.681234 + 3. B(H 3,N 0) 1.0425 0.386641 + 4. A(O 1,N 0,H 3) 105.3452 0.364285 + 5. A(N 0,O 1,O 2) 120.5791 0.449031 + 6. D(O 2,O 1,N 0,H 3) -4.6154 0.050018 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.325552 -0.688817 -0.439844 + O 0.121167 0.488752 -0.592135 + O 0.449357 1.215048 0.444640 + H -0.263681 -0.877139 0.583631 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.615204 -1.301675 -0.831185 + 1 O 8.0000 0 15.999 0.228973 0.923607 -1.118973 + 2 O 8.0000 0 15.999 0.849162 2.296107 0.840247 + 3 H 1.0000 0 1.008 -0.498284 -1.657552 1.102903 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.266529987983 0.00000000 0.00000000 + O 2 1 0 1.306459374374 120.83278319 0.00000000 + H 1 2 3 1.040641997156 105.59861096 346.15384635 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.393394817686 0.00000000 0.00000000 + O 2 1 0 2.468850422662 120.83278319 0.00000000 + H 1 2 3 1.966528378081 105.59861096 346.15384635 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1681 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.261843551274 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.855e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.003 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.5 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.2618435513 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.5 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 1.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5704204737507439 0.00e+00 3.64e-04 3.01e-03 2.84e-02 0.700 0.6 +Warning: op=0 Small HOMO/LUMO gap ( 0.088) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5716149236517367 -1.19e-03 4.38e-04 3.34e-03 2.20e-02 0.700 0.4 + ***Turning on AO-DIIS*** + 3 -205.5726011059810503 -9.86e-04 3.34e-04 2.66e-03 1.56e-02 0.700 0.2 + 4 -205.5732948540918414 -6.94e-04 8.39e-04 6.89e-03 1.10e-02 0.000 0.1 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5749142612407354 -1.62e-03 8.80e-05 1.40e-03 9.53e-04 0.2 + *** Restarting incremental Fock matrix formation *** + 6 -205.5749160832577331 -1.82e-06 3.34e-04 4.38e-03 1.36e-03 0.3 + 7 -205.5747037730799889 2.12e-04 2.63e-04 4.32e-03 8.21e-03 0.2 + 8 -205.5749298321129572 -2.26e-04 5.90e-05 9.64e-04 4.91e-04 0.2 + 9 -205.5749243386151761 5.49e-06 3.83e-05 7.09e-04 1.33e-03 0.2 + 10 -205.5749309369767843 -6.60e-06 6.61e-06 5.30e-05 2.99e-05 0.2 + 11 -205.5749309459847041 -9.01e-09 2.28e-06 2.18e-05 2.20e-05 0.2 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57493094598470 Eh -5593.97826 eV + +Components: +Nuclear Repulsion : 70.26184355127437 Eh 1911.92196 eV +Electronic Energy : -275.83677449725906 Eh -7505.90023 eV +One Electron Energy: -420.15406729494987 Eh -11432.97341 eV +Two Electron Energy: 144.31729279769081 Eh 3927.07319 eV + +Virial components: +Potential Energy : -410.43229116640845 Eh -11168.43043 eV +Kinetic Energy : 204.85736022042374 Eh 5574.45217 eV +Virial Ratio : 2.00350278225195 + +DFT components: +N(Alpha) : 11.999998638438 electrons +N(Beta) : 11.999998638438 electrons +N(Total) : 23.999997276876 electrons +E(X) : -23.352155981583 Eh +E(C) : -0.805009916044 Eh +E(XC) : -24.157165897627 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 9.0079e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.1814e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.2754e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.5344e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.2023e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 4.4487e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.194777 -522.3164 + 1 2.0000 -19.018879 -517.5300 + 2 2.0000 -14.277177 -388.5017 + 3 2.0000 -1.259123 -34.2625 + 4 2.0000 -0.972090 -26.4519 + 5 2.0000 -0.721729 -19.6392 + 6 2.0000 -0.560960 -15.2645 + 7 2.0000 -0.525783 -14.3073 + 8 2.0000 -0.499985 -13.6053 + 9 2.0000 -0.334185 -9.0936 + 10 2.0000 -0.292611 -7.9624 + 11 2.0000 -0.267908 -7.2901 + 12 0.0000 -0.180263 -4.9052 + 13 0.0000 0.027562 0.7500 + 14 0.0000 0.105405 2.8682 + 15 0.0000 0.139108 3.7853 + 16 0.0000 0.222471 6.0537 + 17 0.0000 0.277050 7.5389 + 18 0.0000 0.295708 8.0466 + 19 0.0000 0.331508 9.0208 + 20 0.0000 0.361544 9.8381 + 21 0.0000 0.366806 9.9813 + 22 0.0000 0.395379 10.7588 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.239067 + 1 O : 0.231754 + 2 O : -0.248514 + 3 H : 0.255828 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.858989 s : 3.858989 + pz : 1.347770 p : 3.327898 + px : 1.060848 + py : 0.919281 + dz2 : 0.012711 d : 0.052181 + dxz : 0.000009 + dyz : 0.006887 + dx2y2 : 0.015968 + dxy : 0.016605 + + 1 O s : 3.735911 s : 3.735911 + pz : 1.429858 p : 3.886342 + px : 1.326513 + py : 1.129971 + dz2 : 0.040725 d : 0.145993 + dxz : 0.018145 + dyz : 0.025122 + dx2y2 : 0.030129 + dxy : 0.031873 + + 2 O s : 3.941781 s : 3.941781 + pz : 1.328398 p : 4.285492 + px : 1.453935 + py : 1.503159 + dz2 : -0.000434 d : 0.021241 + dxz : 0.007635 + dyz : 0.009227 + dx2y2 : 0.002411 + dxy : 0.002401 + + 3 H s : 0.716166 s : 0.716166 + pz : 0.018272 p : 0.028007 + px : 0.004920 + py : 0.004815 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.034505 + 1 O : -0.181832 + 2 O : -0.061434 + 3 H : 0.277770 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.347120 s : 3.347120 + pz : 1.310961 p : 3.374423 + px : 1.014907 + py : 1.048555 + dz2 : 0.062328 d : 0.312962 + dxz : 0.010814 + dyz : 0.088723 + dx2y2 : 0.077244 + dxy : 0.073853 + + 1 O s : 3.359192 s : 3.359192 + pz : 1.462324 p : 4.042119 + px : 1.265700 + py : 1.314094 + dz2 : 0.167737 d : 0.780521 + dxz : 0.067457 + dyz : 0.211628 + dx2y2 : 0.165604 + dxy : 0.168095 + + 2 O s : 3.601548 s : 3.601548 + pz : 1.333786 p : 4.209897 + px : 1.386998 + py : 1.489113 + dz2 : 0.080524 d : 0.249990 + dxz : 0.041801 + dyz : 0.067599 + dx2y2 : 0.030152 + dxy : 0.029914 + + 3 H s : 0.649848 s : 0.649848 + pz : 0.050923 p : 0.072381 + px : 0.011819 + py : 0.009640 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2391 7.0000 -0.2391 2.7866 2.7866 -0.0000 + 1 O 7.7682 8.0000 0.2318 2.6556 2.6556 -0.0000 + 2 O 8.2485 8.0000 -0.2485 1.6783 1.6783 0.0000 + 3 H 0.7442 1.0000 0.2558 0.9327 0.9327 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4513 B( 0-N , 2-O ) : 0.4632 B( 0-N , 3-H ) : 0.8721 +B( 1-O , 2-O ) : 1.1794 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 4 sec + +Total time .... 4.647 sec +Sum of individual times .... 4.497 sec ( 96.8%) + +SCF preparation .... 0.646 sec ( 13.9%) +Fock matrix formation .... 1.865 sec ( 40.1%) + Startup .... 0.254 sec ( 13.6% of F) + Split-RI-J .... 0.044 sec ( 2.4% of F) + XC integration .... 0.342 sec ( 18.3% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.012 sec ( 3.6% of XC) + Density eval. .... 0.015 sec ( 4.4% of XC) + XC-Functional eval. .... 0.010 sec ( 3.0% of XC) + XC-Potential eval. .... 0.016 sec ( 4.6% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.360 sec ( 7.8%) +Total Energy calculation .... 0.023 sec ( 0.5%) +Population analysis .... 0.842 sec ( 18.1%) +Orbital Transformation .... 0.307 sec ( 6.6%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.332 sec ( 7.2%) +SOSCF solution .... 0.122 sec ( 2.6%) +Finished LeanSCF after 5.5 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 27.2 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000364326 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007299559 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.567995712875 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001432 -0.000004758 0.000001975 + 2 O : 0.000000130 0.000000522 -0.000000889 + 3 O : 0.000002031 0.000005136 0.000002096 + 4 H : -0.000000730 -0.000000900 -0.000003181 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000087196 +RMS gradient ... 0.0000025171 +MAX gradient ... 0.0000051365 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.006723846 -0.000629087 0.000488071 + 2 O : 0.006159423 0.000697847 -0.002697440 + 3 O : -0.002743483 0.001488858 0.001522738 + 4 H : 0.003307905 -0.001557618 0.000686631 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000435644 0.0000066173 -0.0000715751 + +Norm of the Cartesian gradient ... 0.0108373306 +RMS gradient ... 0.0031284679 +MAX gradient ... 0.0067238456 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.267 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.005 sec ( 1.9%) +RI-J Coulomb gradient .... 0.056 sec ( 21.0%) +XC gradient .... 0.019 sec ( 7.2%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.567995713 Eh +Current gradient norm .... 0.010837331 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999979938 +Lowest eigenvalues of augmented Hessian: + -0.000024521 0.363381760 0.384022020 0.448032400 0.678104580 +Length of the computed step .... 0.006334508 +The final length of the internal step .... 0.006334508 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0025860522 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0015422122 RMS(Int)= 0.0025857035 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000009 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0016454872 0.0001000000 NO + MAX gradient 0.0033728126 0.0003000000 NO + RMS step 0.0025860522 0.0020000000 NO + MAX step 0.0043084998 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0023 Max(Angles) 0.17 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2686 0.003373 -0.0023 1.2663 + 2. B(O 2,O 1) 1.3077 0.001349 -0.0011 1.3067 + 3. B(H 3,N 0) 1.0425 0.001148 -0.0016 1.0409 + 4. A(O 1,N 0,H 3) 105.35 0.000125 -0.02 105.33 + 5. A(N 0,O 1,O 2) 120.58 -0.001310 0.17 120.75 + 6. D(O 2,O 1,N 0,H 3) -4.62 -0.006747 0.00 -4.62 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 1.583 %) +Internal coordinates : 0.000 s ( 0.486 %) +B/P matrices and projection : 0.000 s ( 1.979 %) +Hessian update/contruction : 0.003 s (51.691 %) +Making the step : 0.000 s ( 0.972 %) +Converting the step to Cartesian: 0.000 s ( 0.684 %) +Storing new data : 0.000 s ( 0.594 %) +Checking convergence : 0.000 s ( 0.018 %) +Final printing : 0.002 s (41.976 %) +Total time : 0.006 s + +Time for energy+gradient : 11.191 s +Time for complete geometry iter : 12.198 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.325205 -0.688125 -0.439504 + O 0.120783 0.487442 -0.590427 + O 0.449360 1.215180 0.443883 + H -0.263646 -0.876654 0.582340 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.614549 -1.300367 -0.830542 + 1 O 8.0000 0 15.999 0.228247 0.921131 -1.115745 + 2 O 8.0000 0 15.999 0.849168 2.296358 0.838817 + 3 H 1.0000 0 1.008 -0.498220 -1.656635 1.100463 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.266348749192 0.00000000 0.00000000 + O 2 1 0 1.306660906498 120.74658493 0.00000000 + H 1 2 3 1.040911933427 105.32555421 355.38461526 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.393052326006 0.00000000 0.00000000 + O 2 1 0 2.469231263183 120.74658493 0.00000000 + H 1 2 3 1.967038483708 105.32555421 355.38461526 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1681 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.340739771678 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.841e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.9 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5749324103204572 0.00e+00 7.24e-05 6.09e-04 1.75e-04 0.8 + *** Restarting incremental Fock matrix formation *** + 2 -205.5749396131861317 -7.20e-06 6.13e-05 6.73e-04 2.14e-04 0.6 + 3 -205.5749344295610399 5.18e-06 4.65e-05 7.48e-04 1.28e-03 0.2 + 4 -205.5749399347463964 -5.51e-06 4.15e-05 5.18e-04 2.06e-04 0.3 + 5 -205.5749387498699434 1.18e-06 2.27e-05 3.80e-04 5.95e-04 0.3 + 6 -205.5749402629541009 -1.51e-06 1.57e-05 1.80e-04 6.47e-05 0.2 + 7 -205.5749402177225420 4.52e-08 9.36e-06 1.07e-04 8.43e-05 0.4 + 8 -205.5749403201530185 -1.02e-07 2.02e-07 2.09e-06 1.12e-06 0.2 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57494032015302 Eh -5593.97852 eV + +Components: +Nuclear Repulsion : 70.34073977167817 Eh 1914.06884 eV +Electronic Energy : -275.91568009183118 Eh -7508.04736 eV +One Electron Energy: -420.30298465632745 Eh -11437.02566 eV +Two Electron Energy: 144.38730456449630 Eh 3928.97830 eV + +Virial components: +Potential Energy : -410.44256646391636 Eh -11168.71004 eV +Kinetic Energy : 204.86762614376332 Eh 5574.73152 eV +Virial Ratio : 2.00345254245243 + +DFT components: +N(Alpha) : 11.999998663279 electrons +N(Beta) : 11.999998663279 electrons +N(Total) : 23.999997326557 electrons +E(X) : -23.354904041892 Eh +E(C) : -0.805171117242 Eh +E(XC) : -24.160075159135 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.0243e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.0900e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.0233e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.1697e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.1176e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.0165e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 3 sec +Finished LeanSCF after 5.1 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 27.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000364331 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007293750 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.568010901771 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001430 -0.000004754 0.000001975 + 2 O : 0.000000129 0.000000518 -0.000000882 + 3 O : 0.000002028 0.000005129 0.000002089 + 4 H : -0.000000727 -0.000000894 -0.000003182 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000087092 +RMS gradient ... 0.0000025141 +MAX gradient ... 0.0000051295 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.006081159 0.000910231 0.000709154 + 2 O : 0.005607331 -0.001129677 -0.000702477 + 3 O : -0.002881668 0.001301184 0.000486631 + 4 H : 0.003355497 -0.001081737 -0.000493308 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000400139 0.0000068582 -0.0000700097 + +Norm of the Cartesian gradient ... 0.0097175349 +RMS gradient ... 0.0028052107 +MAX gradient ... 0.0060811591 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.491 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.005 sec ( 1.0%) +RI-J Coulomb gradient .... 0.058 sec ( 11.9%) +XC gradient .... 0.020 sec ( 4.0%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.568010902 Eh +Current gradient norm .... 0.009717535 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999995570 +Lowest eigenvalues of augmented Hessian: + -0.000003745 0.337882253 0.407969481 0.462137803 0.568172937 +Length of the computed step .... 0.002976607 +The final length of the internal step .... 0.002976607 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0012151947 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0007648299 RMS(Int)= 0.0012151506 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000004 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000001873 +Previously predicted energy change .... -0.000012261 +Actually observed energy change .... -0.000015189 +Ratio of predicted to observed change .... 1.238783184 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000151889 0.0000050000 NO + RMS gradient 0.0005305878 0.0001000000 NO + MAX gradient 0.0011441159 0.0003000000 NO + RMS step 0.0012151947 0.0020000000 YES + MAX step 0.0022558344 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0012 Max(Angles) 0.09 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2663 0.001144 -0.0012 1.2652 + 2. B(O 2,O 1) 1.3067 0.000388 -0.0005 1.3062 + 3. B(H 3,N 0) 1.0409 -0.000093 0.0000 1.0410 + 4. A(O 1,N 0,H 3) 105.33 -0.000429 0.09 105.41 + 5. A(N 0,O 1,O 2) 120.75 -0.000191 0.05 120.79 + 6. D(O 2,O 1,N 0,H 3) -4.62 -0.006765 0.00 -4.62 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.034 %) +Internal coordinates : 0.000 s ( 0.015 %) +B/P matrices and projection : 0.000 s ( 0.049 %) +Hessian update/contruction : 0.169 s (91.689 %) +Making the step : 0.000 s ( 0.028 %) +Converting the step to Cartesian: 0.000 s ( 0.020 %) +Storing new data : 0.000 s ( 0.016 %) +Checking convergence : 0.000 s ( 0.005 %) +Final printing : 0.015 s ( 8.144 %) +Total time : 0.184 s + +Time for energy+gradient : 10.291 s +Time for complete geometry iter : 11.458 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.324858 -0.687306 -0.439336 + O 0.120683 0.487174 -0.590020 + O 0.449377 1.215344 0.443342 + H -0.263910 -0.877368 0.582306 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.613893 -1.298821 -0.830224 + 1 O 8.0000 0 15.999 0.228058 0.920625 -1.114976 + 2 O 8.0000 0 15.999 0.849199 2.296668 0.837795 + 3 H 1.0000 0 1.008 -0.498717 -1.657985 1.100398 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.265155013031 0.00000000 0.00000000 + O 2 1 0 1.306180563502 120.79174953 0.00000000 + H 1 2 3 1.040955972689 105.41280861 355.38461526 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.390796491585 0.00000000 0.00000000 + O 2 1 0 2.468323546470 120.79174953 0.00000000 + H 1 2 3 1.967121705851 105.41280861 355.38461526 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1681 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.376911863015 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.834e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22305 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.5 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 1.1 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5749363803356573 0.00e+00 3.43e-05 2.70e-04 7.83e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5749379494438358 -1.57e-06 2.53e-05 2.51e-04 1.21e-04 0.0 + 3 -205.5749373146545622 6.35e-07 1.76e-05 3.00e-04 3.22e-04 0.0 + 4 -205.5749379144369868 -6.00e-07 2.95e-05 4.26e-04 1.99e-04 0.0 + 5 -205.5749365456502460 1.37e-06 2.07e-05 3.41e-04 6.03e-04 0.0 + 6 -205.5749381027238769 -1.56e-06 5.02e-06 5.30e-05 1.97e-05 0.0 + 7 -205.5749381011659693 1.56e-09 2.65e-06 2.74e-05 2.25e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57493810116597 Eh -5593.97846 eV + +Components: +Nuclear Repulsion : 70.37691186301451 Eh 1915.05313 eV +Electronic Energy : -275.95184996418050 Eh -7509.03159 eV +One Electron Energy: -420.37122606275955 Eh -11438.88260 eV +Two Electron Energy: 144.41937609857905 Eh 3929.85101 eV + +Virial components: +Potential Energy : -410.44639693046202 Eh -11168.81427 eV +Kinetic Energy : 204.87145882929607 Eh 5574.83581 eV +Virial Ratio : 2.00343375927467 + +DFT components: +N(Alpha) : 11.999998687652 electrons +N(Beta) : 11.999998687652 electrons +N(Total) : 23.999997375304 electrons +E(X) : -23.355846878091 Eh +E(C) : -0.805237854738 Eh +E(XC) : -24.161084732830 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.5579e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.7410e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.6459e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.9792e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.2460e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.7068e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.7 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 27.5 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000364338 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007289464 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.568012975717 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001430 -0.000004754 0.000001977 + 2 O : 0.000000129 0.000000518 -0.000000881 + 3 O : 0.000002027 0.000005128 0.000002084 + 4 H : -0.000000726 -0.000000893 -0.000003181 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000087065 +RMS gradient ... 0.0000025133 +MAX gradient ... 0.0000051278 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.005670648 0.002011132 0.000610409 + 2 O : 0.005359969 -0.001869763 -0.000141043 + 3 O : -0.003004580 0.001055795 0.000022402 + 4 H : 0.003315259 -0.001197164 -0.000491769 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000380966 0.0000051713 -0.0000699195 + +Norm of the Cartesian gradient ... 0.0095722183 +RMS gradient ... 0.0027632614 +MAX gradient ... 0.0056706482 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.127 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 4.0%) +RI-J Coulomb gradient .... 0.060 sec ( 47.2%) +XC gradient .... 0.021 sec ( 16.2%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.568012976 Eh +Current gradient norm .... 0.009572218 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999725 +Lowest eigenvalues of augmented Hessian: + -0.000000186 0.282231069 0.399029666 0.465386678 0.617349048 +Length of the computed step .... 0.000742035 +The final length of the internal step .... 0.000742035 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0003029346 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0003004795 RMS(Int)= 0.0003029511 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000093 +Previously predicted energy change .... -0.000001873 +Actually observed energy change .... -0.000002074 +Ratio of predicted to observed change .... 1.107488257 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000020739 0.0000050000 YES + RMS gradient 0.0001094888 0.0001000000 NO + MAX gradient 0.0001921224 0.0003000000 YES + RMS step 0.0003029346 0.0020000000 YES + MAX step 0.0006307344 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.04 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2652 0.000087 -0.0001 1.2650 + 2. B(O 2,O 1) 1.3062 -0.000147 0.0001 1.3063 + 3. B(H 3,N 0) 1.0410 -0.000073 0.0001 1.0410 + 4. A(O 1,N 0,H 3) 105.41 -0.000192 0.04 105.45 + 5. A(N 0,O 1,O 2) 120.79 -0.000024 0.01 120.80 + 6. D(O 2,O 1,N 0,H 3) -4.62 -0.006772 -0.00 -4.62 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.151 %) +Internal coordinates : 0.000 s ( 2.915 %) +B/P matrices and projection : 0.000 s (11.558 %) +Hessian update/contruction : 0.000 s (30.955 %) +Making the step : 0.000 s ( 6.332 %) +Converting the step to Cartesian: 0.000 s ( 3.819 %) +Storing new data : 0.000 s ( 3.216 %) +Checking convergence : 0.000 s ( 1.508 %) +Final printing : 0.000 s (29.347 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.324790 -0.687160 -0.439282 + O 0.120676 0.487181 -0.590025 + O 0.449460 1.215601 0.443247 + H -0.264054 -0.877779 0.582352 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.613765 -1.298544 -0.830123 + 1 O 8.0000 0 15.999 0.228045 0.920640 -1.114986 + 2 O 8.0000 0 15.999 0.849357 2.297154 0.837616 + 3 H 1.0000 0 1.008 -0.498990 -1.658762 1.100485 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.265006307121 0.00000000 0.00000000 + O 2 1 0 1.306272019136 120.79983606 0.00000000 + H 1 2 3 1.041038009211 105.44894704 355.38461526 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.390515478143 0.00000000 0.00000000 + O 2 1 0 2.468496372571 120.79983606 0.00000000 + H 1 2 3 1.967276732411 105.44894704 355.38461526 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1681 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.376246301295 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.834e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.3762463013 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5749362780460672 0.00e+00 6.60e-06 5.73e-05 1.71e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5749363477366671 -6.97e-08 4.78e-06 6.17e-05 1.69e-05 0.0 + 3 -205.5749363172481878 3.05e-08 3.60e-06 5.77e-05 9.87e-05 0.0 + 4 -205.5749363506940028 -3.34e-08 2.81e-06 4.33e-05 2.03e-05 0.0 + 5 -205.5749363402534016 1.04e-08 1.75e-06 3.17e-05 5.84e-05 0.0 + 6 -205.5749363527594085 -1.25e-08 4.23e-07 4.33e-06 1.66e-06 0.0 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 6 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57493635275941 Eh -5593.97841 eV + +Components: +Nuclear Repulsion : 70.37624630129469 Eh 1915.03502 eV +Electronic Energy : -275.95118265405409 Eh -7509.01343 eV +One Electron Energy: -420.37105049213920 Eh -11438.87783 eV +Two Electron Energy: 144.41986783808511 Eh 3929.86439 eV + +Virial components: +Potential Energy : -410.44631232017491 Eh -11168.81197 eV +Kinetic Energy : 204.87137596741553 Eh 5574.83356 eV +Virial Ratio : 2.00343415658738 + +DFT components: +N(Alpha) : 11.999998699466 electrons +N(Beta) : 11.999998699466 electrons +N(Total) : 23.999997398931 electrons +E(X) : -23.355964972788 Eh +E(C) : -0.805238347560 Eh +E(XC) : -24.161203320348 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.2506e-08 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.3292e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.2300e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.6037e-05 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.6633e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.5339e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.194913 -522.3201 + 1 2.0000 -19.018560 -517.5213 + 2 2.0000 -14.276908 -388.4944 + 3 2.0000 -1.261064 -34.3153 + 4 2.0000 -0.973720 -26.4963 + 5 2.0000 -0.721512 -19.6333 + 6 2.0000 -0.561515 -15.2796 + 7 2.0000 -0.526966 -14.3395 + 8 2.0000 -0.500672 -13.6240 + 9 2.0000 -0.333611 -9.0780 + 10 2.0000 -0.292749 -7.9661 + 11 2.0000 -0.267743 -7.2857 + 12 0.0000 -0.179401 -4.8818 + 13 0.0000 0.028715 0.7814 + 14 0.0000 0.106406 2.8954 + 15 0.0000 0.140375 3.8198 + 16 0.0000 0.223759 6.0888 + 17 0.0000 0.277111 7.5406 + 18 0.0000 0.295322 8.0361 + 19 0.0000 0.331868 9.0306 + 20 0.0000 0.361617 9.8401 + 21 0.0000 0.366772 9.9804 + 22 0.0000 0.395892 10.7728 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.238225 + 1 O : 0.232837 + 2 O : -0.249611 + 3 H : 0.255000 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.857135 s : 3.857135 + pz : 1.348508 p : 3.328731 + px : 1.060768 + py : 0.919455 + dz2 : 0.012623 d : 0.052359 + dxz : 0.000010 + dyz : 0.006938 + dx2y2 : 0.016071 + dxy : 0.016718 + + 1 O s : 3.733547 s : 3.733547 + pz : 1.431637 p : 3.886978 + px : 1.325558 + py : 1.129783 + dz2 : 0.040899 d : 0.146638 + dxz : 0.018180 + dyz : 0.025028 + dx2y2 : 0.030389 + dxy : 0.032142 + + 2 O s : 3.941376 s : 3.941376 + pz : 1.332347 p : 4.286917 + px : 1.453988 + py : 1.500582 + dz2 : -0.000452 d : 0.021318 + dxz : 0.007618 + dyz : 0.009271 + dx2y2 : 0.002442 + dxy : 0.002439 + + 3 H s : 0.716893 s : 0.716893 + pz : 0.018310 p : 0.028107 + px : 0.004939 + py : 0.004859 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.033559 + 1 O : -0.183041 + 2 O : -0.060594 + 3 H : 0.277194 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.344162 s : 3.344162 + pz : 1.310849 p : 3.375256 + px : 1.014588 + py : 1.049820 + dz2 : 0.062345 d : 0.314142 + dxz : 0.010863 + dyz : 0.089376 + dx2y2 : 0.077476 + dxy : 0.074082 + + 1 O s : 3.356570 s : 3.356570 + pz : 1.463434 p : 4.042940 + px : 1.264830 + py : 1.314676 + dz2 : 0.167885 d : 0.783532 + dxz : 0.067580 + dyz : 0.212597 + dx2y2 : 0.166451 + dxy : 0.169019 + + 2 O s : 3.600477 s : 3.600477 + pz : 1.336341 p : 4.210203 + px : 1.386806 + py : 1.487056 + dz2 : 0.080288 d : 0.249914 + dxz : 0.041658 + dyz : 0.067647 + dx2y2 : 0.030272 + dxy : 0.030050 + + 3 H s : 0.650183 s : 0.650183 + pz : 0.051002 p : 0.072623 + px : 0.011875 + py : 0.009746 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2382 7.0000 -0.2382 2.7881 2.7881 -0.0000 + 1 O 7.7672 8.0000 0.2328 2.6569 2.6569 -0.0000 + 2 O 8.2496 8.0000 -0.2496 1.6776 1.6776 0.0000 + 3 H 0.7450 1.0000 0.2550 0.9331 0.9331 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4529 B( 0-N , 2-O ) : 0.4625 B( 0-N , 3-H ) : 0.8728 +B( 1-O , 2-O ) : 1.1794 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.696 sec +Sum of individual times .... 1.680 sec ( 99.1%) + +SCF preparation .... 0.682 sec ( 40.3%) +Fock matrix formation .... 0.160 sec ( 9.5%) + Startup .... 0.008 sec ( 5.2% of F) + Split-RI-J .... 0.024 sec ( 15.1% of F) + XC integration .... 0.104 sec ( 64.9% of F) + Basis function eval. .... 0.006 sec ( 6.2% of XC) + Density eval. .... 0.009 sec ( 8.9% of XC) + XC-Functional eval. .... 0.005 sec ( 5.2% of XC) + XC-Potential eval. .... 0.009 sec ( 8.2% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.010 sec ( 0.6%) +Total Energy calculation .... 0.013 sec ( 0.8%) +Population analysis .... 0.765 sec ( 45.1%) +Orbital Transformation .... 0.006 sec ( 0.4%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.010 sec ( 0.6%) +SOSCF solution .... 0.033 sec ( 1.9%) +Finished LeanSCF after 2.5 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 27.8 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000364337 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007287587 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.568013102740 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.020.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.020.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.173087 0.672596 -0.318122 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5749363527594085 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.171459282 0.601745569 -0.494711856 +Nuclear contribution : -0.330230703 -1.148518385 0.705600635 + ----------------------------------------- +Total Dipole Moment : -0.158771421 -0.546772816 0.210888779 + ----------------------------------------- +Magnitude (a.u.) : 0.607159743 +Magnitude (Debye) : 1.543277420 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.964543 0.440885 0.383887 +Rotational constants in MHz : 88874.763944 13217.398489 11508.639026 + +Dipole components along the rotational axes: +x,y,z [a.u.] : -0.442695 0.414344 -0.031346 +x,y,z [Debye]: -1.125242 1.053180 -0.079674 + + + +Dipole moment calculation done in 0.3 sec + +Maximum memory used throughout the entire PROP-calculation: 14.9 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 21 * + * * + * Dihedral ( 2, 1, 0, 3) : 4.61538462 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2672 0.793290 + 2. B(O 2,O 1) 1.3075 0.681703 + 3. B(H 3,N 0) 1.0428 0.386079 + 4. A(O 1,N 0,H 3) 105.1923 0.364543 + 5. A(N 0,O 1,O 2) 120.5430 0.449544 + 6. D(O 2,O 1,N 0,H 3) 4.6154 0.050654 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.289552 -0.701288 -0.443848 + O 0.087139 0.499864 -0.588971 + O 0.467662 1.206221 0.443392 + H -0.283957 -0.866953 0.585720 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.547174 -1.325242 -0.838752 + 1 O 8.0000 0 15.999 0.164668 0.944606 -1.112994 + 2 O 8.0000 0 15.999 0.883754 2.279427 0.837889 + 3 H 1.0000 0 1.008 -0.536601 -1.638303 1.106850 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.265006307121 0.00000000 0.00000000 + O 2 1 0 1.306272019136 120.79983606 0.00000000 + H 1 2 3 1.041038009211 105.44894704 355.38461526 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.390515478143 0.00000000 0.00000000 + O 2 1 0 2.468496372571 120.79983606 0.00000000 + H 1 2 3 1.967276732411 105.44894704 355.38461526 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1681 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.310978209213 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.853e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22309 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.3109782092 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5703951363897772 0.00e+00 3.63e-04 3.42e-03 2.89e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.088) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5716003790025752 -1.21e-03 4.39e-04 3.73e-03 2.24e-02 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.5725960316725036 -9.96e-04 3.35e-04 2.74e-03 1.59e-02 0.700 0.0 + 4 -205.5732972766527951 -7.01e-04 8.42e-04 6.81e-03 1.12e-02 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5749342061614016 -1.64e-03 6.61e-05 5.39e-04 5.53e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -205.5749413846211837 -7.18e-06 1.63e-04 1.51e-03 6.11e-04 0.0 + 7 -205.5749398170918880 1.57e-06 1.82e-04 2.10e-03 1.51e-03 0.0 + 8 -205.5749335852583499 6.23e-06 1.69e-04 1.25e-03 1.60e-03 0.0 + 9 -205.5749435196555623 -9.93e-06 1.16e-04 1.17e-03 1.27e-03 0.0 + 10 -205.5749420879866989 1.43e-06 1.14e-04 9.66e-04 1.04e-03 0.0 + 11 -205.5749495763765253 -7.49e-06 1.57e-05 1.19e-04 5.17e-05 0.0 + 12 -205.5749496435401511 -6.72e-08 3.37e-06 2.97e-05 3.16e-05 0.0 + 13 -205.5749496572257158 -1.37e-08 1.63e-06 1.34e-05 6.59e-06 0.0 + 14 -205.5749496585841598 -1.36e-09 5.15e-07 3.97e-06 2.76e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 14 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57494965858416 Eh -5593.97877 eV + +Components: +Nuclear Repulsion : 70.31097820921299 Eh 1913.25899 eV +Electronic Energy : -275.88592786779714 Eh -7507.23776 eV +One Electron Energy: -420.24777781997381 Eh -11435.52341 eV +Two Electron Energy: 144.36184995217670 Eh 3928.28565 eV + +Virial components: +Potential Energy : -410.43696282445262 Eh -11168.55756 eV +Kinetic Energy : 204.86201316586846 Eh 5574.57878 eV +Virial Ratio : 2.00348008145433 + +DFT components: +N(Alpha) : 11.999999892375 electrons +N(Beta) : 11.999999892375 electrons +N(Total) : 23.999999784749 electrons +E(X) : -23.353271018022 Eh +E(C) : -0.805098331863 Eh +E(XC) : -24.158369349886 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.3584e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.9677e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 5.1452e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.5284e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.7642e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.6914e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.194898 -522.3197 + 1 2.0000 -19.018718 -517.5256 + 2 2.0000 -14.277230 -388.5032 + 3 2.0000 -1.259941 -34.2847 + 4 2.0000 -0.972535 -26.4640 + 5 2.0000 -0.721588 -19.6354 + 6 2.0000 -0.561023 -15.2662 + 7 2.0000 -0.526277 -14.3207 + 8 2.0000 -0.500191 -13.6109 + 9 2.0000 -0.334225 -9.0947 + 10 2.0000 -0.292616 -7.9625 + 11 2.0000 -0.267904 -7.2900 + 12 0.0000 -0.180026 -4.8987 + 13 0.0000 0.027704 0.7539 + 14 0.0000 0.105812 2.8793 + 15 0.0000 0.139589 3.7984 + 16 0.0000 0.222754 6.0615 + 17 0.0000 0.277016 7.5380 + 18 0.0000 0.295518 8.0415 + 19 0.0000 0.331666 9.0251 + 20 0.0000 0.361594 9.8395 + 21 0.0000 0.366768 9.9803 + 22 0.0000 0.395400 10.7594 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.238634 + 1 O : 0.231979 + 2 O : -0.249230 + 3 H : 0.255886 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.858836 s : 3.858836 + pz : 1.348574 p : 3.327438 + px : 1.068271 + py : 0.910593 + dz2 : 0.012950 d : 0.052361 + dxz : -0.000601 + dyz : 0.007544 + dx2y2 : 0.015469 + dxy : 0.016999 + + 1 O s : 3.735501 s : 3.735501 + pz : 1.429418 p : 3.886379 + px : 1.329597 + py : 1.127364 + dz2 : 0.040461 d : 0.146142 + dxz : 0.017444 + dyz : 0.025959 + dx2y2 : 0.028177 + dxy : 0.034101 + + 2 O s : 3.941585 s : 3.941585 + pz : 1.328263 p : 4.286342 + px : 1.415706 + py : 1.542372 + dz2 : -0.000075 d : 0.021302 + dxz : 0.007460 + dyz : 0.008968 + dx2y2 : 0.002663 + dxy : 0.002286 + + 3 H s : 0.716125 s : 0.716125 + pz : 0.018407 p : 0.027989 + px : 0.004961 + py : 0.004621 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.034210 + 1 O : -0.182123 + 2 O : -0.061718 + 3 H : 0.278051 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.346639 s : 3.346639 + pz : 1.311326 p : 3.374047 + px : 1.013214 + py : 1.049506 + dz2 : 0.063135 d : 0.313524 + dxz : 0.008571 + dyz : 0.090507 + dx2y2 : 0.080504 + dxy : 0.070807 + + 1 O s : 3.358396 s : 3.358396 + pz : 1.460883 p : 4.042428 + px : 1.263510 + py : 1.318036 + dz2 : 0.165792 d : 0.781299 + dxz : 0.068723 + dyz : 0.212181 + dx2y2 : 0.167305 + dxy : 0.167298 + + 2 O s : 3.601265 s : 3.601265 + pz : 1.333067 p : 4.210395 + px : 1.356003 + py : 1.521325 + dz2 : 0.079430 d : 0.250059 + dxz : 0.044400 + dyz : 0.065341 + dx2y2 : 0.031174 + dxy : 0.029715 + + 3 H s : 0.649662 s : 0.649662 + pz : 0.051309 p : 0.072287 + px : 0.011808 + py : 0.009170 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2386 7.0000 -0.2386 2.7864 2.7864 -0.0000 + 1 O 7.7680 8.0000 0.2320 2.6562 2.6562 -0.0000 + 2 O 8.2492 8.0000 -0.2492 1.6776 1.6776 0.0000 + 3 H 0.7441 1.0000 0.2559 0.9328 0.9328 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4521 B( 0-N , 2-O ) : 0.4623 B( 0-N , 3-H ) : 0.8719 +B( 1-O , 2-O ) : 1.1792 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.100 sec +Sum of individual times .... 2.082 sec ( 99.2%) + +SCF preparation .... 0.669 sec ( 31.9%) +Fock matrix formation .... 0.364 sec ( 17.3%) + Startup .... 0.016 sec ( 4.3% of F) + Split-RI-J .... 0.053 sec ( 14.5% of F) + XC integration .... 0.238 sec ( 65.3% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.017 sec ( 7.1% of XC) + Density eval. .... 0.022 sec ( 9.4% of XC) + XC-Functional eval. .... 0.015 sec ( 6.5% of XC) + XC-Potential eval. .... 0.027 sec ( 11.2% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.025 sec ( 1.2%) +Total Energy calculation .... 0.029 sec ( 1.4%) +Population analysis .... 0.854 sec ( 40.7%) +Orbital Transformation .... 0.015 sec ( 0.7%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.069 sec ( 3.3%) +SOSCF solution .... 0.055 sec ( 2.6%) +Finished LeanSCF after 3.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 28.2 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000364359 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007311520 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.568002497550 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001574 -0.000004685 0.000001990 + 2 O : 0.000000081 0.000000535 -0.000000882 + 3 O : 0.000002031 0.000005103 0.000002096 + 4 H : -0.000000538 -0.000000953 -0.000003204 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000086881 +RMS gradient ... 0.0000025080 +MAX gradient ... 0.0000051031 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.005077298 -0.003692442 -0.001204021 + 2 O : -0.004973276 0.003464570 -0.001004703 + 3 O : 0.003143402 -0.001011134 0.000696504 + 4 H : -0.003247424 0.001239006 0.001512220 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000084456 0.0000185991 -0.0000265201 + +Norm of the Cartesian gradient ... 0.0102159235 +RMS gradient ... 0.0029490831 +MAX gradient ... 0.0050772978 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.627 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.005 sec ( 0.9%) +RI-J Coulomb gradient .... 0.064 sec ( 10.1%) +XC gradient .... 0.021 sec ( 3.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.568002498 Eh +Current gradient norm .... 0.010215923 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999982031 +Lowest eigenvalues of augmented Hessian: + -0.000017260 0.363640354 0.383555036 0.448539120 0.678678602 +Length of the computed step .... 0.005994924 +The final length of the internal step .... 0.005994924 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0024474173 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0021907434 RMS(Int)= 0.0024457979 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000004 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0012273789 0.0001000000 NO + MAX gradient 0.0018170191 0.0003000000 NO + RMS step 0.0024474173 0.0020000000 NO + MAX step 0.0036558540 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0018 Max(Angles) 0.21 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2672 0.001817 -0.0012 1.2659 + 2. B(O 2,O 1) 1.3075 0.000919 -0.0007 1.3068 + 3. B(H 3,N 0) 1.0428 0.001277 -0.0018 1.0411 + 4. A(O 1,N 0,H 3) 105.19 -0.000755 0.12 105.31 + 5. A(N 0,O 1,O 2) 120.54 -0.001640 0.21 120.75 + 6. D(O 2,O 1,N 0,H 3) 4.62 0.006747 0.00 4.62 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.132 %) +Internal coordinates : 0.000 s ( 0.045 %) +B/P matrices and projection : 0.000 s ( 0.180 %) +Hessian update/contruction : 0.047 s (98.897 %) +Making the step : 0.000 s ( 0.134 %) +Converting the step to Cartesian: 0.000 s ( 0.070 %) +Storing new data : 0.000 s ( 0.078 %) +Checking convergence : 0.000 s ( 0.002 %) +Final printing : 0.000 s ( 0.458 %) +Total time : 0.047 s + +Time for energy+gradient : 7.631 s +Time for complete geometry iter : 8.747 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.289403 -0.700799 -0.443025 + O 0.087174 0.499208 -0.587240 + O 0.468242 1.208244 0.442174 + H -0.284721 -0.868809 0.584382 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.546893 -1.324319 -0.837195 + 1 O 8.0000 0 15.999 0.164735 0.943367 -1.109722 + 2 O 8.0000 0 15.999 0.884849 2.283250 0.835588 + 3 H 1.0000 0 1.008 -0.538045 -1.641811 1.104322 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.265948926992 0.00000000 0.00000000 + O 2 1 0 1.306765860126 120.75244785 0.00000000 + H 1 2 3 1.041063741447 105.31128619 4.61538474 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.392296771546 0.00000000 0.00000000 + O 2 1 0 2.469429596795 120.75244785 0.00000000 + H 1 2 3 1.967325359291 105.31128619 4.61538474 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1681 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.347530867736 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.841e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22309 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5749347162449112 0.00e+00 7.75e-05 6.89e-04 2.10e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5749427809816439 -8.06e-06 5.75e-05 7.22e-04 2.24e-04 0.0 + 3 -205.5749389330948134 3.85e-06 4.52e-05 6.78e-04 1.18e-03 0.0 + 4 -205.5749433066451957 -4.37e-06 3.41e-05 4.05e-04 1.39e-04 0.0 + 5 -205.5749430393803436 2.67e-07 1.38e-05 1.99e-04 3.10e-04 0.0 + 6 -205.5749435206601561 -4.81e-07 1.83e-05 2.22e-04 1.04e-04 0.0 + 7 -205.5749434923015428 2.84e-08 1.04e-05 1.28e-04 7.10e-05 0.0 + 8 -205.5749435908564919 -9.86e-08 8.98e-07 9.37e-06 3.44e-06 0.0 + 9 -205.5749435915918752 -7.35e-10 3.37e-07 3.78e-06 1.87e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57494359159188 Eh -5593.97861 eV + +Components: +Nuclear Repulsion : 70.34753086773604 Eh 1914.25363 eV +Electronic Energy : -275.92247445932787 Eh -7508.23224 eV +One Electron Energy: -420.31597709318362 Eh -11437.37920 eV +Two Electron Energy: 144.39350263385572 Eh 3929.14696 eV + +Virial components: +Potential Energy : -410.44322421257186 Eh -11168.72794 eV +Kinetic Energy : 204.86828062097999 Eh 5574.74933 eV +Virial Ratio : 2.00344935276691 + +DFT components: +N(Alpha) : 11.999999906389 electrons +N(Beta) : 11.999999906389 electrons +N(Total) : 23.999999812777 electrons +E(X) : -23.355070022109 Eh +E(C) : -0.805184006054 Eh +E(XC) : -24.160254028163 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 7.3538e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.7804e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.3674e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.7575e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.8650e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 5.0968e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 1.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 28.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000364335 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007294755 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.568013172482 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001579 -0.000004698 0.000001989 + 2 O : 0.000000081 0.000000534 -0.000000878 + 3 O : 0.000002038 0.000005123 0.000002089 + 4 H : -0.000000540 -0.000000959 -0.000003200 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000087064 +RMS gradient ... 0.0000025133 +MAX gradient ... 0.0000051231 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.005357625 -0.002875482 -0.000560185 + 2 O : -0.005171425 0.002343962 0.000398117 + 3 O : 0.003109309 -0.000817222 -0.000062747 + 4 H : -0.003295509 0.001348742 0.000224815 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000077132 0.0000168024 -0.0000262687 + +Norm of the Cartesian gradient ... 0.0096307979 +RMS gradient ... 0.0027801719 +MAX gradient ... 0.0053576251 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.126 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 4.1%) +RI-J Coulomb gradient .... 0.059 sec ( 46.6%) +XC gradient .... 0.020 sec ( 15.6%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.568013172 Eh +Current gradient norm .... 0.009630798 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999995627 +Lowest eigenvalues of augmented Hessian: + -0.000002937 0.283294315 0.406246213 0.479947536 0.635419496 +Length of the computed step .... 0.002957523 +The final length of the internal step .... 0.002957523 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0012074038 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0010356634 RMS(Int)= 0.0012072460 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000002 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000001469 +Previously predicted energy change .... -0.000008630 +Actually observed energy change .... -0.000010675 +Ratio of predicted to observed change .... 1.236924389 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000106749 0.0000050000 NO + RMS gradient 0.0004341594 0.0001000000 NO + MAX gradient 0.0007956842 0.0003000000 NO + RMS step 0.0012074038 0.0020000000 YES + MAX step 0.0021760134 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0008 Max(Angles) 0.12 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2659 0.000796 -0.0008 1.2651 + 2. B(O 2,O 1) 1.3068 0.000415 -0.0005 1.3063 + 3. B(H 3,N 0) 1.0411 -0.000012 -0.0001 1.0409 + 4. A(O 1,N 0,H 3) 105.31 -0.000548 0.12 105.44 + 5. A(N 0,O 1,O 2) 120.75 -0.000158 0.05 120.80 + 6. D(O 2,O 1,N 0,H 3) 4.62 0.006749 0.00 4.62 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 6.871 %) +Internal coordinates : 0.000 s ( 2.945 %) +B/P matrices and projection : 0.000 s (10.184 %) +Hessian update/contruction : 0.000 s (43.926 %) +Making the step : 0.000 s ( 5.153 %) +Converting the step to Cartesian: 0.000 s ( 3.558 %) +Storing new data : 0.000 s ( 3.067 %) +Checking convergence : 0.000 s ( 1.227 %) +Final printing : 0.000 s (22.577 %) +Total time : 0.001 s + +Time for energy+gradient : 5.670 s +Time for complete geometry iter : 6.442 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.289144 -0.700045 -0.442643 + O 0.087242 0.499161 -0.586842 + O 0.468373 1.208814 0.441496 + H -0.285179 -0.870087 0.584281 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.546403 -1.322892 -0.836473 + 1 O 8.0000 0 15.999 0.164863 0.943277 -1.108971 + 2 O 8.0000 0 15.999 0.885097 2.284328 0.834307 + 3 H 1.0000 0 1.008 -0.538910 -1.644226 1.104131 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.265129803820 0.00000000 0.00000000 + O 2 1 0 1.306272893687 120.79927075 0.00000000 + H 1 2 3 1.040913886624 105.43596258 4.61538474 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.390748853080 0.00000000 0.00000000 + O 2 1 0 2.468498025234 120.79927075 0.00000000 + H 1 2 3 1.967042174715 105.43596258 4.61538474 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1681 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.374072234813 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.835e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22309 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5749369055486113 0.00e+00 3.31e-05 2.73e-04 7.87e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5749382432583161 -1.34e-06 1.97e-05 1.73e-04 8.35e-05 0.0 + 3 -205.5749379219815864 3.21e-07 1.48e-05 2.43e-04 2.87e-04 0.0 + 4 -205.5749382227821798 -3.01e-07 2.11e-05 2.92e-04 1.42e-04 0.0 + 5 -205.5749377668578290 4.56e-07 1.23e-05 2.22e-04 3.84e-04 0.0 + 6 -205.5749383427220778 -5.76e-07 6.06e-06 6.74e-05 2.18e-05 0.0 + 7 -205.5749383408723361 1.85e-09 3.16e-06 3.45e-05 2.58e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57493834087234 Eh -5593.97846 eV + +Components: +Nuclear Repulsion : 70.37407223481337 Eh 1914.97586 eV +Electronic Energy : -275.94901057568575 Eh -7508.95433 eV +One Electron Energy: -420.36567652577429 Eh -11438.73159 eV +Two Electron Energy: 144.41666595008857 Eh 3929.77727 eV + +Virial components: +Potential Energy : -410.44622506353392 Eh -11168.80960 eV +Kinetic Energy : 204.87128672266158 Eh 5574.83113 eV +Virial Ratio : 2.00343460340132 + +DFT components: +N(Alpha) : 11.999999903747 electrons +N(Beta) : 11.999999903747 electrons +N(Total) : 23.999999807494 electrons +E(X) : -23.355794294712 Eh +E(C) : -0.805233401799 Eh +E(XC) : -24.161027696511 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.8497e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.4531e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.1624e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 4.4602e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.5761e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.6770e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 28.5 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000364335 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007287902 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.568014773945 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001580 -0.000004702 0.000001991 + 2 O : 0.000000082 0.000000536 -0.000000876 + 3 O : 0.000002039 0.000005127 0.000002083 + 4 H : -0.000000541 -0.000000960 -0.000003198 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000087098 +RMS gradient ... 0.0000025143 +MAX gradient ... 0.0000051272 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.005649513 -0.002022890 -0.000401188 + 2 O : -0.005262776 0.001898619 0.000790579 + 3 O : 0.002984443 -0.001022081 -0.000489685 + 4 H : -0.003371180 0.001146352 0.000100294 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000066152 0.0000162385 -0.0000265699 + +Norm of the Cartesian gradient ... 0.0095381857 +RMS gradient ... 0.0027534370 +MAX gradient ... 0.0056495126 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.138 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.8%) +RI-J Coulomb gradient .... 0.062 sec ( 45.1%) +XC gradient .... 0.020 sec ( 14.4%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.568014774 Eh +Current gradient norm .... 0.009538186 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999884 +Lowest eigenvalues of augmented Hessian: + -0.000000087 0.260308278 0.402421400 0.488316656 0.638843745 +Length of the computed step .... 0.000481603 +The final length of the internal step .... 0.000481603 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0001966138 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001474729 RMS(Int)= 0.0001966220 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000044 +Previously predicted energy change .... -0.000001469 +Actually observed energy change .... -0.000001601 +Ratio of predicted to observed change .... 1.090447697 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000016015 0.0000050000 YES + RMS gradient 0.0000800143 0.0001000000 YES + MAX gradient 0.0001188401 0.0003000000 YES + RMS step 0.0001966138 0.0020000000 YES + MAX step 0.0003478506 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.02 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2651 0.000119 -0.0001 1.2650 + 2. B(O 2,O 1) 1.3063 -0.000069 0.0000 1.3063 + 3. B(H 3,N 0) 1.0409 -0.000102 0.0001 1.0410 + 4. A(O 1,N 0,H 3) 105.44 -0.000091 0.02 105.46 + 5. A(N 0,O 1,O 2) 120.80 0.000029 0.00 120.80 + 6. D(O 2,O 1,N 0,H 3) 4.62 0.006750 -0.00 4.62 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 8.847 %) +Internal coordinates : 0.000 s ( 2.949 %) +B/P matrices and projection : 0.000 s (11.796 %) +Hessian update/contruction : 0.000 s (34.450 %) +Making the step : 0.000 s ( 5.898 %) +Converting the step to Cartesian: 0.000 s ( 3.753 %) +Storing new data : 0.000 s ( 3.217 %) +Checking convergence : 0.000 s ( 1.340 %) +Final printing : 0.000 s (27.346 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.289104 -0.699922 -0.442638 + O 0.087243 0.499160 -0.586875 + O 0.468395 1.208888 0.441452 + H -0.285242 -0.870282 0.584354 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.546327 -1.322661 -0.836466 + 1 O 8.0000 0 15.999 0.164865 0.943276 -1.109034 + 2 O 8.0000 0 15.999 0.885139 2.284467 0.834224 + 3 H 1.0000 0 1.008 -0.539030 -1.644595 1.104268 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.265005993632 0.00000000 0.00000000 + O 2 1 0 1.306310932887 120.79993288 0.00000000 + H 1 2 3 1.041033274695 105.45589295 4.61538474 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.390514885734 0.00000000 0.00000000 + O 2 1 0 2.468569908903 120.79993288 0.00000000 + H 1 2 3 1.967267785473 105.45589295 4.61538474 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1681 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.375064509127 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.835e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22309 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.3750645091 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.5 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5749377076526798 0.00e+00 3.94e-06 4.07e-05 7.17e-06 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5749377314323283 -2.38e-08 2.60e-06 3.19e-05 1.66e-05 0.0 + 3 -205.5749377243544700 7.08e-09 1.68e-06 2.79e-05 4.39e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 3 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57493772435447 Eh -5593.97845 eV + +Components: +Nuclear Repulsion : 70.37506450912674 Eh 1915.00286 eV +Electronic Energy : -275.95000223348120 Eh -7508.98131 eV +One Electron Energy: -420.36852786901488 Eh -11438.80918 eV +Two Electron Energy: 144.41852563553368 Eh 3929.82787 eV + +Virial components: +Potential Energy : -410.44613715231719 Eh -11168.80720 eV +Kinetic Energy : 204.87119942796269 Eh 5574.82876 eV +Virial Ratio : 2.00343502795101 + +DFT components: +N(Alpha) : 11.999999905764 electrons +N(Beta) : 11.999999905764 electrons +N(Total) : 23.999999811529 electrons +E(X) : -23.355923136367 Eh +E(C) : -0.805236568414 Eh +E(XC) : -24.161159704781 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -7.0779e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.7897e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.6812e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.1059e-05 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.3873e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 4.6781e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.195038 -522.3235 + 1 2.0000 -19.018469 -517.5188 + 2 2.0000 -14.276925 -388.4949 + 3 2.0000 -1.261080 -34.3157 + 4 2.0000 -0.973714 -26.4961 + 5 2.0000 -0.721531 -19.6339 + 6 2.0000 -0.561517 -15.2797 + 7 2.0000 -0.526994 -14.3402 + 8 2.0000 -0.500699 -13.6247 + 9 2.0000 -0.333616 -9.0782 + 10 2.0000 -0.292728 -7.9655 + 11 2.0000 -0.267713 -7.2848 + 12 0.0000 -0.179421 -4.8823 + 13 0.0000 0.028695 0.7808 + 14 0.0000 0.106388 2.8950 + 15 0.0000 0.140354 3.8192 + 16 0.0000 0.223745 6.0884 + 17 0.0000 0.277109 7.5405 + 18 0.0000 0.295317 8.0360 + 19 0.0000 0.331862 9.0304 + 20 0.0000 0.361616 9.8401 + 21 0.0000 0.366762 9.9801 + 22 0.0000 0.395890 10.7727 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.238263 + 1 O : 0.232835 + 2 O : -0.249579 + 3 H : 0.255007 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.857105 s : 3.857105 + pz : 1.349591 p : 3.328797 + px : 1.068747 + py : 0.910459 + dz2 : 0.012828 d : 0.052361 + dxz : -0.000599 + dyz : 0.007555 + dx2y2 : 0.015526 + dxy : 0.017051 + + 1 O s : 3.733557 s : 3.733557 + pz : 1.431532 p : 3.886967 + px : 1.328906 + py : 1.126530 + dz2 : 0.040582 d : 0.146641 + dxz : 0.017452 + dyz : 0.025783 + dx2y2 : 0.028460 + dxy : 0.034363 + + 2 O s : 3.941373 s : 3.941373 + pz : 1.333779 p : 4.286889 + px : 1.414977 + py : 1.538133 + dz2 : -0.000120 d : 0.021317 + dxz : 0.007431 + dyz : 0.008981 + dx2y2 : 0.002692 + dxy : 0.002332 + + 3 H s : 0.716886 s : 0.716886 + pz : 0.018442 p : 0.028107 + px : 0.004996 + py : 0.004670 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.033615 + 1 O : -0.183011 + 2 O : -0.060567 + 3 H : 0.277194 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.344148 s : 3.344148 + pz : 1.312027 p : 3.375318 + px : 1.013394 + py : 1.049898 + dz2 : 0.063014 d : 0.314149 + dxz : 0.008604 + dyz : 0.091037 + dx2y2 : 0.080584 + dxy : 0.070910 + + 1 O s : 3.356586 s : 3.356586 + pz : 1.462048 p : 4.042916 + px : 1.262918 + py : 1.317950 + dz2 : 0.165758 d : 0.783509 + dxz : 0.068638 + dyz : 0.212725 + dx2y2 : 0.168108 + dxy : 0.168280 + + 2 O s : 3.600502 s : 3.600502 + pz : 1.336895 p : 4.210171 + px : 1.355228 + py : 1.518047 + dz2 : 0.079099 d : 0.249895 + dxz : 0.044224 + dyz : 0.065405 + dx2y2 : 0.031289 + dxy : 0.029879 + + 3 H s : 0.650182 s : 0.650182 + pz : 0.051389 p : 0.072625 + px : 0.011911 + py : 0.009325 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2383 7.0000 -0.2383 2.7882 2.7882 -0.0000 + 1 O 7.7672 8.0000 0.2328 2.6570 2.6570 -0.0000 + 2 O 8.2496 8.0000 -0.2496 1.6776 1.6776 -0.0000 + 3 H 0.7450 1.0000 0.2550 0.9331 0.9331 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4529 B( 0-N , 2-O ) : 0.4625 B( 0-N , 3-H ) : 0.8728 +B( 1-O , 2-O ) : 1.1794 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.638 sec +Sum of individual times .... 1.626 sec ( 99.3%) + +SCF preparation .... 0.674 sec ( 41.2%) +Fock matrix formation .... 0.086 sec ( 5.3%) + Startup .... 0.005 sec ( 6.0% of F) + Split-RI-J .... 0.011 sec ( 13.3% of F) + XC integration .... 0.060 sec ( 69.2% of F) + Basis function eval. .... 0.003 sec ( 4.9% of XC) + Density eval. .... 0.004 sec ( 7.1% of XC) + XC-Functional eval. .... 0.003 sec ( 4.4% of XC) + XC-Potential eval. .... 0.004 sec ( 7.5% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.005 sec ( 0.3%) +Total Energy calculation .... 0.006 sec ( 0.4%) +Population analysis .... 0.824 sec ( 50.3%) +Orbital Transformation .... 0.006 sec ( 0.4%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.009 sec ( 0.6%) +SOSCF solution .... 0.016 sec ( 1.0%) +Finished LeanSCF after 2.5 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 28.8 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000364336 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007287231 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.568014829557 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.021.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.021.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.182998 0.669100 -0.319060 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5749377243544700 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.166545021 0.603693298 -0.494167601 +Nuclear contribution : -0.355231159 -1.139676887 0.707963283 + ----------------------------------------- +Total Dipole Moment : -0.188686138 -0.535983589 0.213795683 + ----------------------------------------- +Magnitude (a.u.) : 0.607115689 +Magnitude (Debye) : 1.543165445 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.964451 0.440868 0.383873 +Rotational constants in MHz : 88871.998459 13216.903094 11508.216855 + +Dipole components along the rotational axes: +x,y,z [a.u.] : -0.442606 0.414376 0.031342 +x,y,z [Debye]: -1.125014 1.053260 0.079665 + + + +Dipole moment calculation done in 0.3 sec + +Maximum memory used throughout the entire PROP-calculation: 15.4 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 22 * + * * + * Dihedral ( 2, 1, 0, 3) : 13.84615385 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2672 0.793291 + 2. B(O 2,O 1) 1.3075 0.681605 + 3. B(H 3,N 0) 1.0428 0.386085 + 4. A(O 1,N 0,H 3) 105.2001 0.364544 + 5. A(N 0,O 1,O 2) 120.5440 0.449532 + 6. D(O 2,O 1,N 0,H 3) 13.8462 0.050654 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.252772 -0.711420 -0.444846 + O 0.053693 0.510498 -0.581586 + O 0.488054 1.204709 0.437729 + H -0.307683 -0.865943 0.584994 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.477669 -1.344389 -0.840637 + 1 O 8.0000 0 15.999 0.101464 0.964701 -1.099038 + 2 O 8.0000 0 15.999 0.922289 2.276570 0.827188 + 3 H 1.0000 0 1.008 -0.581437 -1.636395 1.105479 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.265005993632 0.00000000 0.00000000 + O 2 1 0 1.306310932887 120.79993288 0.00000000 + H 1 2 3 1.041033274695 105.45589295 4.61538474 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.390514885734 0.00000000 0.00000000 + O 2 1 0 2.468569908903 120.79993288 0.00000000 + H 1 2 3 1.967267785473 105.45589295 4.61538474 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1681 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.298656334515 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.872e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22303 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.2986563345 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5682241120535139 0.00e+00 3.67e-04 3.69e-03 2.87e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.086) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5694258872829607 -1.20e-03 4.42e-04 4.04e-03 2.23e-02 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.5704194850211195 -9.94e-04 3.37e-04 2.95e-03 1.58e-02 0.700 0.0 + 4 -205.5711190407573383 -7.00e-04 8.48e-04 7.16e-03 1.12e-02 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5727531605152478 -1.63e-03 7.82e-05 8.16e-04 8.55e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -205.5727583628335822 -5.20e-06 2.62e-04 3.59e-03 9.56e-04 0.0 + 7 -205.5726580273796174 1.00e-04 1.92e-04 2.93e-03 5.73e-03 0.0 + 8 -205.5727693436511743 -1.11e-04 4.91e-05 5.05e-04 2.43e-04 0.0 + 9 -205.5727680504622015 1.29e-06 2.23e-05 4.08e-04 6.86e-04 0.0 + 10 -205.5727699489154645 -1.90e-06 1.84e-05 1.51e-04 6.53e-05 0.0 + 11 -205.5727699893290890 -4.04e-08 7.21e-06 5.16e-05 4.17e-05 0.0 + 12 -205.5727700270252569 -3.77e-08 1.24e-06 9.60e-06 4.64e-06 0.0 + 13 -205.5727700266315594 3.94e-10 5.52e-07 4.12e-06 3.82e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 13 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57277002663156 Eh -5593.91946 eV + +Components: +Nuclear Repulsion : 70.29865633451496 Eh 1912.92369 eV +Electronic Energy : -275.87142636114652 Eh -7506.84315 eV +One Electron Energy: -420.22406349554109 Eh -11434.87811 eV +Two Electron Energy: 144.35263713439460 Eh 3928.03495 eV + +Virial components: +Potential Energy : -410.43742547330123 Eh -11168.57015 eV +Kinetic Energy : 204.86465544666964 Eh 5574.65068 eV +Virial Ratio : 2.00345649950411 + +DFT components: +N(Alpha) : 12.000001095117 electrons +N(Beta) : 12.000001095117 electrons +N(Total) : 24.000002190235 electrons +E(X) : -23.353167484803 Eh +E(C) : -0.805091582689 Eh +E(XC) : -24.158259067492 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -3.9370e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.1200e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 5.5238e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.5487e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.8181e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.6047e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.194391 -522.3059 + 1 2.0000 -19.019201 -517.5388 + 2 2.0000 -14.276637 -388.4870 + 3 2.0000 -1.259708 -34.2784 + 4 2.0000 -0.972589 -26.4655 + 5 2.0000 -0.721037 -19.6204 + 6 2.0000 -0.561733 -15.2855 + 7 2.0000 -0.525876 -14.3098 + 8 2.0000 -0.500010 -13.6060 + 9 2.0000 -0.334002 -9.0887 + 10 2.0000 -0.291413 -7.9298 + 11 2.0000 -0.267954 -7.2914 + 12 0.0000 -0.181581 -4.9411 + 13 0.0000 0.028959 0.7880 + 14 0.0000 0.104738 2.8501 + 15 0.0000 0.139746 3.8027 + 16 0.0000 0.223515 6.0821 + 17 0.0000 0.275067 7.4849 + 18 0.0000 0.297273 8.0892 + 19 0.0000 0.331637 9.0243 + 20 0.0000 0.358178 9.7465 + 21 0.0000 0.372059 10.1242 + 22 0.0000 0.395757 10.7691 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.240407 + 1 O : 0.228415 + 2 O : -0.244966 + 3 H : 0.256958 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.856355 s : 3.856355 + pz : 1.352162 p : 3.331127 + px : 1.076224 + py : 0.902740 + dz2 : 0.013506 d : 0.052926 + dxz : -0.000838 + dyz : 0.008168 + dx2y2 : 0.014923 + dxy : 0.017167 + + 1 O s : 3.735506 s : 3.735506 + pz : 1.432472 p : 3.890750 + px : 1.332653 + py : 1.125625 + dz2 : 0.039357 d : 0.145329 + dxz : 0.016606 + dyz : 0.026857 + dx2y2 : 0.026430 + dxy : 0.036079 + + 2 O s : 3.941027 s : 3.941027 + pz : 1.338286 p : 4.283093 + px : 1.373840 + py : 1.570968 + dz2 : 0.000476 d : 0.020846 + dxz : 0.006819 + dyz : 0.008451 + dx2y2 : 0.002863 + dxy : 0.002237 + + 3 H s : 0.714978 s : 0.714978 + pz : 0.018370 p : 0.028064 + px : 0.005172 + py : 0.004521 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.035884 + 1 O : -0.182740 + 2 O : -0.059648 + 3 H : 0.278272 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.346049 s : 3.346049 + pz : 1.313921 p : 3.375954 + px : 1.012950 + py : 1.049084 + dz2 : 0.063019 d : 0.313880 + dxz : 0.007137 + dyz : 0.092336 + dx2y2 : 0.083303 + dxy : 0.068086 + + 1 O s : 3.358368 s : 3.358368 + pz : 1.460213 p : 4.043261 + px : 1.262321 + py : 1.320727 + dz2 : 0.161452 d : 0.781110 + dxz : 0.070077 + dyz : 0.212123 + dx2y2 : 0.169503 + dxy : 0.167955 + + 2 O s : 3.601596 s : 3.601596 + pz : 1.340929 p : 4.208283 + px : 1.322543 + py : 1.544811 + dz2 : 0.076808 d : 0.249770 + dxz : 0.046993 + dyz : 0.063012 + dx2y2 : 0.032786 + dxy : 0.030170 + + 3 H s : 0.649326 s : 0.649326 + pz : 0.051213 p : 0.072402 + px : 0.012207 + py : 0.008982 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2404 7.0000 -0.2404 2.7878 2.7878 -0.0000 + 1 O 7.7716 8.0000 0.2284 2.6528 2.6528 0.0000 + 2 O 8.2450 8.0000 -0.2450 1.6774 1.6774 0.0000 + 3 H 0.7430 1.0000 0.2570 0.9321 0.9321 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4498 B( 0-N , 2-O ) : 0.4649 B( 0-N , 3-H ) : 0.8731 +B( 1-O , 2-O ) : 1.1783 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.099 sec +Sum of individual times .... 2.083 sec ( 99.3%) + +SCF preparation .... 0.687 sec ( 32.7%) +Fock matrix formation .... 0.340 sec ( 16.2%) + Startup .... 0.015 sec ( 4.4% of F) + Split-RI-J .... 0.049 sec ( 14.5% of F) + XC integration .... 0.222 sec ( 65.3% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.014 sec ( 6.3% of XC) + Density eval. .... 0.020 sec ( 8.8% of XC) + XC-Functional eval. .... 0.012 sec ( 5.3% of XC) + XC-Potential eval. .... 0.018 sec ( 8.3% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.024 sec ( 1.1%) +Total Energy calculation .... 0.027 sec ( 1.3%) +Population analysis .... 0.872 sec ( 41.6%) +Orbital Transformation .... 0.014 sec ( 0.6%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.070 sec ( 3.4%) +SOSCF solution .... 0.049 sec ( 2.3%) +Finished LeanSCF after 3.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 29.2 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000364329 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007295464 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.565838891300 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001736 -0.000004669 0.000001999 + 2 O : 0.000000032 0.000000550 -0.000000870 + 3 O : 0.000002061 0.000005155 0.000002075 + 4 H : -0.000000358 -0.000001037 -0.000003203 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000087445 +RMS gradient ... 0.0000025243 +MAX gradient ... 0.0000051554 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.017102465 -0.005175141 -0.002362233 + 2 O : -0.015937758 0.004887448 0.002206732 + 3 O : 0.008940428 -0.002838553 -0.001271009 + 4 H : -0.010105134 0.003126246 0.001426510 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000101866 0.0000130252 0.0000102707 + +Norm of the Cartesian gradient ... 0.0284807242 +RMS gradient ... 0.0082216769 +MAX gradient ... 0.0171024646 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.127 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.8%) +RI-J Coulomb gradient .... 0.059 sec ( 46.5%) +XC gradient .... 0.020 sec ( 15.6%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.565838891 Eh +Current gradient norm .... 0.028480724 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999972704 +Lowest eigenvalues of augmented Hessian: + -0.000021929 0.363650500 0.383571965 0.448533643 0.678591631 +Length of the computed step .... 0.007388847 +The final length of the internal step .... 0.007388847 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0030164843 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0036899946 RMS(Int)= 0.0030135833 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0012199032 0.0001000000 NO + MAX gradient 0.0019494637 0.0003000000 NO + RMS step 0.0030164843 0.0020000000 NO + MAX step 0.0045114119 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0020 Max(Angles) 0.26 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2672 0.000182 -0.0001 1.2670 + 2. B(O 2,O 1) 1.3075 0.000473 -0.0004 1.3071 + 3. B(H 3,N 0) 1.0428 0.001476 -0.0020 1.0408 + 4. A(O 1,N 0,H 3) 105.20 -0.001641 0.26 105.46 + 5. A(N 0,O 1,O 2) 120.54 -0.001949 0.25 120.79 + 6. D(O 2,O 1,N 0,H 3) 13.85 0.020048 0.00 13.85 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.245 %) +Internal coordinates : 0.000 s ( 3.255 %) +B/P matrices and projection : 0.000 s (12.630 %) +Hessian update/contruction : 0.000 s (33.594 %) +Making the step : 0.000 s ( 6.510 %) +Converting the step to Cartesian: 0.000 s ( 4.297 %) +Storing new data : 0.000 s ( 3.646 %) +Checking convergence : 0.000 s ( 0.000 %) +Final printing : 0.000 s (26.563 %) +Total time : 0.001 s + +Time for energy+gradient : 6.678 s +Time for complete geometry iter : 7.503 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.252966 -0.711151 -0.443479 + O 0.054249 0.510491 -0.579863 + O 0.489192 1.208579 0.436077 + H -0.309183 -0.870075 0.583557 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.478036 -1.343881 -0.838054 + 1 O 8.0000 0 15.999 0.102516 0.964688 -1.095782 + 2 O 8.0000 0 15.999 0.924438 2.283884 0.824066 + 3 H 1.0000 0 1.008 -0.584272 -1.644203 1.102763 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.267040300926 0.00000000 0.00000000 + O 2 1 0 1.307148087626 120.79301199 0.00000000 + H 1 2 3 1.040778510341 105.45854920 13.84615365 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.394359169392 0.00000000 0.00000000 + O 2 1 0 2.470151902092 120.79301199 0.00000000 + H 1 2 3 1.966786350615 105.45854920 13.84615365 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1681 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.292283680174 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.864e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5727418753317295 0.00e+00 9.50e-05 7.88e-04 3.15e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5727544192081098 -1.25e-05 6.69e-05 7.79e-04 3.46e-04 0.0 + 3 -205.5727506349606699 3.78e-06 5.72e-05 8.02e-04 1.08e-03 0.0 + 4 -205.5727544231826585 -3.79e-06 6.11e-05 8.15e-04 4.37e-04 0.0 + 5 -205.5727495400749660 4.88e-06 3.76e-05 6.84e-04 1.23e-03 0.0 + 6 -205.5727558981709819 -6.36e-06 1.35e-05 1.51e-04 4.16e-05 0.0 + 7 -205.5727559242866107 -2.61e-08 5.01e-06 6.10e-05 2.55e-05 0.0 + 8 -205.5727559409620824 -1.67e-08 1.32e-06 1.44e-05 4.85e-06 0.0 + 9 -205.5727559424506410 -1.49e-09 5.98e-07 6.08e-06 3.48e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57275594245064 Eh -5593.91908 eV + +Components: +Nuclear Repulsion : 70.29228368017382 Eh 1912.75028 eV +Electronic Energy : -275.86503962262452 Eh -7506.66936 eV +One Electron Energy: -420.20970428309562 Eh -11434.48737 eV +Two Electron Energy: 144.34466466047112 Eh 3927.81801 eV + +Virial components: +Potential Energy : -410.43974410457321 Eh -11168.63324 eV +Kinetic Energy : 204.86698816212257 Eh 5574.71416 eV +Virial Ratio : 2.00344500491104 + +DFT components: +N(Alpha) : 12.000001088201 electrons +N(Beta) : 12.000001088201 electrons +N(Total) : 24.000002176402 electrons +E(X) : -23.353935208081 Eh +E(C) : -0.805099935750 Eh +E(XC) : -24.159035143830 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.4886e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.0801e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 5.9758e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.3065e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.4837e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.0084e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 2.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 29.4 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000364275 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007268264 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.565851953361 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001746 -0.000004699 0.000001996 + 2 O : 0.000000034 0.000000552 -0.000000868 + 3 O : 0.000002078 0.000005202 0.000002068 + 4 H : -0.000000366 -0.000001055 -0.000003195 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000087915 +RMS gradient ... 0.0000025379 +MAX gradient ... 0.0000052022 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.016978540 -0.005163130 -0.001203349 + 2 O : -0.015813891 0.004573689 0.002988300 + 3 O : 0.008988512 -0.002276860 -0.001741266 + 4 H : -0.010153161 0.002866300 -0.000043686 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000048639 0.0000128276 0.0000075618 + +Norm of the Cartesian gradient ... 0.0282244255 +RMS gradient ... 0.0081476898 +MAX gradient ... 0.0169785402 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.120 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.1%) +RI-J Coulomb gradient .... 0.057 sec ( 47.7%) +XC gradient .... 0.016 sec ( 13.6%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.565851953 Eh +Current gradient norm .... 0.028224426 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999995874 +Lowest eigenvalues of augmented Hessian: + -0.000002435 0.267767697 0.396718071 0.469746484 0.678817449 +Length of the computed step .... 0.002872741 +The final length of the internal step .... 0.002872741 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0011727914 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0012214804 RMS(Int)= 0.0011725800 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000001218 +Previously predicted energy change .... -0.000010965 +Actually observed energy change .... -0.000013062 +Ratio of predicted to observed change .... 1.191252729 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000130621 0.0000050000 NO + RMS gradient 0.0003693056 0.0001000000 NO + MAX gradient 0.0006615888 0.0003000000 NO + RMS step 0.0011727914 0.0020000000 YES + MAX step 0.0025465973 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0004 Max(Angles) 0.15 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2670 0.000425 -0.0004 1.2667 + 2. B(O 2,O 1) 1.3071 0.000422 -0.0004 1.3067 + 3. B(H 3,N 0) 1.0408 0.000067 -0.0002 1.0405 + 4. A(O 1,N 0,H 3) 105.46 -0.000662 0.15 105.60 + 5. A(N 0,O 1,O 2) 120.79 -0.000130 0.04 120.83 + 6. D(O 2,O 1,N 0,H 3) 13.85 0.019997 0.00 13.85 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 8.058 %) +Internal coordinates : 0.000 s ( 3.038 %) +B/P matrices and projection : 0.000 s (12.417 %) +Hessian update/contruction : 0.000 s (40.423 %) +Making the step : 0.000 s ( 4.888 %) +Converting the step to Cartesian: 0.000 s ( 3.831 %) +Storing new data : 0.000 s ( 3.170 %) +Checking convergence : 0.000 s ( 2.510 %) +Final printing : 0.000 s (21.400 %) +Total time : 0.001 s + +Time for energy+gradient : 5.952 s +Time for complete geometry iter : 6.809 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.252838 -0.710535 -0.442953 + O 0.054475 0.510681 -0.579580 + O 0.489397 1.209399 0.435380 + H -0.309742 -0.871701 0.583445 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.477794 -1.342716 -0.837059 + 1 O 8.0000 0 15.999 0.102942 0.965047 -1.095247 + 2 O 8.0000 0 15.999 0.924826 2.285433 0.822748 + 3 H 1.0000 0 1.008 -0.585328 -1.647276 1.102551 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.266678686780 0.00000000 0.00000000 + O 2 1 0 1.306716373026 120.82995443 0.00000000 + H 1 2 3 1.040530744313 105.60445848 13.84615365 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.393675817688 0.00000000 0.00000000 + O 2 1 0 2.469336079730 120.82995443 0.00000000 + H 1 2 3 1.966318140678 105.60445848 13.84615365 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1681 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.306247412277 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.859e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22305 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5727482726138931 0.00e+00 2.95e-05 2.57e-04 6.26e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5727493001291180 -1.03e-06 1.33e-05 1.15e-04 5.94e-05 0.0 + 3 -205.5727492629658002 3.72e-08 1.47e-05 1.77e-04 1.68e-04 0.0 + 4 -205.5727492437800095 1.92e-08 1.51e-05 1.44e-04 1.33e-04 0.0 + 5 -205.5727493330100799 -8.92e-08 6.27e-06 1.07e-04 9.29e-05 0.0 + 6 -205.5727493222458122 1.08e-08 7.00e-06 6.66e-05 9.53e-05 0.0 + 7 -205.5727493710641340 -4.88e-08 2.57e-06 2.68e-05 1.46e-05 0.0 + 8 -205.5727493727782473 -1.71e-09 9.74e-07 1.07e-05 8.10e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57274937277825 Eh -5593.91890 eV + +Components: +Nuclear Repulsion : 70.30624741227669 Eh 1913.13025 eV +Electronic Energy : -275.87899678505494 Eh -7507.04915 eV +One Electron Energy: -420.23692550234040 Eh -11435.22810 eV +Two Electron Energy: 144.35792871728546 Eh 3928.17895 eV + +Virial components: +Potential Energy : -410.44145946378080 Eh -11168.67992 eV +Kinetic Energy : 204.86871009100258 Eh 5574.76102 eV +Virial Ratio : 2.00343653885195 + +DFT components: +N(Alpha) : 12.000001073221 electrons +N(Beta) : 12.000001073221 electrons +N(Total) : 24.000002146442 electrons +E(X) : -23.354511097611 Eh +E(C) : -0.805129588868 Eh +E(XC) : -24.159640686479 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.7141e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.0653e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 9.7408e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.1925e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 8.0994e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 9.4982e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 2.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 29.5 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000364268 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007260343 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.565853298390 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001749 -0.000004706 0.000001997 + 2 O : 0.000000035 0.000000554 -0.000000868 + 3 O : 0.000002081 0.000005211 0.000002062 + 4 H : -0.000000368 -0.000001059 -0.000003191 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000087996 +RMS gradient ... 0.0000025402 +MAX gradient ... 0.0000052106 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.017115882 -0.004675903 -0.000824375 + 2 O : -0.015763482 0.004521586 0.003117222 + 3 O : 0.008872994 -0.002432187 -0.002057652 + 4 H : -0.010225394 0.002586504 -0.000235195 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000124558 0.0000146612 0.0000078620 + +Norm of the Cartesian gradient ... 0.0281838558 +RMS gradient ... 0.0081359784 +MAX gradient ... 0.0171158816 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.124 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.1%) +RI-J Coulomb gradient .... 0.060 sec ( 47.9%) +XC gradient .... 0.019 sec ( 15.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.565853298 Eh +Current gradient norm .... 0.028183856 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999887 +Lowest eigenvalues of augmented Hessian: + -0.000000107 0.254864703 0.397600823 0.469595880 0.661861283 +Length of the computed step .... 0.000476339 +The final length of the internal step .... 0.000476339 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0001944647 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001184330 RMS(Int)= 0.0001944682 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000053 +Previously predicted energy change .... -0.000001218 +Actually observed energy change .... -0.000001345 +Ratio of predicted to observed change .... 1.104611759 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000013450 0.0000050000 YES + RMS gradient 0.0001017050 0.0001000000 NO + MAX gradient 0.0002280902 0.0003000000 YES + RMS step 0.0001944647 0.0020000000 YES + MAX step 0.0003474412 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0002 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2667 0.000228 -0.0002 1.2665 + 2. B(O 2,O 1) 1.3067 0.000056 -0.0001 1.3066 + 3. B(H 3,N 0) 1.0405 -0.000075 0.0001 1.0406 + 4. A(O 1,N 0,H 3) 105.60 -0.000036 0.01 105.62 + 5. A(N 0,O 1,O 2) 120.83 -0.000000 0.00 120.83 + 6. D(O 2,O 1,N 0,H 3) 13.85 0.019988 -0.00 13.85 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.030 %) +Internal coordinates : 0.000 s ( 2.830 %) +B/P matrices and projection : 0.000 s (11.860 %) +Hessian update/contruction : 0.000 s (34.097 %) +Making the step : 0.000 s ( 5.121 %) +Converting the step to Cartesian: 0.000 s ( 4.717 %) +Storing new data : 0.000 s ( 3.639 %) +Checking convergence : 0.000 s ( 1.348 %) +Final printing : 0.000 s (27.358 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.252799 -0.710389 -0.442949 + O 0.054483 0.510646 -0.579548 + O 0.489389 1.209404 0.435305 + H -0.309780 -0.871817 0.583484 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.477721 -1.342441 -0.837053 + 1 O 8.0000 0 15.999 0.102957 0.964982 -1.095188 + 2 O 8.0000 0 15.999 0.924810 2.285442 0.822608 + 3 H 1.0000 0 1.008 -0.585400 -1.647496 1.102626 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.266494828804 0.00000000 0.00000000 + O 2 1 0 1.306649705961 120.83451352 0.00000000 + H 1 2 3 1.040611296012 105.61858738 13.84615365 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.393328376466 0.00000000 0.00000000 + O 2 1 0 2.469210097235 120.83451352 0.00000000 + H 1 2 3 1.966470361328 105.61858738 13.84615365 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1681 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.311471597825 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.858e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22305 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.3114715978 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5727489142250874 0.00e+00 5.15e-06 4.44e-05 1.03e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5727489495208715 -3.53e-08 3.77e-06 4.84e-05 2.26e-05 0.0 + 3 -205.5727489384559021 1.11e-08 1.86e-06 3.35e-05 6.09e-05 0.0 + 4 -205.5727489535450445 -1.51e-08 2.30e-06 3.40e-05 1.06e-05 0.0 + 5 -205.5727489424401710 1.11e-08 1.87e-06 2.99e-05 5.46e-05 0.0 + 6 -205.5727489543090201 -1.19e-08 6.39e-07 6.66e-06 2.56e-06 0.0 + 7 -205.5727489549565803 -6.48e-10 3.27e-07 3.62e-06 2.88e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57274895495658 Eh -5593.91889 eV + +Components: +Nuclear Repulsion : 70.31147159782454 Eh 1913.27241 eV +Electronic Energy : -275.88422055278113 Eh -7507.19130 eV +One Electron Energy: -420.24645590063875 Eh -11435.48743 eV +Two Electron Energy: 144.36223534785759 Eh 3928.29613 eV + +Virial components: +Potential Energy : -410.44193089477073 Eh -11168.69275 eV +Kinetic Energy : 204.86918193981413 Eh 5574.77386 eV +Virial Ratio : 2.00343422572629 + +DFT components: +N(Alpha) : 12.000001071914 electrons +N(Beta) : 12.000001071914 electrons +N(Total) : 24.000002143828 electrons +E(X) : -23.354582883263 Eh +E(C) : -0.805138048134 Eh +E(XC) : -24.159720931397 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 6.4756e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.6232e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.2731e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.5910e-05 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.8839e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.2802e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.194351 -522.3049 + 1 2.0000 -19.019267 -517.5406 + 2 2.0000 -14.276320 -388.4784 + 3 2.0000 -1.259983 -34.2859 + 4 2.0000 -0.973316 -26.4853 + 5 2.0000 -0.721164 -19.6239 + 6 2.0000 -0.562186 -15.2979 + 7 2.0000 -0.526065 -14.3149 + 8 2.0000 -0.500302 -13.6139 + 9 2.0000 -0.333415 -9.0727 + 10 2.0000 -0.291526 -7.9328 + 11 2.0000 -0.267827 -7.2879 + 12 0.0000 -0.181243 -4.9319 + 13 0.0000 0.029732 0.8090 + 14 0.0000 0.104956 2.8560 + 15 0.0000 0.140013 3.8099 + 16 0.0000 0.224196 6.1007 + 17 0.0000 0.275157 7.4874 + 18 0.0000 0.297275 8.0893 + 19 0.0000 0.331650 9.0247 + 20 0.0000 0.358207 9.7473 + 21 0.0000 0.371993 10.1224 + 22 0.0000 0.396215 10.7816 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.240384 + 1 O : 0.228983 + 2 O : -0.244630 + 3 H : 0.256031 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.854741 s : 3.854741 + pz : 1.353488 p : 3.332903 + px : 1.077184 + py : 0.902231 + dz2 : 0.013351 d : 0.052741 + dxz : -0.000836 + dyz : 0.008133 + dx2y2 : 0.014947 + dxy : 0.017146 + + 1 O s : 3.734012 s : 3.734012 + pz : 1.434885 p : 3.891318 + px : 1.332275 + py : 1.124158 + dz2 : 0.039416 d : 0.145687 + dxz : 0.016594 + dyz : 0.026616 + dx2y2 : 0.026751 + dxy : 0.036309 + + 2 O s : 3.941009 s : 3.941009 + pz : 1.345093 p : 4.282827 + px : 1.372607 + py : 1.565127 + dz2 : 0.000405 d : 0.020795 + dxz : 0.006781 + dyz : 0.008433 + dx2y2 : 0.002883 + dxy : 0.002293 + + 3 H s : 0.715761 s : 0.715761 + pz : 0.018405 p : 0.028208 + px : 0.005228 + py : 0.004575 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.035519 + 1 O : -0.183284 + 2 O : -0.058317 + 3 H : 0.277121 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.344011 s : 3.344011 + pz : 1.315486 p : 3.377585 + px : 1.013654 + py : 1.048445 + dz2 : 0.062759 d : 0.313923 + dxz : 0.007167 + dyz : 0.092707 + dx2y2 : 0.083229 + dxy : 0.068060 + + 1 O s : 3.357406 s : 3.357406 + pz : 1.461449 p : 4.043423 + px : 1.262094 + py : 1.319880 + dz2 : 0.161259 d : 0.782454 + dxz : 0.069810 + dyz : 0.212186 + dx2y2 : 0.170255 + dxy : 0.168945 + + 2 O s : 3.601162 s : 3.601162 + pz : 1.345841 p : 4.207621 + px : 1.321389 + py : 1.540391 + dz2 : 0.076412 d : 0.249535 + dxz : 0.046782 + dyz : 0.063087 + dx2y2 : 0.032890 + dxy : 0.030364 + + 3 H s : 0.650023 s : 0.650023 + pz : 0.051305 p : 0.072856 + px : 0.012369 + py : 0.009182 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2404 7.0000 -0.2404 2.7898 2.7898 -0.0000 + 1 O 7.7710 8.0000 0.2290 2.6529 2.6529 0.0000 + 2 O 8.2446 8.0000 -0.2446 1.6782 1.6782 0.0000 + 3 H 0.7440 1.0000 0.2560 0.9322 0.9322 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4498 B( 0-N , 2-O ) : 0.4660 B( 0-N , 3-H ) : 0.8740 +B( 1-O , 2-O ) : 1.1786 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.004 sec +Sum of individual times .... 1.986 sec ( 99.1%) + +SCF preparation .... 0.725 sec ( 36.2%) +Fock matrix formation .... 0.194 sec ( 9.7%) + Startup .... 0.010 sec ( 5.1% of F) + Split-RI-J .... 0.031 sec ( 15.7% of F) + XC integration .... 0.123 sec ( 63.5% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.008 sec ( 6.2% of XC) + Density eval. .... 0.010 sec ( 7.9% of XC) + XC-Functional eval. .... 0.007 sec ( 5.5% of XC) + XC-Potential eval. .... 0.010 sec ( 8.3% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.012 sec ( 0.6%) +Total Energy calculation .... 0.016 sec ( 0.8%) +Population analysis .... 0.980 sec ( 48.9%) +Orbital Transformation .... 0.007 sec ( 0.3%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.011 sec ( 0.5%) +SOSCF solution .... 0.041 sec ( 2.1%) +Finished LeanSCF after 3.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 29.9 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000364270 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007259862 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.565853363119 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.022.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.022.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.194877 0.670863 -0.318511 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5727489549565803 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.166140605 0.615772748 -0.483842694 +Nuclear contribution : -0.384344176 -1.141905211 0.706880867 + ----------------------------------------- +Total Dipole Moment : -0.218203570 -0.526132463 0.223038173 + ----------------------------------------- +Magnitude (a.u.) : 0.611697796 +Magnitude (Debye) : 1.554812234 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.965307 0.439328 0.383356 +Rotational constants in MHz : 88897.659273 13170.713787 11492.722652 + +Dipole components along the rotational axes: +x,y,z [a.u.] : 0.442391 0.411866 -0.093976 +x,y,z [Debye]: 1.124468 1.046879 -0.238867 + + + +Dipole moment calculation done in 0.4 sec + +Maximum memory used throughout the entire PROP-calculation: 15.9 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 23 * + * * + * Dihedral ( 2, 1, 0, 3) : 23.07692308 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2686 0.788964 + 2. B(O 2,O 1) 1.3079 0.680758 + 3. B(H 3,N 0) 1.0424 0.386684 + 4. A(O 1,N 0,H 3) 105.3676 0.364300 + 5. A(N 0,O 1,O 2) 120.5834 0.448984 + 6. D(O 2,O 1,N 0,H 3) 23.0769 0.050033 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.216084 -0.719115 -0.442717 + O 0.021630 0.520454 -0.570147 + O 0.510209 1.210364 0.427797 + H -0.334464 -0.873859 0.581359 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.408339 -1.358930 -0.836614 + 1 O 8.0000 0 15.999 0.040876 0.983515 -1.077422 + 2 O 8.0000 0 15.999 0.964156 2.287257 0.808419 + 3 H 1.0000 0 1.008 -0.632046 -1.651355 1.098610 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.266494828804 0.00000000 0.00000000 + O 2 1 0 1.306649705961 120.83451352 0.00000000 + H 1 2 3 1.040611296012 105.61858738 13.84615365 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.393328376466 0.00000000 0.00000000 + O 2 1 0 2.469210097235 120.83451352 0.00000000 + H 1 2 3 1.966470361328 105.61858738 13.84615365 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1681 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.224983416600 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.900e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22305 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.2249834166 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.7 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5639959184686063 0.00e+00 3.73e-04 3.81e-03 2.78e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.082) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5651802084341853 -1.18e-03 4.45e-04 4.22e-03 2.16e-02 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.5661601350632282 -9.80e-04 3.39e-04 3.04e-03 1.53e-02 0.700 0.0 + 4 -205.5668485776929515 -6.88e-04 8.53e-04 7.38e-03 1.08e-02 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5684596879290211 -1.61e-03 1.05e-04 1.32e-03 1.32e-03 0.0 + *** Restarting incremental Fock matrix formation *** + 6 -205.5684597091157571 -2.12e-08 4.22e-04 6.30e-03 1.68e-03 0.0 + 7 -205.5680961635630979 3.64e-04 3.43e-04 5.41e-03 1.02e-02 0.0 + 8 -205.5684800974672726 -3.84e-04 1.57e-05 1.41e-04 1.33e-04 0.0 + 9 -205.5684802326290992 -1.35e-07 6.02e-06 5.34e-05 3.39e-05 0.0 + 10 -205.5684802522206951 -1.96e-08 4.10e-06 5.31e-05 5.47e-05 0.0 + 11 -205.5684802533952507 -1.17e-09 3.05e-06 2.72e-05 4.03e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56848025339525 Eh -5593.80273 eV + +Components: +Nuclear Repulsion : 70.22498341659976 Eh 1910.91895 eV +Electronic Energy : -275.79346366999494 Eh -7504.72168 eV +One Electron Energy: -420.08252929343797 Eh -11431.02676 eV +Two Electron Energy: 144.28906562344301 Eh 3926.30509 eV + +Virial components: +Potential Energy : -410.43339406126518 Eh -11168.46045 eV +Kinetic Energy : 204.86491380786993 Eh 5574.65771 eV +Virial Ratio : 2.00343429449410 + +DFT components: +N(Alpha) : 12.000000870020 electrons +N(Beta) : 12.000000870020 electrons +N(Total) : 24.000001740040 electrons +E(X) : -23.351755967524 Eh +E(C) : -0.804991485349 Eh +E(XC) : -24.156747452873 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.1746e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.7219e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.0481e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.3187e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.0251e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 4.5274e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.193256 -522.2750 + 1 2.0000 -19.020473 -517.5734 + 2 2.0000 -14.275411 -388.4537 + 3 2.0000 -1.258430 -34.2436 + 4 2.0000 -0.972274 -26.4569 + 5 2.0000 -0.720138 -19.5959 + 6 2.0000 -0.562939 -15.3183 + 7 2.0000 -0.524710 -14.2781 + 8 2.0000 -0.499451 -13.5908 + 9 2.0000 -0.333685 -9.0800 + 10 2.0000 -0.288924 -7.8620 + 11 2.0000 -0.268156 -7.2969 + 12 0.0000 -0.184803 -5.0287 + 13 0.0000 0.031032 0.8444 + 14 0.0000 0.102348 2.7850 + 15 0.0000 0.139609 3.7990 + 16 0.0000 0.224702 6.1145 + 17 0.0000 0.272019 7.4020 + 18 0.0000 0.300155 8.1676 + 19 0.0000 0.331091 9.0094 + 20 0.0000 0.356360 9.6970 + 21 0.0000 0.377364 10.2686 + 22 0.0000 0.396380 10.7860 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.244537 + 1 O : 0.222148 + 2 O : -0.236683 + 3 H : 0.259072 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.851972 s : 3.851972 + pz : 1.358554 p : 3.338790 + px : 1.084761 + py : 0.895475 + dz2 : 0.014282 d : 0.053775 + dxz : -0.000680 + dyz : 0.008722 + dx2y2 : 0.014407 + dxy : 0.017044 + + 1 O s : 3.735885 s : 3.735885 + pz : 1.438479 p : 3.898389 + px : 1.335535 + py : 1.124375 + dz2 : 0.037499 d : 0.143578 + dxz : 0.015629 + dyz : 0.027775 + dx2y2 : 0.025118 + dxy : 0.037557 + + 2 O s : 3.940521 s : 3.940521 + pz : 1.357178 p : 4.276265 + px : 1.330445 + py : 1.588643 + dz2 : 0.001137 d : 0.019896 + dxz : 0.005833 + dyz : 0.007727 + dx2y2 : 0.002904 + dxy : 0.002294 + + 3 H s : 0.712695 s : 0.712695 + pz : 0.018166 p : 0.028233 + px : 0.005564 + py : 0.004503 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.039571 + 1 O : -0.183553 + 2 O : -0.055326 + 3 H : 0.278450 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.345277 s : 3.345277 + pz : 1.318880 p : 3.380281 + px : 1.014471 + py : 1.046930 + dz2 : 0.061971 d : 0.314013 + dxz : 0.006577 + dyz : 0.094133 + dx2y2 : 0.085396 + dxy : 0.065936 + + 1 O s : 3.359121 s : 3.359121 + pz : 1.460221 p : 4.044524 + px : 1.262271 + py : 1.322031 + dz2 : 0.154902 d : 0.779909 + dxz : 0.071404 + dyz : 0.211398 + dx2y2 : 0.171892 + dxy : 0.170313 + + 2 O s : 3.602543 s : 3.602543 + pz : 1.355727 p : 4.203622 + px : 1.288244 + py : 1.559651 + dz2 : 0.072842 d : 0.249161 + dxz : 0.049501 + dyz : 0.060604 + dx2y2 : 0.034957 + dxy : 0.031257 + + 3 H s : 0.648812 s : 0.648812 + pz : 0.050653 p : 0.072738 + px : 0.013059 + py : 0.009026 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2445 7.0000 -0.2445 2.7900 2.7900 0.0000 + 1 O 7.7779 8.0000 0.2221 2.6451 2.6451 -0.0000 + 2 O 8.2367 8.0000 -0.2367 1.6775 1.6775 -0.0000 + 3 H 0.7409 1.0000 0.2591 0.9303 0.9303 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4444 B( 0-N , 2-O ) : 0.4706 B( 0-N , 3-H ) : 0.8750 +B( 1-O , 2-O ) : 1.1761 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.028 sec +Sum of individual times .... 2.015 sec ( 99.4%) + +SCF preparation .... 0.697 sec ( 34.4%) +Fock matrix formation .... 0.267 sec ( 13.2%) + Startup .... 0.013 sec ( 4.7% of F) + Split-RI-J .... 0.039 sec ( 14.6% of F) + XC integration .... 0.174 sec ( 65.2% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.009 sec ( 4.9% of XC) + Density eval. .... 0.016 sec ( 9.4% of XC) + XC-Functional eval. .... 0.010 sec ( 5.5% of XC) + XC-Potential eval. .... 0.018 sec ( 10.1% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.019 sec ( 0.9%) +Total Energy calculation .... 0.023 sec ( 1.1%) +Population analysis .... 0.893 sec ( 44.1%) +Orbital Transformation .... 0.014 sec ( 0.7%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.067 sec ( 3.3%) +SOSCF solution .... 0.036 sec ( 1.8%) +Finished LeanSCF after 3.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 30.2 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000364231 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007254254 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.561590230804 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001914 -0.000004708 0.000001999 + 2 O : -0.000000014 0.000000567 -0.000000854 + 3 O : 0.000002125 0.000005292 0.000002033 + 4 H : -0.000000197 -0.000001151 -0.000003178 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000088878 +RMS gradient ... 0.0000025657 +MAX gradient ... 0.0000052920 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.028611916 -0.005100178 -0.002834659 + 2 O : -0.026047637 0.004928072 0.006698431 + 3 O : 0.014286565 -0.003849595 -0.004208863 + 4 H : -0.016850844 0.004021701 0.000345091 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000199663 0.0000090136 0.0000265999 + +Norm of the Cartesian gradient ... 0.0462299371 +RMS gradient ... 0.0133454333 +MAX gradient ... 0.0286119165 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.118 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.9%) +RI-J Coulomb gradient .... 0.054 sec ( 46.3%) +XC gradient .... 0.019 sec ( 16.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.561590231 Eh +Current gradient norm .... 0.046229937 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999956847 +Lowest eigenvalues of augmented Hessian: + -0.000034871 0.363421609 0.384095122 0.448001823 0.677660719 +Length of the computed step .... 0.009290417 +The final length of the internal step .... 0.009290417 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0037927968 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0049486227 RMS(Int)= 0.0037894545 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0015636373 0.0001000000 NO + MAX gradient 0.0024009702 0.0003000000 NO + RMS step 0.0037927968 0.0020000000 NO + MAX step 0.0066062241 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0023 Max(Angles) 0.38 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2686 -0.001401 0.0009 1.2695 + 2. B(O 2,O 1) 1.3079 0.000097 -0.0001 1.3078 + 3. B(H 3,N 0) 1.0424 0.001654 -0.0023 1.0402 + 4. A(O 1,N 0,H 3) 105.37 -0.002401 0.38 105.75 + 5. A(N 0,O 1,O 2) 120.58 -0.002049 0.26 120.85 + 6. D(O 2,O 1,N 0,H 3) 23.08 0.032690 0.00 23.08 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (11.327 %) +Internal coordinates : 0.000 s ( 4.045 %) +B/P matrices and projection : 0.000 s (18.932 %) +Hessian update/contruction : 0.000 s (27.023 %) +Making the step : 0.000 s ( 6.311 %) +Converting the step to Cartesian: 0.000 s ( 5.340 %) +Storing new data : 0.000 s ( 4.045 %) +Checking convergence : 0.000 s ( 0.000 %) +Final printing : 0.000 s (22.654 %) +Total time : 0.001 s + +Time for energy+gradient : 7.134 s +Time for complete geometry iter : 8.045 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.216700 -0.719074 -0.440825 + O 0.022720 0.521100 -0.568599 + O 0.511746 1.215565 0.425861 + H -0.336475 -0.879746 0.579855 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.409504 -1.358854 -0.833038 + 1 O 8.0000 0 15.999 0.042935 0.984735 -1.074497 + 2 O 8.0000 0 15.999 0.967060 2.297085 0.804761 + 3 H 1.0000 0 1.008 -0.635845 -1.662479 1.095766 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.269519476211 0.00000000 0.00000000 + O 2 1 0 1.307814871761 120.84543486 0.00000000 + H 1 2 3 1.040166953523 105.74612475 23.07692314 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.399044131719 0.00000000 0.00000000 + O 2 1 0 2.471411941498 120.84543486 0.00000000 + H 1 2 3 1.965630675714 105.74612475 23.07692314 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1681 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.181028993922 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.896e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22307 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5684463559465200 0.00e+00 1.12e-04 8.81e-04 3.90e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5684644425443537 -1.81e-05 7.86e-05 8.04e-04 4.23e-04 0.1 + 3 -205.5684605909880531 3.85e-06 6.24e-05 9.75e-04 1.03e-03 0.0 + 4 -205.5684645610274117 -3.97e-06 8.14e-05 1.25e-03 6.86e-04 0.0 + 5 -205.5684521452843967 1.24e-05 5.73e-05 9.24e-04 1.58e-03 0.0 + 6 -205.5684669365120101 -1.48e-05 1.07e-05 8.92e-05 4.37e-05 0.0 + 7 -205.5684669704849910 -3.40e-08 3.11e-06 2.52e-05 1.62e-05 0.0 + 8 -205.5684669770989501 -6.61e-09 4.13e-07 4.03e-06 1.70e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56846697709895 Eh -5593.80237 eV + +Components: +Nuclear Repulsion : 70.18102899392173 Eh 1909.72289 eV +Electronic Energy : -275.74949597102068 Eh -7503.52526 eV +One Electron Energy: -419.99574198249979 Eh -11428.66516 eV +Two Electron Energy: 144.24624601147914 Eh 3925.13990 eV + +Virial components: +Potential Energy : -410.43238120700107 Eh -11168.43288 eV +Kinetic Energy : 204.86391422990209 Eh 5574.63051 eV +Virial Ratio : 2.00343912567445 + +DFT components: +N(Alpha) : 12.000000839894 electrons +N(Beta) : 12.000000839894 electrons +N(Total) : 24.000001679788 electrons +E(X) : -23.351572310884 Eh +E(C) : -0.804932035479 Eh +E(XC) : -24.156504346363 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 6.6140e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.0281e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.1274e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.5067e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.6954e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 4.0629e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 2.3 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 30.4 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000364150 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007220336 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.561610791234 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001929 -0.000004752 0.000001993 + 2 O : -0.000000011 0.000000572 -0.000000855 + 3 O : 0.000002151 0.000005360 0.000002026 + 4 H : -0.000000211 -0.000001180 -0.000003165 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000089583 +RMS gradient ... 0.0000025860 +MAX gradient ... 0.0000053601 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.028105912 -0.005881127 -0.001129273 + 2 O : -0.025676517 0.005499265 0.006807328 + 3 O : 0.014375332 -0.003054924 -0.004389110 + 4 H : -0.016804727 0.003436786 -0.001288945 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000009326 0.0000009517 0.0000224249 + +Norm of the Cartesian gradient ... 0.0457470123 +RMS gradient ... 0.0132060249 +MAX gradient ... 0.0281059123 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.137 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.006 sec ( 4.3%) +RI-J Coulomb gradient .... 0.066 sec ( 48.3%) +XC gradient .... 0.021 sec ( 15.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.561610791 Eh +Current gradient norm .... 0.045747012 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999995965 +Lowest eigenvalues of augmented Hessian: + -0.000002373 0.280624624 0.389846384 0.458469413 0.682991138 +Length of the computed step .... 0.002840891 +The final length of the internal step .... 0.002840891 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0011597888 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0012999450 RMS(Int)= 0.0011595731 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000001186 +Previously predicted energy change .... -0.000017437 +Actually observed energy change .... -0.000020560 +Ratio of predicted to observed change .... 1.179112533 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000205604 0.0000050000 NO + RMS gradient 0.0003511817 0.0001000000 NO + MAX gradient 0.0007279087 0.0003000000 NO + RMS step 0.0011597888 0.0020000000 YES + MAX step 0.0026322533 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0004 Max(Angles) 0.15 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2695 0.000012 0.0000 1.2695 + 2. B(O 2,O 1) 1.3078 0.000416 -0.0004 1.3074 + 3. B(H 3,N 0) 1.0402 0.000140 -0.0003 1.0399 + 4. A(O 1,N 0,H 3) 105.75 -0.000728 0.15 105.90 + 5. A(N 0,O 1,O 2) 120.85 -0.000132 0.03 120.87 + 6. D(O 2,O 1,N 0,H 3) 23.08 0.032540 0.00 23.08 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 5.801 %) +Internal coordinates : 0.000 s ( 2.262 %) +B/P matrices and projection : 0.000 s ( 9.243 %) +Hessian update/contruction : 0.000 s (35.202 %) +Making the step : 0.000 s ( 4.130 %) +Converting the step to Cartesian: 0.000 s ( 3.048 %) +Storing new data : 0.000 s ( 2.557 %) +Checking convergence : 0.000 s ( 1.082 %) +Final printing : 0.000 s (36.382 %) +Total time : 0.001 s + +Time for energy+gradient : 6.537 s +Time for complete geometry iter : 7.392 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.216698 -0.718615 -0.440220 + O 0.023058 0.521471 -0.568408 + O 0.511986 1.216492 0.425192 + H -0.337054 -0.881504 0.579729 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.409500 -1.357986 -0.831895 + 1 O 8.0000 0 15.999 0.043573 0.985438 -1.074136 + 2 O 8.0000 0 15.999 0.967513 2.298837 0.803496 + 3 H 1.0000 0 1.008 -0.636940 -1.665802 1.095528 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.269539293962 0.00000000 0.00000000 + O 2 1 0 1.307419336850 120.87407093 0.00000000 + H 1 2 3 1.039862034583 105.89694176 23.07692314 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.399081581840 0.00000000 0.00000000 + O 2 1 0 2.470664488840 120.87407093 0.00000000 + H 1 2 3 1.965054462423 105.89694176 23.07692314 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1680 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.185296320767 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.892e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22307 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5684593001787164 0.00e+00 2.76e-05 2.56e-04 5.91e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5684602395856189 -9.39e-07 1.12e-05 8.10e-05 5.73e-05 0.0 + 3 -205.5684603023350689 -6.27e-08 7.01e-06 7.96e-05 5.93e-05 0.0 + 4 -205.5684602704827455 3.19e-08 6.10e-06 7.42e-05 7.99e-05 0.0 + 5 -205.5684603058191158 -3.53e-08 8.83e-06 1.18e-04 5.35e-05 0.0 + 6 -205.5684601766247681 1.29e-07 7.46e-06 8.84e-05 1.26e-04 0.0 + 7 -205.5684603186781771 -1.42e-07 3.71e-07 3.61e-06 1.65e-06 0.0 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56846031867818 Eh -5593.80219 eV + +Components: +Nuclear Repulsion : 70.18529632076738 Eh 1909.83901 eV +Electronic Energy : -275.75375663944556 Eh -7503.64120 eV +One Electron Energy: -420.00392068300380 Eh -11428.88772 eV +Two Electron Energy: 144.25016404355821 Eh 3925.24652 eV + +Virial components: +Potential Energy : -410.43306862893087 Eh -11168.45159 eV +Kinetic Energy : 204.86460831025269 Eh 5574.64940 eV +Virial Ratio : 2.00343569352574 + +DFT components: +N(Alpha) : 12.000000823457 electrons +N(Beta) : 12.000000823457 electrons +N(Total) : 24.000001646914 electrons +E(X) : -23.351823477294 Eh +E(C) : -0.804943113031 Eh +E(XC) : -24.156766590325 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.4205e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.6109e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.7083e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.5436e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.6505e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.9811e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 2.1 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 30.6 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000364139 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007212381 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.561612076945 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000001932 -0.000004760 0.000001994 + 2 O : -0.000000009 0.000000575 -0.000000855 + 3 O : 0.000002155 0.000005371 0.000002021 + 4 H : -0.000000214 -0.000001186 -0.000003161 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000089695 +RMS gradient ... 0.0000025893 +MAX gradient ... 0.0000053712 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.028119712 -0.005694925 -0.000628279 + 2 O : -0.025541619 0.005748659 0.006765969 + 3 O : 0.014264505 -0.003179102 -0.004617854 + 4 H : -0.016842599 0.003125368 -0.001519835 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000044156 0.0000001497 0.0000237127 + +Norm of the Cartesian gradient ... 0.0456662143 +RMS gradient ... 0.0131827006 +MAX gradient ... 0.0281197118 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.126 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.006 sec ( 5.1%) +RI-J Coulomb gradient .... 0.058 sec ( 45.8%) +XC gradient .... 0.021 sec ( 16.4%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.561612077 Eh +Current gradient norm .... 0.045666214 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999910 +Lowest eigenvalues of augmented Hessian: + -0.000000084 0.261358617 0.390443848 0.459611108 0.661337837 +Length of the computed step .... 0.000423095 +The final length of the internal step .... 0.000423095 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0001727277 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001297743 RMS(Int)= 0.0001727268 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000042 +Previously predicted energy change .... -0.000001186 +Actually observed energy change .... -0.000001286 +Ratio of predicted to observed change .... 1.083680930 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000012857 0.0000050000 YES + RMS gradient 0.0000902824 0.0001000000 YES + MAX gradient 0.0001625439 0.0003000000 YES + RMS step 0.0001727277 0.0020000000 YES + MAX step 0.0002401489 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2695 0.000163 -0.0001 1.2694 + 2. B(O 2,O 1) 1.3074 0.000135 -0.0001 1.3073 + 3. B(H 3,N 0) 1.0399 -0.000030 0.0000 1.0399 + 4. A(O 1,N 0,H 3) 105.90 -0.000037 0.01 105.91 + 5. A(N 0,O 1,O 2) 120.87 -0.000044 0.01 120.88 + 6. D(O 2,O 1,N 0,H 3) 23.08 0.032509 -0.00 23.08 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.141 %) +Internal coordinates : 0.000 s ( 3.047 %) +B/P matrices and projection : 0.000 s (11.911 %) +Hessian update/contruction : 0.000 s (33.657 %) +Making the step : 0.000 s ( 7.341 %) +Converting the step to Cartesian: 0.000 s ( 3.878 %) +Storing new data : 0.000 s ( 3.186 %) +Checking convergence : 0.000 s ( 1.801 %) +Final printing : 0.000 s (25.900 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.216682 -0.718506 -0.440192 + O 0.023096 0.521465 -0.568333 + O 0.511981 1.216535 0.425086 + H -0.337103 -0.881650 0.579731 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.409470 -1.357779 -0.831843 + 1 O 8.0000 0 15.999 0.043646 0.985426 -1.073994 + 2 O 8.0000 0 15.999 0.967505 2.298918 0.803297 + 3 H 1.0000 0 1.008 -0.637033 -1.666077 1.095533 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.269425576215 0.00000000 0.00000000 + O 2 1 0 1.307292255517 120.88254145 0.00000000 + H 1 2 3 1.039885246785 105.90992874 23.07692314 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.398866686442 0.00000000 0.00000000 + O 2 1 0 2.470424339923 120.88254145 0.00000000 + H 1 2 3 1.965098327129 105.90992874 23.07692314 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1681 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.190248769914 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.890e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22307 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.1902487699 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5684596008574943 0.00e+00 5.41e-06 5.27e-05 1.02e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5684596331862224 -3.23e-08 3.05e-06 2.87e-05 1.17e-05 0.0 + 3 -205.5684596285873624 4.60e-09 1.92e-06 2.98e-05 3.46e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 3 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56845962858736 Eh -5593.80217 eV + +Components: +Nuclear Repulsion : 70.19024876991406 Eh 1909.97377 eV +Electronic Energy : -275.75870839850143 Eh -7503.77594 eV +One Electron Energy: -420.01300781787916 Eh -11429.13499 eV +Two Electron Energy: 144.25429941937776 Eh 3925.35905 eV + +Virial components: +Potential Energy : -410.43331940667582 Eh -11168.45841 eV +Kinetic Energy : 204.86485977808846 Eh 5574.65624 eV +Virial Ratio : 2.00343445845842 + +DFT components: +N(Alpha) : 12.000000821893 electrons +N(Beta) : 12.000000821893 electrons +N(Total) : 24.000001643787 electrons +E(X) : -23.351924668607 Eh +E(C) : -0.804953026056 Eh +E(XC) : -24.156877694663 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -4.5989e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.9806e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.9160e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.3591e-05 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.4650e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 6.0136e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.193395 -522.2788 + 1 2.0000 -19.020744 -517.5808 + 2 2.0000 -14.274978 -388.4419 + 3 2.0000 -1.257994 -34.2318 + 4 2.0000 -0.972547 -26.4643 + 5 2.0000 -0.720477 -19.6052 + 6 2.0000 -0.563302 -15.3282 + 7 2.0000 -0.524526 -14.2731 + 8 2.0000 -0.499598 -13.5947 + 9 2.0000 -0.333177 -9.0662 + 10 2.0000 -0.288977 -7.8635 + 11 2.0000 -0.268105 -7.2955 + 12 0.0000 -0.184748 -5.0272 + 13 0.0000 0.031516 0.8576 + 14 0.0000 0.102392 2.7862 + 15 0.0000 0.139333 3.7914 + 16 0.0000 0.224997 6.1225 + 17 0.0000 0.272121 7.4048 + 18 0.0000 0.300336 8.1725 + 19 0.0000 0.330898 9.0042 + 20 0.0000 0.356485 9.7004 + 21 0.0000 0.377175 10.2634 + 22 0.0000 0.396728 10.7955 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.244911 + 1 O : 0.222489 + 2 O : -0.235714 + 3 H : 0.258137 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.850560 s : 3.850560 + pz : 1.360213 p : 3.340942 + px : 1.086141 + py : 0.894589 + dz2 : 0.014096 d : 0.053409 + dxz : -0.000684 + dyz : 0.008645 + dx2y2 : 0.014405 + dxy : 0.016947 + + 1 O s : 3.734906 s : 3.734906 + pz : 1.440927 p : 3.898788 + px : 1.335481 + py : 1.122381 + dz2 : 0.037501 d : 0.143817 + dxz : 0.015609 + dyz : 0.027512 + dx2y2 : 0.025464 + dxy : 0.037732 + + 2 O s : 3.940655 s : 3.940655 + pz : 1.364399 p : 4.275267 + px : 1.329028 + py : 1.581840 + dz2 : 0.001049 d : 0.019793 + dxz : 0.005794 + dyz : 0.007684 + dx2y2 : 0.002909 + dxy : 0.002357 + + 3 H s : 0.713460 s : 0.713460 + pz : 0.018203 p : 0.028403 + px : 0.005639 + py : 0.004561 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.039459 + 1 O : -0.183613 + 2 O : -0.053981 + 3 H : 0.277053 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.343750 s : 3.343750 + pz : 1.321288 p : 3.382249 + px : 1.015716 + py : 1.045244 + dz2 : 0.061592 d : 0.313460 + dxz : 0.006604 + dyz : 0.094308 + dx2y2 : 0.085184 + dxy : 0.065771 + + 1 O s : 3.359016 s : 3.359016 + pz : 1.461464 p : 4.044281 + px : 1.262404 + py : 1.320413 + dz2 : 0.154632 d : 0.780316 + dxz : 0.071005 + dyz : 0.210949 + dx2y2 : 0.172553 + dxy : 0.171177 + + 2 O s : 3.602393 s : 3.602393 + pz : 1.361104 p : 4.202645 + px : 1.286946 + py : 1.554595 + dz2 : 0.072462 d : 0.248943 + dxz : 0.049272 + dyz : 0.060690 + dx2y2 : 0.035044 + dxy : 0.031475 + + 3 H s : 0.649639 s : 0.649639 + pz : 0.050768 p : 0.073308 + px : 0.013277 + py : 0.009263 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2449 7.0000 -0.2449 2.7920 2.7920 0.0000 + 1 O 7.7775 8.0000 0.2225 2.6447 2.6447 0.0000 + 2 O 8.2357 8.0000 -0.2357 1.6789 1.6789 0.0000 + 3 H 0.7419 1.0000 0.2581 0.9304 0.9304 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4438 B( 0-N , 2-O ) : 0.4724 B( 0-N , 3-H ) : 0.8758 +B( 1-O , 2-O ) : 1.1764 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.901 sec +Sum of individual times .... 1.888 sec ( 99.3%) + +SCF preparation .... 0.719 sec ( 37.9%) +Fock matrix formation .... 0.092 sec ( 4.8%) + Startup .... 0.006 sec ( 6.1% of F) + Split-RI-J .... 0.014 sec ( 15.1% of F) + XC integration .... 0.061 sec ( 66.3% of F) + Basis function eval. .... 0.004 sec ( 5.9% of XC) + Density eval. .... 0.005 sec ( 8.1% of XC) + XC-Functional eval. .... 0.003 sec ( 5.3% of XC) + XC-Potential eval. .... 0.005 sec ( 8.1% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.005 sec ( 0.3%) +Total Energy calculation .... 0.007 sec ( 0.3%) +Population analysis .... 1.030 sec ( 54.2%) +Orbital Transformation .... 0.007 sec ( 0.4%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.010 sec ( 0.5%) +SOSCF solution .... 0.018 sec ( 0.9%) +Finished LeanSCF after 3.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 30.9 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000364140 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007211646 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.561612122581 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.023.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.023.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.208449 0.677438 -0.316470 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5684596285873624 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.170182373 0.638326714 -0.464400494 +Nuclear contribution : -0.416899284 -1.154295219 0.702338585 + ----------------------------------------- +Total Dipole Moment : -0.246716911 -0.515968505 0.237938090 + ----------------------------------------- +Magnitude (a.u.) : 0.619441093 +Magnitude (Debye) : 1.574494130 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.966555 0.436433 0.382388 +Rotational constants in MHz : 88935.083620 13083.937206 11463.704905 + +Dipole components along the rotational axes: +x,y,z [a.u.] : 0.441050 0.405852 -0.156418 +x,y,z [Debye]: 1.121060 1.031593 -0.397582 + + + +Dipole moment calculation done in 0.4 sec + +Maximum memory used throughout the entire PROP-calculation: 16.4 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 24 * + * * + * Dihedral ( 2, 1, 0, 3) : 32.30769231 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2714 0.780515 + 2. B(O 2,O 1) 1.3086 0.679153 + 3. B(H 3,N 0) 1.0418 0.387717 + 4. A(O 1,N 0,H 3) 105.6673 0.363795 + 5. A(N 0,O 1,O 2) 120.6396 0.447917 + 6. D(O 2,O 1,N 0,H 3) 32.3077 0.048833 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.180257 -0.724506 -0.437406 + O -0.008416 0.529690 -0.555011 + O 0.533632 1.222323 0.413950 + H -0.363668 -0.889663 0.574759 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.340636 -1.369119 -0.826577 + 1 O 8.0000 0 15.999 -0.015904 1.000970 -1.048819 + 2 O 8.0000 0 15.999 1.008419 2.309856 0.782253 + 3 H 1.0000 0 1.008 -0.687232 -1.681220 1.086137 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.269425576215 0.00000000 0.00000000 + O 2 1 0 1.307292255517 120.88254145 0.00000000 + H 1 2 3 1.039885246785 105.90992874 23.07692314 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.398866686442 0.00000000 0.00000000 + O 2 1 0 2.470424339923 120.88254145 0.00000000 + H 1 2 3 1.965098327129 105.90992874 23.07692314 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1680 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.095501003338 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.915e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22302 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.0955010033 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5578495285810163 0.00e+00 3.77e-04 3.81e-03 2.64e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.078) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5590058160231592 -1.16e-03 4.48e-04 4.24e-03 2.05e-02 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.5599629785717184 -9.57e-04 3.41e-04 3.04e-03 1.45e-02 0.700 0.1 + 4 -205.5606328233315594 -6.70e-04 8.57e-04 7.40e-03 1.03e-02 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5622063961055233 -1.57e-03 1.17e-04 1.47e-03 1.76e-03 0.0 + *** Restarting incremental Fock matrix formation *** + 6 -205.5622066406036765 -2.44e-07 4.65e-04 6.63e-03 1.73e-03 0.0 + 7 -205.5617587375640483 4.48e-04 3.81e-04 5.89e-03 1.05e-02 0.0 + 8 -205.5622303433787579 -4.72e-04 2.54e-05 3.27e-04 1.55e-04 0.0 + 9 -205.5622298049888741 5.38e-07 1.50e-05 2.76e-04 4.18e-04 0.0 + 10 -205.5622306466738110 -8.42e-07 7.17e-06 8.71e-05 2.55e-05 0.0 + 11 -205.5622306600281490 -1.34e-08 3.14e-06 3.97e-05 2.03e-05 0.0 + 12 -205.5622306737377016 -1.37e-08 6.96e-07 7.99e-06 4.95e-06 0.0 + 13 -205.5622306734264839 3.11e-10 2.86e-07 3.20e-06 3.71e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 13 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56223067342648 Eh -5593.63267 eV + +Components: +Nuclear Repulsion : 70.09550100333803 Eh 1907.39555 eV +Electronic Energy : -275.65773167676457 Eh -7501.02822 eV +One Electron Energy: -419.83222878230987 Eh -11424.21574 eV +Two Electron Energy: 144.17449710554533 Eh 3923.18752 eV + +Virial components: +Potential Energy : -410.42544527841346 Eh -11168.24415 eV +Kinetic Energy : 204.86321460498698 Eh 5574.61148 eV +Virial Ratio : 2.00341211119716 + +DFT components: +N(Alpha) : 11.999999458538 electrons +N(Beta) : 11.999999458538 electrons +N(Total) : 23.999998917076 electrons +E(X) : -23.348935691874 Eh +E(C) : -0.804814149876 Eh +E(XC) : -24.153749841750 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -3.1122e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.2042e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.8587e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.7641e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.7059e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.6805e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.191964 -522.2399 + 1 2.0000 -19.022518 -517.6290 + 2 2.0000 -14.273459 -388.4006 + 3 2.0000 -1.256326 -34.1864 + 4 2.0000 -0.971634 -26.4395 + 5 2.0000 -0.718975 -19.5643 + 6 2.0000 -0.564374 -15.3574 + 7 2.0000 -0.523171 -14.2362 + 8 2.0000 -0.498636 -13.5686 + 9 2.0000 -0.333497 -9.0749 + 10 2.0000 -0.285015 -7.7557 + 11 2.0000 -0.268654 -7.3104 + 12 0.0000 -0.189483 -5.1561 + 13 0.0000 0.033419 0.9094 + 14 0.0000 0.099132 2.6975 + 15 0.0000 0.139173 3.7871 + 16 0.0000 0.226160 6.1541 + 17 0.0000 0.268552 7.3077 + 18 0.0000 0.303502 8.2587 + 19 0.0000 0.329860 8.9760 + 20 0.0000 0.356302 9.6955 + 21 0.0000 0.381838 10.3903 + 22 0.0000 0.397008 10.8031 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.251594 + 1 O : 0.214948 + 2 O : -0.225613 + 3 H : 0.262259 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.846735 s : 3.846735 + pz : 1.368075 p : 3.350147 + px : 1.093713 + py : 0.888360 + dz2 : 0.015080 d : 0.054712 + dxz : -0.000154 + dyz : 0.009196 + dx2y2 : 0.013988 + dxy : 0.016602 + + 1 O s : 3.736659 s : 3.736659 + pz : 1.446382 p : 3.907414 + px : 1.338033 + py : 1.122998 + dz2 : 0.035109 d : 0.140980 + dxz : 0.014569 + dyz : 0.028655 + dx2y2 : 0.024342 + dxy : 0.038305 + + 2 O s : 3.940579 s : 3.940579 + pz : 1.382201 p : 4.266494 + px : 1.288164 + py : 1.596129 + dz2 : 0.001830 d : 0.018540 + dxz : 0.004684 + dyz : 0.006843 + dx2y2 : 0.002697 + dxy : 0.002485 + + 3 H s : 0.709250 s : 0.709250 + pz : 0.017810 p : 0.028491 + px : 0.006125 + py : 0.004556 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.045455 + 1 O : -0.184257 + 2 O : -0.048998 + 3 H : 0.278710 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.344278 s : 3.344278 + pz : 1.326582 p : 3.387311 + px : 1.017962 + py : 1.042767 + dz2 : 0.060034 d : 0.313866 + dxz : 0.006851 + dyz : 0.095823 + dx2y2 : 0.086656 + dxy : 0.064502 + + 1 O s : 3.360653 s : 3.360653 + pz : 1.460659 p : 4.045991 + px : 1.263348 + py : 1.321984 + dz2 : 0.146496 d : 0.777613 + dxz : 0.072563 + dyz : 0.209992 + dx2y2 : 0.174260 + dxy : 0.174303 + + 2 O s : 3.604017 s : 3.604017 + pz : 1.374488 p : 4.196584 + px : 1.255329 + py : 1.566767 + dz2 : 0.067854 d : 0.248397 + dxz : 0.051833 + dyz : 0.058132 + dx2y2 : 0.037636 + dxy : 0.032942 + + 3 H s : 0.648002 s : 0.648002 + pz : 0.049678 p : 0.073288 + px : 0.014354 + py : 0.009256 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2516 7.0000 -0.2516 2.7913 2.7913 0.0000 + 1 O 7.7851 8.0000 0.2149 2.6329 2.6329 0.0000 + 2 O 8.2256 8.0000 -0.2256 1.6773 1.6773 0.0000 + 3 H 0.7377 1.0000 0.2623 0.9274 0.9274 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4364 B( 0-N , 2-O ) : 0.4785 B( 0-N , 3-H ) : 0.8765 +B( 1-O , 2-O ) : 1.1722 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.360 sec +Sum of individual times .... 2.345 sec ( 99.4%) + +SCF preparation .... 0.766 sec ( 32.4%) +Fock matrix formation .... 0.332 sec ( 14.1%) + Startup .... 0.015 sec ( 4.5% of F) + Split-RI-J .... 0.051 sec ( 15.3% of F) + XC integration .... 0.211 sec ( 63.6% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.014 sec ( 6.5% of XC) + Density eval. .... 0.017 sec ( 8.2% of XC) + XC-Functional eval. .... 0.012 sec ( 5.6% of XC) + XC-Potential eval. .... 0.017 sec ( 8.3% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.029 sec ( 1.2%) +Total Energy calculation .... 0.028 sec ( 1.2%) +Population analysis .... 1.054 sec ( 44.7%) +Orbital Transformation .... 0.014 sec ( 0.6%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.070 sec ( 3.0%) +SOSCF solution .... 0.052 sec ( 2.2%) +Finished LeanSCF after 3.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 31.2 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000364062 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007196255 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.555398479891 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000002105 -0.000004796 0.000001987 + 2 O : -0.000000057 0.000000585 -0.000000834 + 3 O : 0.000002224 0.000005506 0.000001972 + 4 H : -0.000000062 -0.000001295 -0.000003125 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000091116 +RMS gradient ... 0.0000026303 +MAX gradient ... 0.0000055061 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.038991889 -0.003664807 -0.002481806 + 2 O : -0.034770037 0.003778782 0.012047054 + 3 O : 0.018889574 -0.004090462 -0.007855684 + 4 H : -0.023111427 0.003976486 -0.001709564 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000599 0.0000050952 0.0000312905 + +Norm of the Cartesian gradient ... 0.0624216031 +RMS gradient ... 0.0180195647 +MAX gradient ... 0.0389918892 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.128 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.1%) +RI-J Coulomb gradient .... 0.058 sec ( 45.8%) +XC gradient .... 0.022 sec ( 16.9%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.555398480 Eh +Current gradient norm .... 0.062421603 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999940265 +Lowest eigenvalues of augmented Hessian: + -0.000050993 0.362934954 0.384976398 0.446956016 0.675888578 +Length of the computed step .... 0.010930754 +The final length of the internal step .... 0.010930754 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0044624615 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0057266520 RMS(Int)= 0.0044594587 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0019879274 0.0001000000 NO + MAX gradient 0.0029415871 0.0003000000 NO + RMS step 0.0044624615 0.0020000000 NO + MAX step 0.0081043915 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0024 Max(Angles) 0.46 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2714 -0.002843 0.0019 1.2733 + 2. B(O 2,O 1) 1.3086 -0.000156 0.0001 1.3087 + 3. B(H 3,N 0) 1.0418 0.001778 -0.0024 1.0394 + 4. A(O 1,N 0,H 3) 105.67 -0.002942 0.46 106.13 + 5. A(N 0,O 1,O 2) 120.64 -0.001947 0.25 120.89 + 6. D(O 2,O 1,N 0,H 3) 32.31 0.044366 0.00 32.31 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.720 %) +Internal coordinates : 0.000 s ( 4.448 %) +B/P matrices and projection : 0.000 s (14.662 %) +Hessian update/contruction : 0.000 s (26.359 %) +Making the step : 0.000 s ( 7.578 %) +Converting the step to Cartesian: 0.000 s ( 4.942 %) +Storing new data : 0.000 s ( 3.954 %) +Checking convergence : 0.000 s ( 0.165 %) +Final printing : 0.000 s (27.677 %) +Total time : 0.001 s + +Time for energy+gradient : 7.840 s +Time for complete geometry iter : 8.666 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.181291 -0.724736 -0.435075 + O -0.006887 0.530972 -0.553771 + O 0.535389 1.228225 0.411910 + H -0.365919 -0.896617 0.573229 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.342591 -1.369553 -0.822173 + 1 O 8.0000 0 15.999 -0.013014 1.003393 -1.046476 + 2 O 8.0000 0 15.999 1.011738 2.321009 0.778397 + 3 H 1.0000 0 1.008 -0.691486 -1.694361 1.083245 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.273306710935 0.00000000 0.00000000 + O 2 1 0 1.308726066447 120.88912883 0.00000000 + H 1 2 3 1.039378424300 106.13166560 32.30769205 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.406200968150 0.00000000 0.00000000 + O 2 1 0 2.473133849910 120.88912883 0.00000000 + H 1 2 3 1.964140571434 106.13166560 32.30769205 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1680 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.021744459563 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.915e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22303 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5621979438231506 0.00e+00 1.23e-04 1.00e-03 4.23e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5622206889244694 -2.27e-05 8.86e-05 1.02e-03 4.85e-04 0.0 + 3 -205.5622167116863466 3.98e-06 5.45e-05 8.03e-04 1.23e-03 0.0 + 4 -205.5622232394934485 -6.53e-06 8.00e-05 1.30e-03 4.48e-04 0.0 + 5 -205.5622092826269522 1.40e-05 6.24e-05 1.07e-03 1.49e-03 0.0 + 6 -205.5622242155621962 -1.49e-05 9.18e-06 8.59e-05 3.00e-05 0.0 + 7 -205.5622242293033537 -1.37e-08 3.55e-06 3.50e-05 2.44e-05 0.0 + 8 -205.5622242449994133 -1.57e-08 1.03e-06 9.29e-06 3.09e-06 0.0 + 9 -205.5622242459267000 -9.27e-10 3.76e-07 3.02e-06 1.65e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56222424592670 Eh -5593.63250 eV + +Components: +Nuclear Repulsion : 70.02174445956344 Eh 1905.38853 eV +Electronic Energy : -275.58396870549018 Eh -7499.02103 eV +One Electron Energy: -419.68908800703872 Eh -11420.32068 eV +Two Electron Energy: 144.10511930154857 Eh 3921.29965 eV + +Virial components: +Potential Energy : -410.42110006902556 Eh -11168.12591 eV +Kinetic Energy : 204.85887582309883 Eh 5574.49341 eV +Virial Ratio : 2.00343333145807 + +DFT components: +N(Alpha) : 11.999999469990 electrons +N(Beta) : 11.999999469990 electrons +N(Total) : 23.999998939980 electrons +E(X) : -23.348033231618 Eh +E(C) : -0.804702891926 Eh +E(XC) : -24.152736123544 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 9.2729e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.0233e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.7621e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.6459e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.6463e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 6.4077e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 2.5 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 31.4 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000363959 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007159951 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.555428254428 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000002122 -0.000004849 0.000001981 + 2 O : -0.000000053 0.000000593 -0.000000837 + 3 O : 0.000002257 0.000005589 0.000001965 + 4 H : -0.000000081 -0.000001332 -0.000003108 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000091993 +RMS gradient ... 0.0000026556 +MAX gradient ... 0.0000055888 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.038142762 -0.005265007 -0.000259891 + 2 O : -0.034262347 0.005271585 0.011505901 + 3 O : 0.019010775 -0.003179310 -0.007765387 + 4 H : -0.022891191 0.003172732 -0.003480622 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000005260 0.0000063617 0.0000316073 + +Norm of the Cartesian gradient ... 0.0616015285 +RMS gradient ... 0.0177828295 +MAX gradient ... 0.0381427621 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.137 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.006 sec ( 4.3%) +RI-J Coulomb gradient .... 0.063 sec ( 45.7%) +XC gradient .... 0.022 sec ( 16.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.555428254 Eh +Current gradient norm .... 0.061601529 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999995731 +Lowest eigenvalues of augmented Hessian: + -0.000002728 0.295350923 0.387901349 0.452182835 0.680954061 +Length of the computed step .... 0.002921918 +The final length of the internal step .... 0.002921918 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0011928680 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0013497827 RMS(Int)= 0.0011926857 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000001364 +Previously predicted energy change .... -0.000025500 +Actually observed energy change .... -0.000029775 +Ratio of predicted to observed change .... 1.167643032 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000297745 0.0000050000 NO + RMS gradient 0.0003975311 0.0001000000 NO + MAX gradient 0.0007470435 0.0003000000 NO + RMS step 0.0011928680 0.0020000000 YES + MAX step 0.0026317778 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0004 Max(Angles) 0.15 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2733 -0.000376 0.0003 1.2737 + 2. B(O 2,O 1) 1.3087 0.000454 -0.0004 1.3083 + 3. B(H 3,N 0) 1.0394 0.000166 -0.0003 1.0391 + 4. A(O 1,N 0,H 3) 106.13 -0.000747 0.15 106.28 + 5. A(N 0,O 1,O 2) 120.89 -0.000122 0.02 120.91 + 6. D(O 2,O 1,N 0,H 3) 32.31 0.044101 -0.00 32.31 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 1.324 %) +Internal coordinates : 0.000 s ( 0.485 %) +B/P matrices and projection : 0.000 s ( 1.839 %) +Hessian update/contruction : 0.006 s (90.747 %) +Making the step : 0.000 s ( 0.912 %) +Converting the step to Cartesian: 0.000 s ( 0.647 %) +Storing new data : 0.000 s ( 0.530 %) +Checking convergence : 0.000 s ( 0.177 %) +Final printing : 0.000 s ( 3.310 %) +Total time : 0.007 s + +Time for energy+gradient : 6.956 s +Time for complete geometry iter : 7.927 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.181394 -0.724423 -0.434424 + O -0.006459 0.531514 -0.553638 + O 0.535638 1.229192 0.411258 + H -0.366494 -0.898439 0.573096 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.342785 -1.368960 -0.820943 + 1 O 8.0000 0 15.999 -0.012205 1.004416 -1.046225 + 2 O 8.0000 0 15.999 1.012210 2.322836 0.777166 + 3 H 1.0000 0 1.008 -0.692573 -1.697804 1.082995 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.273652561043 0.00000000 0.00000000 + O 2 1 0 1.308300177723 120.91274800 0.00000000 + H 1 2 3 1.039058043857 106.28245537 32.30769205 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.406854530140 0.00000000 0.00000000 + O 2 1 0 2.472329036857 120.91274800 0.00000000 + H 1 2 3 1.963535140138 106.28245537 32.30769205 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1680 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.019246139108 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.911e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22305 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5622169086469171 0.00e+00 2.81e-05 2.69e-04 6.29e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5622179719241558 -1.06e-06 1.57e-05 1.75e-04 6.32e-05 0.0 + 3 -205.5622178457384166 1.26e-07 1.41e-05 1.81e-04 1.76e-04 0.0 + 4 -205.5622179473402298 -1.02e-07 1.54e-05 2.18e-04 1.35e-04 0.0 + 5 -205.5622177499499230 1.97e-07 9.85e-06 1.67e-04 2.64e-04 0.0 + 6 -205.5622180771174499 -3.27e-07 5.36e-06 4.43e-05 2.91e-05 0.0 + 7 -205.5622180859640480 -8.85e-09 1.87e-06 1.32e-05 8.22e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56221808596405 Eh -5593.63233 eV + +Components: +Nuclear Repulsion : 70.01924613910825 Eh 1905.32055 eV +Electronic Energy : -275.58146422507230 Eh -7498.95288 eV +One Electron Energy: -419.68443135549728 Eh -11420.19397 eV +Two Electron Energy: 144.10296713042499 Eh 3921.24109 eV + +Virial components: +Potential Energy : -410.42095121691523 Eh -11168.12186 eV +Kinetic Energy : 204.85873313095121 Eh 5574.48953 eV +Virial Ratio : 2.00343400031945 + +DFT components: +N(Alpha) : 11.999999464163 electrons +N(Beta) : 11.999999464163 electrons +N(Total) : 23.999998928326 electrons +E(X) : -23.348095122860 Eh +E(C) : -0.804702997146 Eh +E(XC) : -24.152798120006 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 8.8466e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.3214e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.8724e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.7126e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 8.2158e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 4.1481e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 2.3 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 31.6 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000363945 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007152316 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.555429714596 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000002125 -0.000004859 0.000001981 + 2 O : -0.000000051 0.000000596 -0.000000837 + 3 O : 0.000002262 0.000005602 0.000001960 + 4 H : -0.000000085 -0.000001339 -0.000003103 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000092127 +RMS gradient ... 0.0000026595 +MAX gradient ... 0.0000056017 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.038061654 -0.005346856 0.000312738 + 2 O : -0.034070907 0.005791966 0.011364311 + 3 O : 0.018895570 -0.003291695 -0.007948215 + 4 H : -0.022886317 0.002846585 -0.003728835 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000003859 0.0000072724 0.0000372174 + +Norm of the Cartesian gradient ... 0.0614633227 +RMS gradient ... 0.0177429330 +MAX gradient ... 0.0380616539 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.126 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.8%) +RI-J Coulomb gradient .... 0.058 sec ( 46.0%) +XC gradient .... 0.018 sec ( 14.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.555429715 Eh +Current gradient norm .... 0.061463323 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999906 +Lowest eigenvalues of augmented Hessian: + -0.000000092 0.279585886 0.388191767 0.453024574 0.642251837 +Length of the computed step .... 0.000432895 +The final length of the internal step .... 0.000432895 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0001767287 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001305597 RMS(Int)= 0.0001767271 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000046 +Previously predicted energy change .... -0.000001364 +Actually observed energy change .... -0.000001460 +Ratio of predicted to observed change .... 1.070477975 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000014602 0.0000050000 YES + RMS gradient 0.0000934712 0.0001000000 YES + MAX gradient 0.0002133035 0.0003000000 YES + RMS step 0.0001767287 0.0020000000 YES + MAX step 0.0003631054 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0002 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2737 0.000060 -0.0000 1.2736 + 2. B(O 2,O 1) 1.3083 0.000213 -0.0002 1.3081 + 3. B(H 3,N 0) 1.0391 -0.000015 0.0000 1.0391 + 4. A(O 1,N 0,H 3) 106.28 -0.000021 0.01 106.29 + 5. A(N 0,O 1,O 2) 120.91 -0.000052 0.01 120.92 + 6. D(O 2,O 1,N 0,H 3) 32.31 0.044047 0.00 32.31 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.068 %) +Internal coordinates : 0.000 s ( 3.193 %) +B/P matrices and projection : 0.000 s (11.877 %) +Hessian update/contruction : 0.000 s (34.227 %) +Making the step : 0.000 s ( 4.981 %) +Converting the step to Cartesian: 0.000 s ( 3.959 %) +Storing new data : 0.000 s ( 3.193 %) +Checking convergence : 0.000 s ( 1.405 %) +Final printing : 0.000 s (27.842 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.181395 -0.724355 -0.434390 + O -0.006395 0.531552 -0.553545 + O 0.535622 1.229226 0.411138 + H -0.366541 -0.898579 0.573089 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.342786 -1.368833 -0.820879 + 1 O 8.0000 0 15.999 -0.012085 1.004487 -1.046049 + 2 O 8.0000 0 15.999 1.012179 2.322901 0.776939 + 3 H 1.0000 0 1.008 -0.692661 -1.698067 1.082981 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.273626360921 0.00000000 0.00000000 + O 2 1 0 1.308108030609 120.92163090 0.00000000 + H 1 2 3 1.039060913477 106.29221851 32.30769205 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.406805019084 0.00000000 0.00000000 + O 2 1 0 2.471965931434 120.92163090 0.00000000 + H 1 2 3 1.963540562933 106.29221851 32.30769205 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1680 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.023797295372 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.909e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22305 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.0237972954 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5622174215873770 0.00e+00 5.93e-06 6.34e-05 9.34e-06 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5622174627546315 -4.12e-08 4.11e-06 5.37e-05 1.50e-05 0.1 + 3 -205.5622174422261423 2.05e-08 2.97e-06 4.51e-05 7.52e-05 0.0 + 4 -205.5622174650882812 -2.29e-08 2.25e-06 2.50e-05 1.20e-05 0.0 + 5 -205.5622174623270553 2.76e-09 1.12e-06 1.95e-05 2.56e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56221746232706 Eh -5593.63231 eV + +Components: +Nuclear Repulsion : 70.02379729537164 Eh 1905.44440 eV +Electronic Energy : -275.58601475769871 Eh -7499.07671 eV +One Electron Energy: -419.69339515536359 Eh -11420.43789 eV +Two Electron Energy: 144.10738039766488 Eh 3921.36118 eV + +Virial components: +Potential Energy : -410.42155583292140 Eh -11168.13831 eV +Kinetic Energy : 204.85933837059434 Eh 5574.50600 eV +Virial Ratio : 2.00343103271407 + +DFT components: +N(Alpha) : 11.999999462748 electrons +N(Beta) : 11.999999462748 electrons +N(Total) : 23.999998925497 electrons +E(X) : -23.348247110647 Eh +E(C) : -0.804713048228 Eh +E(XC) : -24.152960158875 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -2.7612e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.9517e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.1163e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.6000e-05 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.5566e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.2558e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.191756 -522.2342 + 1 2.0000 -19.022960 -517.6411 + 2 2.0000 -14.273022 -388.3887 + 3 2.0000 -1.255182 -34.1552 + 4 2.0000 -0.971397 -26.4331 + 5 2.0000 -0.719484 -19.5782 + 6 2.0000 -0.564508 -15.3610 + 7 2.0000 -0.522571 -14.2199 + 8 2.0000 -0.498535 -13.5658 + 9 2.0000 -0.333112 -9.0644 + 10 2.0000 -0.285003 -7.7553 + 11 2.0000 -0.268634 -7.3099 + 12 0.0000 -0.189580 -5.1587 + 13 0.0000 0.033686 0.9166 + 14 0.0000 0.099191 2.6991 + 15 0.0000 0.138440 3.7671 + 16 0.0000 0.226115 6.1529 + 17 0.0000 0.268707 7.3119 + 18 0.0000 0.303796 8.2667 + 19 0.0000 0.329526 8.9669 + 20 0.0000 0.356528 9.7016 + 21 0.0000 0.381569 10.3830 + 22 0.0000 0.397234 10.8093 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.252479 + 1 O : 0.215100 + 2 O : -0.223983 + 3 H : 0.261362 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.845628 s : 3.845628 + pz : 1.370075 p : 3.352662 + px : 1.095458 + py : 0.887129 + dz2 : 0.014872 d : 0.054189 + dxz : -0.000174 + dyz : 0.009090 + dx2y2 : 0.013962 + dxy : 0.016439 + + 1 O s : 3.736206 s : 3.736206 + pz : 1.448590 p : 3.907548 + px : 1.338289 + py : 1.120669 + dz2 : 0.035078 d : 0.141146 + dxz : 0.014551 + dyz : 0.028416 + dx2y2 : 0.024678 + dxy : 0.038422 + + 2 O s : 3.940796 s : 3.940796 + pz : 1.388833 p : 4.264775 + px : 1.286714 + py : 1.589228 + dz2 : 0.001744 d : 0.018413 + dxz : 0.004650 + dyz : 0.006785 + dx2y2 : 0.002682 + dxy : 0.002551 + + 3 H s : 0.709956 s : 0.709956 + pz : 0.017850 p : 0.028682 + px : 0.006215 + py : 0.004617 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.045681 + 1 O : -0.183836 + 2 O : -0.047638 + 3 H : 0.277155 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.343312 s : 3.343312 + pz : 1.329734 p : 3.389615 + px : 1.019730 + py : 1.040152 + dz2 : 0.059569 d : 0.312753 + dxz : 0.006867 + dyz : 0.095785 + dx2y2 : 0.086344 + dxy : 0.064189 + + 1 O s : 3.361312 s : 3.361312 + pz : 1.461868 p : 4.045362 + px : 1.263773 + py : 1.319720 + dz2 : 0.146262 d : 0.777163 + dxz : 0.072105 + dyz : 0.209064 + dx2y2 : 0.174815 + dxy : 0.174917 + + 2 O s : 3.604011 s : 3.604011 + pz : 1.379602 p : 4.195308 + px : 1.253987 + py : 1.561719 + dz2 : 0.067575 d : 0.248319 + dxz : 0.051614 + dyz : 0.058236 + dx2y2 : 0.037715 + dxy : 0.033179 + + 3 H s : 0.648895 s : 0.648895 + pz : 0.049818 p : 0.073950 + px : 0.014614 + py : 0.009518 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2525 7.0000 -0.2525 2.7929 2.7929 -0.0000 + 1 O 7.7849 8.0000 0.2151 2.6322 2.6322 -0.0000 + 2 O 8.2240 8.0000 -0.2240 1.6793 1.6793 -0.0000 + 3 H 0.7386 1.0000 0.2614 0.9274 0.9274 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4352 B( 0-N , 2-O ) : 0.4806 B( 0-N , 3-H ) : 0.8771 +B( 1-O , 2-O ) : 1.1726 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.109 sec +Sum of individual times .... 2.094 sec ( 99.3%) + +SCF preparation .... 0.787 sec ( 37.3%) +Fock matrix formation .... 0.140 sec ( 6.7%) + Startup .... 0.007 sec ( 5.3% of F) + Split-RI-J .... 0.019 sec ( 13.5% of F) + XC integration .... 0.095 sec ( 67.6% of F) + Basis function eval. .... 0.005 sec ( 5.7% of XC) + Density eval. .... 0.008 sec ( 8.2% of XC) + XC-Functional eval. .... 0.005 sec ( 4.8% of XC) + XC-Potential eval. .... 0.007 sec ( 7.8% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.009 sec ( 0.4%) +Total Energy calculation .... 0.010 sec ( 0.5%) +Population analysis .... 1.104 sec ( 52.4%) +Orbital Transformation .... 0.006 sec ( 0.3%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.010 sec ( 0.5%) +SOSCF solution .... 0.028 sec ( 1.3%) +Finished LeanSCF after 3.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 31.9 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000363945 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007151634 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.555429773110 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.024.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.024.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.223362 0.688107 -0.312932 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5622174623270553 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.178556032 0.671818599 -0.436656278 +Nuclear contribution : -0.452089129 -1.175367747 0.694329366 + ----------------------------------------- +Total Dipole Moment : -0.273533097 -0.503549148 0.257673088 + ----------------------------------------- +Magnitude (a.u.) : 0.628313234 +Magnitude (Debye) : 1.597045321 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.968480 0.432492 0.381085 +Rotational constants in MHz : 88992.783615 12965.781974 11424.648200 + +Dipole components along the rotational axes: +x,y,z [a.u.] : 0.437025 0.395026 -0.218498 +x,y,z [Debye]: 1.110829 1.004076 -0.555377 + + + +Dipole moment calculation done in 0.4 sec + +Maximum memory used throughout the entire PROP-calculation: 16.9 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 25 * + * * + * Dihedral ( 2, 1, 0, 3) : 41.53846154 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2754 0.768562 + 2. B(O 2,O 1) 1.3095 0.677120 + 3. B(H 3,N 0) 1.0411 0.388893 + 4. A(O 1,N 0,H 3) 106.0609 0.363025 + 5. A(N 0,O 1,O 2) 120.6893 0.446423 + 6. D(O 2,O 1,N 0,H 3) 41.5385 0.047167 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.145839 -0.727831 -0.428921 + O -0.036054 0.538258 -0.536532 + O 0.557766 1.239341 0.396581 + H -0.394582 -0.911925 0.565164 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.275596 -1.375400 -0.810543 + 1 O 8.0000 0 15.999 -0.068131 1.017161 -1.013899 + 2 O 8.0000 0 15.999 1.054026 2.342015 0.749429 + 3 H 1.0000 0 1.008 -0.745652 -1.723288 1.068006 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.273626360921 0.00000000 0.00000000 + O 2 1 0 1.308108030609 120.92163090 0.00000000 + H 1 2 3 1.039060913477 106.29221851 32.30769205 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.406805019084 0.00000000 0.00000000 + O 2 1 0 2.471965931434 120.92163090 0.00000000 + H 1 2 3 1.963540562933 106.29221851 32.30769205 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1680 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.922906526317 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.904e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22299 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5575 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.9229065263 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5499539195623697 0.00e+00 3.84e-04 3.68e-03 2.45e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.073) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5510766438572432 -1.12e-03 4.56e-04 4.12e-03 1.90e-02 0.700 0.1 + ***Turning on AO-DIIS*** + 3 -205.5520060623107952 -9.29e-04 3.45e-04 2.94e-03 1.35e-02 0.700 0.0 + 4 -205.5526535174712421 -6.47e-04 8.66e-04 7.20e-03 9.51e-03 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5541820501114785 -1.53e-03 1.17e-04 1.53e-03 1.87e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -205.5541849941310488 -2.94e-06 4.48e-04 6.21e-03 1.48e-03 0.0 + 7 -205.5537864517401658 3.99e-04 3.62e-04 5.59e-03 9.03e-03 0.0 + 8 -205.5542075480566382 -4.21e-04 3.73e-05 5.52e-04 2.49e-04 0.0 + 9 -205.5542057207429707 1.83e-06 2.39e-05 4.38e-04 6.56e-04 0.0 + 10 -205.5542081333208557 -2.41e-06 6.21e-06 7.51e-05 2.13e-05 0.0 + 11 -205.5542081407826345 -7.46e-09 2.64e-06 3.37e-05 1.69e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.55420814078263 Eh -5593.41437 eV + +Components: +Nuclear Repulsion : 69.92290652631677 Eh 1902.69902 eV +Electronic Energy : -275.47711466709939 Eh -7496.11339 eV +One Electron Energy: -419.49927405085117 Eh -11415.15558 eV +Two Electron Energy: 144.02215938375178 Eh 3919.04220 eV + +Virial components: +Potential Energy : -410.41318419149150 Eh -11167.91051 eV +Kinetic Energy : 204.85897605070886 Eh 5574.49614 eV +Virial Ratio : 2.00339371065636 + +DFT components: +N(Alpha) : 11.999998572131 electrons +N(Beta) : 11.999998572131 electrons +N(Total) : 23.999997144261 electrons +E(X) : -23.345034306027 Eh +E(C) : -0.804592307998 Eh +E(XC) : -24.149626614024 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 7.4618e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.3692e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.6406e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.8660e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.6937e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.2988e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.190284 -522.1942 + 1 2.0000 -19.025443 -517.7086 + 2 2.0000 -14.270566 -388.3218 + 3 2.0000 -1.253508 -34.1097 + 4 2.0000 -0.970644 -26.4126 + 5 2.0000 -0.717574 -19.5262 + 6 2.0000 -0.565672 -15.3927 + 7 2.0000 -0.521453 -14.1895 + 8 2.0000 -0.497535 -13.5386 + 9 2.0000 -0.333552 -9.0764 + 10 2.0000 -0.279644 -7.6095 + 11 2.0000 -0.269533 -7.3344 + 12 0.0000 -0.195230 -5.3125 + 13 0.0000 0.035632 0.9696 + 14 0.0000 0.095747 2.6054 + 15 0.0000 0.138546 3.7700 + 16 0.0000 0.227823 6.1994 + 17 0.0000 0.265071 7.2129 + 18 0.0000 0.306958 8.3528 + 19 0.0000 0.328282 8.9330 + 20 0.0000 0.357616 9.7312 + 21 0.0000 0.384785 10.4705 + 22 0.0000 0.397329 10.8119 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.262351 + 1 O : 0.208445 + 2 O : -0.212370 + 3 H : 0.266276 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.842061 s : 3.842061 + pz : 1.381137 p : 3.364803 + px : 1.102758 + py : 0.880908 + dz2 : 0.015644 d : 0.055486 + dxz : 0.000659 + dyz : 0.009619 + dx2y2 : 0.013708 + dxy : 0.015855 + + 1 O s : 3.737894 s : 3.737894 + pz : 1.454985 p : 3.915941 + px : 1.339960 + py : 1.120996 + dz2 : 0.032484 d : 0.137720 + dxz : 0.013559 + dyz : 0.029467 + dx2y2 : 0.024088 + dxy : 0.038122 + + 2 O s : 3.941293 s : 3.941293 + pz : 1.409667 p : 4.254131 + px : 1.249509 + py : 1.594955 + dz2 : 0.002527 d : 0.016947 + dxz : 0.003531 + dyz : 0.005834 + dx2y2 : 0.002213 + dxy : 0.002841 + + 3 H s : 0.704899 s : 0.704899 + pz : 0.017328 p : 0.028826 + px : 0.006827 + py : 0.004671 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.053719 + 1 O : -0.184544 + 2 O : -0.040923 + 3 H : 0.279187 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.342938 s : 3.342938 + pz : 1.337471 p : 3.397394 + px : 1.023454 + py : 1.036469 + dz2 : 0.057308 d : 0.313387 + dxz : 0.007821 + dyz : 0.097349 + dx2y2 : 0.087084 + dxy : 0.063825 + + 1 O s : 3.362857 s : 3.362857 + pz : 1.461204 p : 4.047353 + px : 1.265349 + py : 1.320800 + dz2 : 0.136730 d : 0.774335 + dxz : 0.073403 + dyz : 0.207991 + dx2y2 : 0.176559 + dxy : 0.179652 + + 2 O s : 3.605821 s : 3.605821 + pz : 1.393689 p : 4.187398 + px : 1.226119 + py : 1.567590 + dz2 : 0.062228 d : 0.247704 + dxz : 0.053892 + dyz : 0.055630 + dx2y2 : 0.040764 + dxy : 0.035189 + + 3 H s : 0.646802 s : 0.646802 + pz : 0.048347 p : 0.074011 + px : 0.016041 + py : 0.009623 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2624 7.0000 -0.2624 2.7891 2.7891 0.0000 + 1 O 7.7916 8.0000 0.2084 2.6168 2.6168 0.0000 + 2 O 8.2124 8.0000 -0.2124 1.6764 1.6764 0.0000 + 3 H 0.7337 1.0000 0.2663 0.9235 0.9235 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4262 B( 0-N , 2-O ) : 0.4865 B( 0-N , 3-H ) : 0.8763 +B( 1-O , 2-O ) : 1.1666 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.607 sec +Sum of individual times .... 2.594 sec ( 99.5%) + +SCF preparation .... 1.036 sec ( 39.7%) +Fock matrix formation .... 0.270 sec ( 10.3%) + Startup .... 0.013 sec ( 4.7% of F) + Split-RI-J .... 0.039 sec ( 14.5% of F) + XC integration .... 0.174 sec ( 64.6% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.012 sec ( 6.7% of XC) + Density eval. .... 0.016 sec ( 9.2% of XC) + XC-Functional eval. .... 0.010 sec ( 5.6% of XC) + XC-Potential eval. .... 0.015 sec ( 8.8% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.026 sec ( 1.0%) +Total Energy calculation .... 0.023 sec ( 0.9%) +Population analysis .... 1.120 sec ( 43.0%) +Orbital Transformation .... 0.014 sec ( 0.5%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.069 sec ( 2.6%) +SOSCF solution .... 0.037 sec ( 1.4%) +Finished LeanSCF after 3.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 32.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000363821 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007131377 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.547440584703 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000002301 -0.000004925 0.000001963 + 2 O : -0.000000098 0.000000605 -0.000000810 + 3 O : 0.000002356 0.000005788 0.000001891 + 4 H : 0.000000043 -0.000001468 -0.000003043 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000094062 +RMS gradient ... 0.0000027153 +MAX gradient ... 0.0000057876 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.047776276 -0.001211527 -0.001276962 + 2 O : -0.041703806 0.001766006 0.017900714 + 3 O : 0.022517809 -0.003747324 -0.012008479 + 4 H : -0.028590280 0.003192845 -0.004615273 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000005736 -0.0000168444 0.0000076996 + +Norm of the Cartesian gradient ... 0.0765678106 +RMS gradient ... 0.0221032230 +MAX gradient ... 0.0477762764 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.127 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.9%) +RI-J Coulomb gradient .... 0.061 sec ( 47.6%) +XC gradient .... 0.018 sec ( 13.9%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.547440585 Eh +Current gradient norm .... 0.076567811 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999924987 +Lowest eigenvalues of augmented Hessian: + -0.000067854 0.362181873 0.385945343 0.445487610 0.673621196 +Length of the computed step .... 0.012249165 +The final length of the internal step .... 0.012249165 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0050007007 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0061167189 RMS(Int)= 0.0049985030 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0023906642 0.0001000000 NO + MAX gradient 0.0041157234 0.0003000000 NO + RMS step 0.0050007007 0.0020000000 NO + MAX step 0.0091109549 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0029 Max(Angles) 0.52 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2754 -0.004116 0.0029 1.2782 + 2. B(O 2,O 1) 1.3095 -0.000352 0.0003 1.3098 + 3. B(H 3,N 0) 1.0411 0.001860 -0.0025 1.0386 + 4. A(O 1,N 0,H 3) 106.06 -0.003300 0.52 106.58 + 5. A(N 0,O 1,O 2) 120.69 -0.001697 0.22 120.91 + 6. D(O 2,O 1,N 0,H 3) 41.54 0.054876 0.00 41.54 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (11.098 %) +Internal coordinates : 0.000 s ( 3.699 %) +B/P matrices and projection : 0.000 s (13.873 %) +Hessian update/contruction : 0.000 s (30.289 %) +Making the step : 0.000 s ( 5.665 %) +Converting the step to Cartesian: 0.000 s ( 4.509 %) +Storing new data : 0.000 s ( 3.699 %) +Checking convergence : 0.000 s ( 0.116 %) +Final printing : 0.000 s (26.821 %) +Total time : 0.001 s + +Time for energy+gradient : 8.079 s +Time for complete geometry iter : 8.891 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.147230 -0.728369 -0.426237 + O -0.034237 0.540153 -0.535697 + O 0.559625 1.245464 0.394587 + H -0.396866 -0.919403 0.563639 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.278224 -1.376418 -0.805471 + 1 O 8.0000 0 15.999 -0.064699 1.020741 -1.012321 + 2 O 8.0000 0 15.999 1.057537 2.353585 0.745661 + 3 H 1.0000 0 1.008 -0.749968 -1.737421 1.065124 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.278239705574 0.00000000 0.00000000 + O 2 1 0 1.309794989809 120.90750575 0.00000000 + H 1 2 3 1.038588785705 106.58290078 41.53846153 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.415522977038 0.00000000 0.00000000 + O 2 1 0 2.475153822322 120.90750575 0.00000000 + H 1 2 3 1.962648370745 106.58290078 41.53846153 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1679 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.825288081129 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.908e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22300 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5575 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5541819864759532 0.00e+00 1.30e-04 1.12e-03 4.24e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5542082583083925 -2.63e-05 1.00e-04 1.18e-03 5.50e-04 0.0 + 3 -205.5542026646946283 5.59e-06 5.21e-05 8.83e-04 1.30e-03 0.0 + 4 -205.5542125425830591 -9.88e-06 4.07e-05 5.45e-04 1.35e-04 0.0 + 5 -205.5542096687611320 2.87e-06 3.30e-05 5.41e-04 7.85e-04 0.0 + 6 -205.5542127515804509 -3.08e-06 1.58e-05 1.34e-04 5.64e-05 0.0 + 7 -205.5542127502798166 1.30e-09 7.69e-06 7.58e-05 5.58e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.55421275027982 Eh -5593.41449 eV + +Components: +Nuclear Repulsion : 69.82528808112856 Eh 1900.04268 eV +Electronic Energy : -275.37950083140839 Eh -7493.45718 eV +One Electron Energy: -419.31245533246397 Eh -11410.07199 eV +Two Electron Energy: 143.93295450105558 Eh 3916.61481 eV + +Virial components: +Potential Energy : -410.40626220533369 Eh -11167.72215 eV +Kinetic Energy : 204.85204945505387 Eh 5574.30766 eV +Virial Ratio : 2.00342766058281 + +DFT components: +N(Alpha) : 11.999998659198 electrons +N(Beta) : 11.999998659198 electrons +N(Total) : 23.999997318396 electrons +E(X) : -23.343689514173 Eh +E(C) : -0.804441893549 Eh +E(XC) : -24.148131407722 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.3006e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.5761e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 7.6850e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.7891e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 5.5796e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 8.5280e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 2.3 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 32.4 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000363701 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007095740 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.547480711388 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000002320 -0.000004983 0.000001955 + 2 O : -0.000000093 0.000000615 -0.000000815 + 3 O : 0.000002394 0.000005880 0.000001884 + 4 H : 0.000000020 -0.000001512 -0.000003024 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000095062 +RMS gradient ... 0.0000027442 +MAX gradient ... 0.0000058798 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.046680602 -0.003564557 0.001369126 + 2 O : -0.041214618 0.004118998 0.016728993 + 3 O : 0.022694348 -0.002820335 -0.011639681 + 4 H : -0.028160332 0.002265894 -0.006458437 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000056763 -0.0000203604 0.0000253435 + +Norm of the Cartesian gradient ... 0.0754151782 +RMS gradient ... 0.0217704867 +MAX gradient ... 0.0466806015 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.126 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.006 sec ( 4.5%) +RI-J Coulomb gradient .... 0.059 sec ( 46.5%) +XC gradient .... 0.019 sec ( 15.0%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.547480711 Eh +Current gradient norm .... 0.075415178 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999994719 +Lowest eigenvalues of augmented Hessian: + -0.000003757 0.306024491 0.387217395 0.445788210 0.673813059 +Length of the computed step .... 0.003249859 +The final length of the internal step .... 0.003249859 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0013267494 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0014912375 RMS(Int)= 0.0013265961 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000001879 +Previously predicted energy change .... -0.000033932 +Actually observed energy change .... -0.000040127 +Ratio of predicted to observed change .... 1.182556192 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000401267 0.0000050000 NO + RMS gradient 0.0005013308 0.0001000000 NO + MAX gradient 0.0007852477 0.0003000000 NO + RMS step 0.0013267494 0.0020000000 YES + MAX step 0.0026862504 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0007 Max(Angles) 0.15 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2782 -0.000785 0.0007 1.2789 + 2. B(O 2,O 1) 1.3098 0.000504 -0.0005 1.3093 + 3. B(H 3,N 0) 1.0386 0.000198 -0.0004 1.0382 + 4. A(O 1,N 0,H 3) 106.58 -0.000756 0.15 106.74 + 5. A(N 0,O 1,O 2) 120.91 -0.000163 0.03 120.94 + 6. D(O 2,O 1,N 0,H 3) 41.54 0.054503 -0.00 41.54 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 7.635 %) +Internal coordinates : 0.000 s ( 2.833 %) +B/P matrices and projection : 0.000 s (11.700 %) +Hessian update/contruction : 0.000 s (42.857 %) +Making the step : 0.000 s ( 5.296 %) +Converting the step to Cartesian: 0.000 s ( 4.064 %) +Storing new data : 0.000 s ( 3.571 %) +Checking convergence : 0.000 s ( 1.232 %) +Final printing : 0.000 s (20.320 %) +Total time : 0.001 s + +Time for energy+gradient : 6.561 s +Time for complete geometry iter : 7.594 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.147454 -0.728236 -0.425524 + O -0.033702 0.540881 -0.535560 + O 0.559912 1.246575 0.393914 + H -0.397465 -0.921377 0.563462 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.278647 -1.376166 -0.804123 + 1 O 8.0000 0 15.999 -0.063687 1.022117 -1.012062 + 2 O 8.0000 0 15.999 1.058080 2.355686 0.744390 + 3 H 1.0000 0 1.008 -0.751100 -1.741150 1.064789 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.278946600669 0.00000000 0.00000000 + O 2 1 0 1.309314383069 120.93628952 0.00000000 + H 1 2 3 1.038220656499 106.73681160 41.53846154 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.416858815174 0.00000000 0.00000000 + O 2 1 0 2.474245607205 120.93628952 0.00000000 + H 1 2 3 1.961952707364 106.73681160 41.53846154 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.815197544948 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.904e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22300 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5575 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5542052558608361 0.00e+00 3.23e-05 2.92e-04 7.58e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5542068123999684 -1.56e-06 2.60e-05 3.50e-04 9.85e-05 0.0 + 3 -205.5542059708001830 8.42e-07 2.11e-05 3.09e-04 3.62e-04 0.0 + 4 -205.5542068491828900 -8.78e-07 2.46e-05 3.93e-04 1.55e-04 0.0 + 5 -205.5542058510655465 9.98e-07 1.70e-05 2.98e-04 4.67e-04 0.0 + 6 -205.5542070369357361 -1.19e-06 1.99e-06 1.54e-05 6.63e-06 0.0 + 7 -205.5542070367874317 1.48e-10 8.27e-07 8.69e-06 5.67e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.55420703678743 Eh -5593.41434 eV + +Components: +Nuclear Repulsion : 69.81519754494791 Eh 1899.76811 eV +Electronic Energy : -275.36940458173535 Eh -7493.18244 eV +One Electron Energy: -419.29057028673850 Eh -11409.47646 eV +Two Electron Energy: 143.92116570500312 Eh 3916.29402 eV + +Virial components: +Potential Energy : -410.40548663681022 Eh -11167.70105 eV +Kinetic Energy : 204.85127960002279 Eh 5574.28671 eV +Virial Ratio : 2.00343140369021 + +DFT components: +N(Alpha) : 11.999998664762 electrons +N(Beta) : 11.999998664762 electrons +N(Total) : 23.999997329524 electrons +E(X) : -23.343265050923 Eh +E(C) : -0.804423317719 Eh +E(XC) : -24.147688368642 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.4830e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.6888e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 8.2700e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 4.0920e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 5.6746e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 8.5660e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 2.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 32.6 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000363680 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007087856 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.547482860567 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000002324 -0.000004995 0.000001955 + 2 O : -0.000000091 0.000000620 -0.000000815 + 3 O : 0.000002400 0.000005896 0.000001879 + 4 H : 0.000000015 -0.000001521 -0.000003018 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000095239 +RMS gradient ... 0.0000027493 +MAX gradient ... 0.0000058962 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.046485383 -0.003905600 0.001979553 + 2 O : -0.040955254 0.004869728 0.016550837 + 3 O : 0.022567433 -0.002896285 -0.011799855 + 4 H : -0.028097561 0.001932157 -0.006730535 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000013235 -0.0000141637 0.0000112062 + +Norm of the Cartesian gradient ... 0.0751695473 +RMS gradient ... 0.0216995792 +MAX gradient ... 0.0464853825 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.133 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.006 sec ( 4.2%) +RI-J Coulomb gradient .... 0.062 sec ( 46.6%) +XC gradient .... 0.017 sec ( 13.0%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.547482861 Eh +Current gradient norm .... 0.075169547 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999836 +Lowest eigenvalues of augmented Hessian: + -0.000000168 0.299944475 0.387023356 0.444102426 0.603456698 +Length of the computed step .... 0.000572539 +The final length of the internal step .... 0.000572539 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0002337382 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001366545 RMS(Int)= 0.0002337387 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000084 +Previously predicted energy change .... -0.000001879 +Actually observed energy change .... -0.000002149 +Ratio of predicted to observed change .... 1.143956785 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000021492 0.0000050000 YES + RMS gradient 0.0001251687 0.0001000000 NO + MAX gradient 0.0002938602 0.0003000000 YES + RMS step 0.0002337382 0.0020000000 YES + MAX step 0.0005153855 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0003 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2789 -0.000086 0.0001 1.2791 + 2. B(O 2,O 1) 1.3093 0.000294 -0.0003 1.3090 + 3. B(H 3,N 0) 1.0382 -0.000004 -0.0000 1.0382 + 4. A(O 1,N 0,H 3) 106.74 0.000008 0.01 106.74 + 5. A(N 0,O 1,O 2) 120.94 -0.000011 0.00 120.94 + 6. D(O 2,O 1,N 0,H 3) 41.54 0.054401 0.00 41.54 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (22.963 %) +Internal coordinates : 0.000 s ( 1.756 %) +B/P matrices and projection : 0.000 s (20.506 %) +Hessian update/contruction : 0.000 s (30.267 %) +Making the step : 0.000 s ( 3.371 %) +Converting the step to Cartesian: 0.000 s ( 2.037 %) +Storing new data : 0.000 s ( 1.896 %) +Checking convergence : 0.000 s ( 0.772 %) +Final printing : 0.000 s (15.941 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.147458 -0.728219 -0.425473 + O -0.033621 0.541000 -0.535481 + O 0.559872 1.246558 0.393789 + H -0.397502 -0.921495 0.563457 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.278655 -1.376135 -0.804028 + 1 O 8.0000 0 15.999 -0.063534 1.022343 -1.011913 + 2 O 8.0000 0 15.999 1.058006 2.355654 0.744154 + 3 H 1.0000 0 1.008 -0.751170 -1.741374 1.064779 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.279054193922 0.00000000 0.00000000 + O 2 1 0 1.309041652819 120.93997273 0.00000000 + H 1 2 3 1.038200232773 106.74387951 41.53846154 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.417062136957 0.00000000 0.00000000 + O 2 1 0 2.473730221724 120.93997273 0.00000000 + H 1 2 3 1.961914112115 106.74387951 41.53846154 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.819045411029 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.901e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22300 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5575 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.8190454110 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5542066398305678 0.00e+00 7.41e-06 8.71e-05 1.37e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5542067189617796 -7.91e-08 7.78e-06 1.10e-04 2.86e-05 0.0 + 3 -205.5542066013846352 1.18e-07 6.27e-06 9.56e-05 1.56e-04 0.0 + 4 -205.5542067272588156 -1.26e-07 1.14e-06 1.53e-05 7.55e-06 0.0 + 5 -205.5542067261822581 1.08e-09 7.04e-07 1.22e-05 1.90e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.55420672618226 Eh -5593.41433 eV + +Components: +Nuclear Repulsion : 69.81904541102928 Eh 1899.87281 eV +Electronic Energy : -275.37325213721152 Eh -7493.28714 eV +One Electron Energy: -419.29756882944952 Eh -11409.66690 eV +Two Electron Energy: 143.92431669223799 Eh 3916.37976 eV + +Virial components: +Potential Energy : -410.40588152511759 Eh -11167.71179 eV +Kinetic Energy : 204.85167479893531 Eh 5574.29746 eV +Virial Ratio : 2.00342946635870 + +DFT components: +N(Alpha) : 11.999998658832 electrons +N(Beta) : 11.999998658832 electrons +N(Total) : 23.999997317664 electrons +E(X) : -23.343328961331 Eh +E(C) : -0.804431392664 Eh +E(XC) : -24.147760353994 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.0766e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.2164e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 7.0361e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.1525e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.9041e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.5292e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.190287 -522.1943 + 1 2.0000 -19.026075 -517.7258 + 2 2.0000 -14.270119 -388.3097 + 3 2.0000 -1.251954 -34.0674 + 4 2.0000 -0.970000 -26.3950 + 5 2.0000 -0.718312 -19.5463 + 6 2.0000 -0.565633 -15.3916 + 7 2.0000 -0.520684 -14.1685 + 8 2.0000 -0.497353 -13.5337 + 9 2.0000 -0.333303 -9.0696 + 10 2.0000 -0.279636 -7.6093 + 11 2.0000 -0.269600 -7.3362 + 12 0.0000 -0.195528 -5.3206 + 13 0.0000 0.035498 0.9660 + 14 0.0000 0.096032 2.6132 + 15 0.0000 0.137261 3.7351 + 16 0.0000 0.227339 6.1862 + 17 0.0000 0.265288 7.2189 + 18 0.0000 0.307289 8.3618 + 19 0.0000 0.327883 8.9222 + 20 0.0000 0.357880 9.7384 + 21 0.0000 0.384442 10.4612 + 22 0.0000 0.397339 10.8122 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.263625 + 1 O : 0.208444 + 2 O : -0.210211 + 3 H : 0.265392 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.841270 s : 3.841270 + pz : 1.383475 p : 3.367539 + px : 1.104748 + py : 0.879317 + dz2 : 0.015420 d : 0.054816 + dxz : 0.000615 + dyz : 0.009492 + dx2y2 : 0.013654 + dxy : 0.015634 + + 1 O s : 3.737976 s : 3.737976 + pz : 1.456836 p : 3.915752 + px : 1.340490 + py : 1.118427 + dz2 : 0.032442 d : 0.137828 + dxz : 0.013542 + dyz : 0.029268 + dx2y2 : 0.024385 + dxy : 0.038190 + + 2 O s : 3.941567 s : 3.941567 + pz : 1.415210 p : 4.251822 + px : 1.248117 + py : 1.588495 + dz2 : 0.002460 d : 0.016822 + dxz : 0.003503 + dyz : 0.005770 + dx2y2 : 0.002180 + dxy : 0.002909 + + 3 H s : 0.705570 s : 0.705570 + pz : 0.017374 p : 0.029037 + px : 0.006929 + py : 0.004735 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.054201 + 1 O : -0.183614 + 2 O : -0.039664 + 3 H : 0.277480 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.342565 s : 3.342565 + pz : 1.341326 p : 3.399935 + px : 1.025655 + py : 1.032954 + dz2 : 0.056780 d : 0.311701 + dxz : 0.007815 + dyz : 0.097068 + dx2y2 : 0.086699 + dxy : 0.063339 + + 1 O s : 3.364242 s : 3.364242 + pz : 1.462381 p : 4.046335 + px : 1.265999 + py : 1.317954 + dz2 : 0.136599 d : 0.773037 + dxz : 0.072937 + dyz : 0.206594 + dx2y2 : 0.176999 + dxy : 0.179908 + + 2 O s : 3.605887 s : 3.605887 + pz : 1.398173 p : 4.185946 + px : 1.224818 + py : 1.562955 + dz2 : 0.062087 d : 0.247830 + dxz : 0.053705 + dyz : 0.055754 + dx2y2 : 0.040842 + dxy : 0.035442 + + 3 H s : 0.647762 s : 0.647762 + pz : 0.048517 p : 0.074758 + px : 0.016333 + py : 0.009908 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2636 7.0000 -0.2636 2.7903 2.7903 -0.0000 + 1 O 7.7916 8.0000 0.2084 2.6158 2.6158 -0.0000 + 2 O 8.2102 8.0000 -0.2102 1.6790 1.6790 -0.0000 + 3 H 0.7346 1.0000 0.2654 0.9236 0.9236 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4246 B( 0-N , 2-O ) : 0.4889 B( 0-N , 3-H ) : 0.8767 +B( 1-O , 2-O ) : 1.1672 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.439 sec +Sum of individual times .... 2.424 sec ( 99.4%) + +SCF preparation .... 0.911 sec ( 37.4%) +Fock matrix formation .... 0.126 sec ( 5.2%) + Startup .... 0.007 sec ( 5.8% of F) + Split-RI-J .... 0.018 sec ( 14.4% of F) + XC integration .... 0.081 sec ( 64.4% of F) + Basis function eval. .... 0.006 sec ( 7.6% of XC) + Density eval. .... 0.007 sec ( 8.5% of XC) + XC-Functional eval. .... 0.005 sec ( 5.7% of XC) + XC-Potential eval. .... 0.007 sec ( 9.1% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.008 sec ( 0.3%) +Total Energy calculation .... 0.011 sec ( 0.4%) +Population analysis .... 1.324 sec ( 54.3%) +Orbital Transformation .... 0.006 sec ( 0.3%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.010 sec ( 0.4%) +SOSCF solution .... 0.028 sec ( 1.1%) +Finished LeanSCF after 3.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 32.9 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000363680 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007087428 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.547482979044 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.025.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.025.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.239301 0.702226 -0.307842 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5542067261822581 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.190808955 0.715837986 -0.402159810 +Nuclear contribution : -0.489202548 -1.203764423 0.682730575 + ----------------------------------------- +Total Dipole Moment : -0.298393593 -0.487926438 0.280570765 + ----------------------------------------- +Magnitude (a.u.) : 0.637048585 +Magnitude (Debye) : 1.619248819 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.972039 0.427716 0.379462 +Rotational constants in MHz : 89099.478232 12822.615036 11375.977008 + +Dipole components along the rotational axes: +x,y,z [a.u.] : 0.430103 0.377586 -0.279769 +x,y,z [Debye]: 1.093235 0.959748 -0.711117 + + + +Dipole moment calculation done in 0.6 sec + +Maximum memory used throughout the entire PROP-calculation: 17.4 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 26 * + * * + * Dihedral ( 2, 1, 0, 3) : 50.76923077 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2806 0.753389 + 2. B(O 2,O 1) 1.3106 0.674802 + 3. B(H 3,N 0) 1.0404 0.390125 + 4. A(O 1,N 0,H 3) 106.5261 0.361986 + 5. A(N 0,O 1,O 2) 120.7200 0.444537 + 6. D(O 2,O 1,N 0,H 3) 50.7692 0.045103 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.113235 -0.729475 -0.417199 + O -0.061057 0.546331 -0.515024 + O 0.582176 1.260367 0.376043 + H -0.426592 -0.939378 0.552473 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.213984 -1.378508 -0.788392 + 1 O 8.0000 0 15.999 -0.115380 1.032416 -0.973254 + 2 O 8.0000 0 15.999 1.100153 2.381748 0.710618 + 3 H 1.0000 0 1.008 -0.806142 -1.775168 1.044022 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.279054193922 0.00000000 0.00000000 + O 2 1 0 1.309041652819 120.93997273 0.00000000 + H 1 2 3 1.038200232773 106.74387951 41.53846154 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.417062136957 0.00000000 0.00000000 + O 2 1 0 2.473730221724 120.93997273 0.00000000 + H 1 2 3 1.961914112115 106.74387951 41.53846154 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.714127027273 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.874e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22302 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.7141270273 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5404908026364978 0.00e+00 4.01e-04 3.45e-03 2.23e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.067) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5415802010713264 -1.09e-03 4.74e-04 3.88e-03 1.73e-02 0.700 0.1 + ***Turning on AO-DIIS*** + 3 -205.5424821137308982 -9.02e-04 3.57e-04 2.75e-03 1.22e-02 0.700 0.0 + 4 -205.5431071595577919 -6.25e-04 8.89e-04 6.90e-03 8.65e-03 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5445910165150849 -1.48e-03 1.12e-04 1.51e-03 1.79e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -205.5445963632456596 -5.35e-06 4.21e-04 5.69e-03 1.27e-03 0.0 + 7 -205.5442710995745870 3.25e-04 3.31e-04 5.07e-03 6.91e-03 0.0 + 8 -205.5446168049379025 -3.46e-04 4.75e-05 7.03e-04 3.03e-04 0.0 + 9 -205.5446136329985052 3.17e-06 3.11e-05 5.59e-04 7.89e-04 0.0 + 10 -205.5446176962564095 -4.06e-06 6.92e-06 7.72e-05 2.23e-05 0.0 + 11 -205.5446177038718361 -7.62e-09 2.84e-06 3.51e-05 1.95e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.54461770387184 Eh -5593.15340 eV + +Components: +Nuclear Repulsion : 69.71412702727345 Eh 1897.01784 eV +Electronic Energy : -275.25874473114527 Eh -7490.17124 eV +One Electron Energy: -419.09474754927152 Eh -11404.14786 eV +Two Electron Energy: 143.83600281812625 Eh 3913.97662 eV + +Virial components: +Potential Energy : -410.39682557163439 Eh -11167.46537 eV +Kinetic Energy : 204.85220786776256 Eh 5574.31197 eV +Virial Ratio : 2.00338004575746 + +DFT components: +N(Alpha) : 11.999998851408 electrons +N(Beta) : 11.999998851408 electrons +N(Total) : 23.999997702817 electrons +E(X) : -23.339904330060 Eh +E(C) : -0.804334896744 Eh +E(XC) : -24.144239226804 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 7.6154e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.5118e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.8428e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.7930e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.9482e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.1337e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.188623 -522.1490 + 1 2.0000 -19.029355 -517.8151 + 2 2.0000 -14.266738 -388.2177 + 3 2.0000 -1.250245 -34.0209 + 4 2.0000 -0.969378 -26.3781 + 5 2.0000 -0.716062 -19.4850 + 6 2.0000 -0.566656 -15.4195 + 7 2.0000 -0.519880 -14.1467 + 8 2.0000 -0.496315 -13.5054 + 9 2.0000 -0.333905 -9.0860 + 10 2.0000 -0.273214 -7.4345 + 11 2.0000 -0.270661 -7.3651 + 12 0.0000 -0.201833 -5.4921 + 13 0.0000 0.036952 1.0055 + 14 0.0000 0.092966 2.5297 + 15 0.0000 0.137667 3.7461 + 16 0.0000 0.229410 6.2426 + 17 0.0000 0.261848 7.1252 + 18 0.0000 0.310294 8.4435 + 19 0.0000 0.326834 8.8936 + 20 0.0000 0.359833 9.7916 + 21 0.0000 0.385326 10.4853 + 22 0.0000 0.396952 10.8016 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.277646 + 1 O : 0.203444 + 2 O : -0.196548 + 3 H : 0.270749 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.839018 s : 3.839018 + pz : 1.398364 p : 3.382808 + px : 1.111857 + py : 0.872587 + dz2 : 0.015751 d : 0.055820 + dxz : 0.001636 + dyz : 0.010024 + dx2y2 : 0.013570 + dxy : 0.014838 + + 1 O s : 3.739816 s : 3.739816 + pz : 1.463291 p : 3.922724 + px : 1.341204 + py : 1.118230 + dz2 : 0.029836 d : 0.134015 + dxz : 0.012788 + dyz : 0.030230 + dx2y2 : 0.024326 + dxy : 0.036835 + + 2 O s : 3.942258 s : 3.942258 + pz : 1.435480 p : 4.238923 + px : 1.216449 + py : 1.586994 + dz2 : 0.003256 d : 0.015367 + dxz : 0.002459 + dyz : 0.004746 + dx2y2 : 0.001517 + dxy : 0.003389 + + 3 H s : 0.700016 s : 0.700016 + pz : 0.016757 p : 0.029235 + px : 0.007641 + py : 0.004837 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.064647 + 1 O : -0.184041 + 2 O : -0.031306 + 3 H : 0.279994 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.341064 s : 3.341064 + pz : 1.352181 p : 3.411177 + px : 1.031169 + py : 1.027828 + dz2 : 0.053922 d : 0.312405 + dxz : 0.009276 + dyz : 0.098595 + dx2y2 : 0.086766 + dxy : 0.063846 + + 1 O s : 3.365726 s : 3.365726 + pz : 1.461464 p : 4.048142 + px : 1.267980 + py : 1.318699 + dz2 : 0.126124 d : 0.770172 + dxz : 0.073749 + dyz : 0.205496 + dx2y2 : 0.178835 + dxy : 0.185968 + + 2 O s : 3.607858 s : 3.607858 + pz : 1.409972 p : 4.176231 + px : 1.202540 + py : 1.563719 + dz2 : 0.056313 d : 0.247217 + dxz : 0.055577 + dyz : 0.053128 + dx2y2 : 0.044248 + dxy : 0.037951 + + 3 H s : 0.645127 s : 0.645127 + pz : 0.046741 p : 0.074880 + px : 0.018052 + py : 0.010087 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2776 7.0000 -0.2776 2.7810 2.7810 -0.0000 + 1 O 7.7966 8.0000 0.2034 2.5980 2.5980 0.0000 + 2 O 8.1965 8.0000 -0.1965 1.6752 1.6752 0.0000 + 3 H 0.7293 1.0000 0.2707 0.9190 0.9190 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4143 B( 0-N , 2-O ) : 0.4930 B( 0-N , 3-H ) : 0.8737 +B( 1-O , 2-O ) : 1.1604 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.538 sec +Sum of individual times .... 2.523 sec ( 99.4%) + +SCF preparation .... 0.830 sec ( 32.7%) +Fock matrix formation .... 0.281 sec ( 11.1%) + Startup .... 0.012 sec ( 4.4% of F) + Split-RI-J .... 0.040 sec ( 14.3% of F) + XC integration .... 0.185 sec ( 65.9% of F) + Basis function eval. .... 0.012 sec ( 6.4% of XC) + Density eval. .... 0.017 sec ( 9.2% of XC) + XC-Functional eval. .... 0.010 sec ( 5.5% of XC) + XC-Potential eval. .... 0.017 sec ( 9.0% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.039 sec ( 1.5%) +Total Energy calculation .... 0.023 sec ( 0.9%) +Population analysis .... 1.231 sec ( 48.5%) +Orbital Transformation .... 0.014 sec ( 0.6%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.067 sec ( 2.6%) +SOSCF solution .... 0.038 sec ( 1.5%) +Finished LeanSCF after 3.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 33.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000363502 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007066800 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.537914405458 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000002500 -0.000005086 0.000001924 + 2 O : -0.000000135 0.000000627 -0.000000782 + 3 O : 0.000002520 0.000006129 0.000001791 + 4 H : 0.000000115 -0.000001671 -0.000002932 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000097657 +RMS gradient ... 0.0000028191 +MAX gradient ... 0.0000061294 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.054716136 0.001788836 0.000697030 + 2 O : -0.046768638 -0.000711536 0.023803952 + 3 O : 0.025143458 -0.002979462 -0.016347226 + 4 H : -0.033090956 0.001902162 -0.008153756 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000031844 0.0000067262 -0.0000280354 + +Norm of the Cartesian gradient ... 0.0884612741 +RMS gradient ... 0.0255365702 +MAX gradient ... 0.0547161362 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.124 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 4.0%) +RI-J Coulomb gradient .... 0.058 sec ( 46.9%) +XC gradient .... 0.019 sec ( 15.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.537914405 Eh +Current gradient norm .... 0.088461274 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999909863 +Lowest eigenvalues of augmented Hessian: + -0.000084908 0.361160222 0.386937785 0.443629377 0.671022333 +Length of the computed step .... 0.013427511 +The final length of the internal step .... 0.013427511 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0054817583 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0062797712 RMS(Int)= 0.0054803057 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0027380735 0.0001000000 NO + MAX gradient 0.0051262355 0.0003000000 NO + RMS step 0.0054817583 0.0020000000 NO + MAX step 0.0098385890 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0036 Max(Angles) 0.56 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2806 -0.005126 0.0036 1.2842 + 2. B(O 2,O 1) 1.3106 -0.000399 0.0003 1.3109 + 3. B(H 3,N 0) 1.0404 0.001983 -0.0027 1.0377 + 4. A(O 1,N 0,H 3) 106.53 -0.003554 0.56 107.09 + 5. A(N 0,O 1,O 2) 120.72 -0.001409 0.18 120.90 + 6. D(O 2,O 1,N 0,H 3) 50.77 0.064137 0.00 50.77 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.016 %) +Internal coordinates : 0.000 s ( 3.716 %) +B/P matrices and projection : 0.000 s (14.701 %) +Hessian update/contruction : 0.000 s (28.110 %) +Making the step : 0.000 s ( 6.462 %) +Converting the step to Cartesian: 0.000 s ( 4.847 %) +Storing new data : 0.000 s ( 3.716 %) +Checking convergence : 0.000 s ( 0.162 %) +Final printing : 0.000 s (27.948 %) +Total time : 0.001 s + +Time for energy+gradient : 8.165 s +Time for complete geometry iter : 9.121 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.114919 -0.730302 -0.414184 + O -0.059080 0.548785 -0.514575 + O 0.584059 1.266401 0.374142 + H -0.428767 -0.947039 0.550910 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.217166 -1.380071 -0.782694 + 1 O 8.0000 0 15.999 -0.111646 1.037053 -0.972406 + 2 O 8.0000 0 15.999 1.103712 2.393151 0.707025 + 3 H 1.0000 0 1.008 -0.810253 -1.789645 1.041068 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.284235293351 0.00000000 0.00000000 + O 2 1 0 1.310884939281 120.90188372 0.00000000 + H 1 2 3 1.037728919814 107.08980268 50.76923102 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.426852995949 0.00000000 0.00000000 + O 2 1 0 2.477213528323 120.90188372 0.00000000 + H 1 2 3 1.961023459698 107.08980268 50.76923102 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.600790077641 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.880e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5446000694327324 0.00e+00 1.37e-04 1.19e-03 4.02e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5446296243735844 -2.96e-05 1.14e-04 1.29e-03 5.88e-04 0.0 + 3 -205.5446203165206782 9.31e-06 6.80e-05 9.37e-04 1.30e-03 0.0 + 4 -205.5446331312831774 -1.28e-05 1.30e-04 2.05e-03 5.12e-04 0.0 + 5 -205.5446006257030547 3.25e-05 1.05e-04 1.71e-03 1.92e-03 0.0 + 6 -205.5446352480410894 -3.46e-05 1.17e-05 1.18e-04 4.53e-05 0.0 + 7 -205.5446352526832072 -4.64e-09 5.58e-06 6.17e-05 4.36e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.54463525268321 Eh -5593.15388 eV + +Components: +Nuclear Repulsion : 69.60079007764145 Eh 1893.93378 eV +Electronic Energy : -275.14542533032466 Eh -7487.08766 eV +One Electron Energy: -418.87711778355595 Eh -11398.22585 eV +Two Electron Energy: 143.73169245323129 Eh 3911.13819 eV + +Virial components: +Potential Energy : -410.38824472049487 Eh -11167.23187 eV +Kinetic Energy : 204.84360946781163 Eh 5574.07799 eV +Virial Ratio : 2.00342224874231 + +DFT components: +N(Alpha) : 11.999998927216 electrons +N(Beta) : 11.999998927216 electrons +N(Total) : 23.999997854433 electrons +E(X) : -23.338046846691 Eh +E(C) : -0.804152396507 Eh +E(XC) : -24.142199243198 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 4.6421e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.1723e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 5.5779e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.8778e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.3605e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.3233e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 2.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 33.5 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000363367 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007033079 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.537965540752 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000002519 -0.000005147 0.000001914 + 2 O : -0.000000129 0.000000640 -0.000000788 + 3 O : 0.000002560 0.000006227 0.000001784 + 4 H : 0.000000088 -0.000001720 -0.000002910 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000098743 +RMS gradient ... 0.0000028505 +MAX gradient ... 0.0000062271 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.053405101 -0.001173108 0.003696482 + 2 O : -0.046361307 0.002326869 0.022168724 + 3 O : 0.025368604 -0.002100540 -0.015784074 + 4 H : -0.032412399 0.000946780 -0.010081131 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000006559 0.0000054808 -0.0000261468 + +Norm of the Cartesian gradient ... 0.0869688844 +RMS gradient ... 0.0251057544 +MAX gradient ... 0.0534051007 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.135 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.8%) +RI-J Coulomb gradient .... 0.063 sec ( 46.3%) +XC gradient .... 0.019 sec ( 14.2%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.537965541 Eh +Current gradient norm .... 0.086968884 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999992465 +Lowest eigenvalues of augmented Hessian: + -0.000005736 0.310338634 0.387538646 0.442820700 0.654613561 +Length of the computed step .... 0.003882087 +The final length of the internal step .... 0.003882087 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0015848552 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0016892138 RMS(Int)= 0.0015847535 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000002868 +Previously predicted energy change .... -0.000042462 +Actually observed energy change .... -0.000051135 +Ratio of predicted to observed change .... 1.204270018 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000511353 0.0000050000 NO + RMS gradient 0.0006418786 0.0001000000 NO + MAX gradient 0.0011849158 0.0003000000 NO + RMS step 0.0015848552 0.0020000000 YES + MAX step 0.0029197439 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0011 Max(Angles) 0.17 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2842 -0.001185 0.0011 1.2853 + 2. B(O 2,O 1) 1.3109 0.000595 -0.0006 1.3103 + 3. B(H 3,N 0) 1.0377 0.000229 -0.0004 1.0373 + 4. A(O 1,N 0,H 3) 107.09 -0.000796 0.17 107.26 + 5. A(N 0,O 1,O 2) 120.90 -0.000169 0.03 120.93 + 6. D(O 2,O 1,N 0,H 3) 50.77 0.063641 -0.00 50.77 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 8.102 %) +Internal coordinates : 0.000 s ( 2.878 %) +B/P matrices and projection : 0.000 s (15.245 %) +Hessian update/contruction : 0.000 s (42.111 %) +Making the step : 0.000 s ( 4.904 %) +Converting the step to Cartesian: 0.000 s ( 3.412 %) +Storing new data : 0.000 s ( 2.559 %) +Checking convergence : 0.000 s ( 1.066 %) +Final printing : 0.000 s (19.403 %) +Total time : 0.001 s + +Time for energy+gradient : 6.512 s +Time for complete geometry iter : 7.414 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.115258 -0.730333 -0.413358 + O -0.058429 0.549766 -0.514463 + O 0.584378 1.267638 0.373427 + H -0.429399 -0.949228 0.550686 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.217806 -1.380128 -0.781133 + 1 O 8.0000 0 15.999 -0.110415 1.038908 -0.972194 + 2 O 8.0000 0 15.999 1.104314 2.395489 0.705674 + 3 H 1.0000 0 1.008 -0.811446 -1.793781 1.040646 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.285342314054 0.00000000 0.00000000 + O 2 1 0 1.310300994349 120.93204627 0.00000000 + H 1 2 3 1.037294306880 107.25709168 50.76923102 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.428944961902 0.00000000 0.00000000 + O 2 1 0 2.476110032325 120.93204627 0.00000000 + H 1 2 3 1.960202160278 107.25709168 50.76923102 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.583714614223 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.876e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5446274284980177 0.00e+00 3.94e-05 3.32e-04 9.16e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5446298988456419 -2.47e-06 3.91e-05 5.33e-04 1.33e-04 0.0 + 3 -205.5446275760160120 2.32e-06 3.21e-05 4.51e-04 5.93e-04 0.0 + 4 -205.5446300042216876 -2.43e-06 3.46e-05 5.55e-04 2.04e-04 0.0 + 5 -205.5446279017688198 2.10e-06 2.49e-05 4.20e-04 6.24e-04 0.0 + 6 -205.5446303257742215 -2.42e-06 2.43e-06 2.49e-05 8.82e-06 0.0 + 7 -205.5446303256255192 1.49e-10 1.15e-06 1.30e-05 8.92e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.54463032562552 Eh -5593.15374 eV + +Components: +Nuclear Repulsion : 69.58371461422286 Eh 1893.46914 eV +Electronic Energy : -275.12834493984838 Eh -7486.62288 eV +One Electron Energy: -418.84231026625008 Eh -11397.27869 eV +Two Electron Energy: 143.71396532640173 Eh 3910.65581 eV + +Virial components: +Potential Energy : -410.38667915093117 Eh -11167.18927 eV +Kinetic Energy : 204.84204882530565 Eh 5574.03553 eV +Virial Ratio : 2.00342986952312 + +DFT components: +N(Alpha) : 11.999998932794 electrons +N(Beta) : 11.999998932794 electrons +N(Total) : 23.999997865588 electrons +E(X) : -23.337508763714 Eh +E(C) : -0.804123575880 Eh +E(XC) : -24.141632339594 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.4870e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.3035e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.1512e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.4666e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 8.9226e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 6.9741e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 2.6 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 33.6 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000363340 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007024851 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.537968813843 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000002523 -0.000005161 0.000001913 + 2 O : -0.000000126 0.000000646 -0.000000789 + 3 O : 0.000002568 0.000006247 0.000001779 + 4 H : 0.000000082 -0.000001732 -0.000002904 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000098966 +RMS gradient ... 0.0000028569 +MAX gradient ... 0.0000062472 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.053122176 -0.001806929 0.004419718 + 2 O : -0.046073582 0.003389095 0.021884163 + 3 O : 0.025233605 -0.002172865 -0.015902536 + 4 H : -0.032282199 0.000590698 -0.010401344 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000012657 0.0000096113 -0.0000318778 + +Norm of the Cartesian gradient ... 0.0866196631 +RMS gradient ... 0.0250049429 +MAX gradient ... 0.0531221763 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.142 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.006 sec ( 4.1%) +RI-J Coulomb gradient .... 0.064 sec ( 45.0%) +XC gradient .... 0.018 sec ( 12.6%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.537968814 Eh +Current gradient norm .... 0.086619663 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999611 +Lowest eigenvalues of augmented Hessian: + -0.000000386 0.308977193 0.386944111 0.440239397 0.556825542 +Length of the computed step .... 0.000882542 +The final length of the internal step .... 0.000882542 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0003602962 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001899276 RMS(Int)= 0.0003602985 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000193 +Previously predicted energy change .... -0.000002868 +Actually observed energy change .... -0.000003273 +Ratio of predicted to observed change .... 1.141241959 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000032731 0.0000050000 YES + RMS gradient 0.0001848145 0.0001000000 NO + MAX gradient 0.0004116220 0.0003000000 NO + RMS step 0.0003602962 0.0020000000 YES + MAX step 0.0007534084 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0004 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2853 -0.000179 0.0002 1.2856 + 2. B(O 2,O 1) 1.3103 0.000412 -0.0004 1.3099 + 3. B(H 3,N 0) 1.0373 -0.000016 -0.0000 1.0373 + 4. A(O 1,N 0,H 3) 107.26 0.000054 0.00 107.26 + 5. A(N 0,O 1,O 2) 120.93 -0.000018 0.01 120.94 + 6. D(O 2,O 1,N 0,H 3) 50.77 0.063497 0.00 50.77 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.557 %) +Internal coordinates : 0.000 s ( 3.047 %) +B/P matrices and projection : 0.000 s (12.188 %) +Hessian update/contruction : 0.000 s (32.964 %) +Making the step : 0.000 s ( 5.125 %) +Converting the step to Cartesian: 0.000 s ( 3.878 %) +Storing new data : 0.000 s ( 3.047 %) +Checking convergence : 0.000 s ( 1.385 %) +Final printing : 0.000 s (28.670 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.115270 -0.730368 -0.413307 + O -0.058311 0.549964 -0.514348 + O 0.584315 1.267612 0.373266 + H -0.429443 -0.949364 0.550681 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.217828 -1.380196 -0.781038 + 1 O 8.0000 0 15.999 -0.110191 1.039282 -0.971977 + 2 O 8.0000 0 15.999 1.104195 2.395439 0.705371 + 3 H 1.0000 0 1.008 -0.811529 -1.794038 1.040636 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.285575792448 0.00000000 0.00000000 + O 2 1 0 1.309902307804 120.93778721 0.00000000 + H 1 2 3 1.037273701931 107.26115677 50.76923102 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.429386172125 0.00000000 0.00000000 + O 2 1 0 2.475356623942 120.93778721 0.00000000 + H 1 2 3 1.960163222568 107.26115677 50.76923102 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.587587623859 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.872e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.5875876239 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.5 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5446299096652751 0.00e+00 1.13e-05 1.26e-04 1.95e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5446301079012983 -1.98e-07 1.35e-05 1.87e-04 4.03e-05 0.0 + 3 -205.5446297470813874 3.61e-07 1.11e-05 1.66e-04 2.31e-04 0.0 + 4 -205.5446301310214494 -3.84e-07 2.88e-06 4.85e-05 2.00e-05 0.0 + 5 -205.5446301156357549 1.54e-08 2.05e-06 3.57e-05 5.31e-05 0.0 + 6 -205.5446301334197869 -1.78e-08 1.68e-07 1.42e-06 1.07e-06 0.0 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 6 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.54463013341979 Eh -5593.15374 eV + +Components: +Nuclear Repulsion : 69.58758762385928 Eh 1893.57453 eV +Electronic Energy : -275.13221775727908 Eh -7486.72826 eV +One Electron Energy: -418.84918017558681 Eh -11397.46563 eV +Two Electron Energy: 143.71696241830773 Eh 3910.73737 eV + +Virial components: +Potential Energy : -410.38695523172953 Eh -11167.19678 eV +Kinetic Energy : 204.84232509830974 Eh 5574.04304 eV +Virial Ratio : 2.00342851524836 + +DFT components: +N(Alpha) : 11.999998924075 electrons +N(Beta) : 11.999998924075 electrons +N(Total) : 23.999997848150 electrons +E(X) : -23.337543634263 Eh +E(C) : -0.804131662971 Eh +E(XC) : -24.141675297234 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.7784e-08 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.4163e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.6830e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.6591e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.0692e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.6485e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.188626 -522.1491 + 1 2.0000 -19.030190 -517.8378 + 2 2.0000 -14.266257 -388.2046 + 3 2.0000 -1.248405 -33.9708 + 4 2.0000 -0.968346 -26.3500 + 5 2.0000 -0.717007 -19.5108 + 6 2.0000 -0.566429 -15.4133 + 7 2.0000 -0.518973 -14.1220 + 8 2.0000 -0.496050 -13.4982 + 9 2.0000 -0.333744 -9.0816 + 10 2.0000 -0.273332 -7.4377 + 11 2.0000 -0.270693 -7.3659 + 12 0.0000 -0.202223 -5.5028 + 13 0.0000 0.036451 0.9919 + 14 0.0000 0.093687 2.5494 + 15 0.0000 0.135879 3.6975 + 16 0.0000 0.228538 6.2188 + 17 0.0000 0.262181 7.1343 + 18 0.0000 0.310590 8.4516 + 19 0.0000 0.326503 8.8846 + 20 0.0000 0.360097 9.7987 + 21 0.0000 0.384907 10.4738 + 22 0.0000 0.396792 10.7973 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.279183 + 1 O : 0.203430 + 2 O : -0.194055 + 3 H : 0.269808 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.838389 s : 3.838389 + pz : 1.401094 p : 3.385776 + px : 1.114057 + py : 0.870625 + dz2 : 0.015516 d : 0.055018 + dxz : 0.001561 + dyz : 0.009892 + dx2y2 : 0.013482 + dxy : 0.014569 + + 1 O s : 3.740344 s : 3.740344 + pz : 1.464795 p : 3.922134 + px : 1.341869 + py : 1.115470 + dz2 : 0.029801 d : 0.134093 + dxz : 0.012772 + dyz : 0.030071 + dx2y2 : 0.024570 + dxy : 0.036878 + + 2 O s : 3.942579 s : 3.942579 + pz : 1.439814 p : 4.236196 + px : 1.215102 + py : 1.581279 + dz2 : 0.003219 d : 0.015280 + dxz : 0.002439 + dyz : 0.004690 + dx2y2 : 0.001473 + dxy : 0.003459 + + 3 H s : 0.700720 s : 0.700720 + pz : 0.016813 p : 0.029472 + px : 0.007754 + py : 0.004905 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.065337 + 1 O : -0.182611 + 2 O : -0.030149 + 3 H : 0.278097 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.341195 s : 3.341195 + pz : 1.356738 p : 3.413982 + px : 1.033758 + py : 1.023485 + dz2 : 0.053348 d : 0.310160 + dxz : 0.009240 + dyz : 0.098070 + dx2y2 : 0.086331 + dxy : 0.063170 + + 1 O s : 3.367682 s : 3.367682 + pz : 1.462678 p : 4.046745 + px : 1.268726 + py : 1.315340 + dz2 : 0.126161 d : 0.768185 + dxz : 0.073329 + dyz : 0.203675 + dx2y2 : 0.179184 + dxy : 0.185836 + + 2 O s : 3.607845 s : 3.607845 + pz : 1.413707 p : 4.174687 + px : 1.201274 + py : 1.559706 + dz2 : 0.056328 d : 0.247617 + dxz : 0.055443 + dyz : 0.053273 + dx2y2 : 0.044346 + dxy : 0.038227 + + 3 H s : 0.646184 s : 0.646184 + pz : 0.046947 p : 0.075719 + px : 0.018375 + py : 0.010397 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2792 7.0000 -0.2792 2.7816 2.7816 0.0000 + 1 O 7.7966 8.0000 0.2034 2.5971 2.5971 -0.0000 + 2 O 8.1941 8.0000 -0.1941 1.6784 1.6784 0.0000 + 3 H 0.7302 1.0000 0.2698 0.9191 0.9191 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4121 B( 0-N , 2-O ) : 0.4955 B( 0-N , 3-H ) : 0.8739 +B( 1-O , 2-O ) : 1.1613 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.528 sec +Sum of individual times .... 2.512 sec ( 99.3%) + +SCF preparation .... 0.867 sec ( 34.3%) +Fock matrix formation .... 0.166 sec ( 6.6%) + Startup .... 0.009 sec ( 5.2% of F) + Split-RI-J .... 0.025 sec ( 15.0% of F) + XC integration .... 0.108 sec ( 65.1% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.007 sec ( 6.6% of XC) + Density eval. .... 0.011 sec ( 9.9% of XC) + XC-Functional eval. .... 0.006 sec ( 5.8% of XC) + XC-Potential eval. .... 0.011 sec ( 9.8% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.011 sec ( 0.4%) +Total Energy calculation .... 0.013 sec ( 0.5%) +Population analysis .... 1.404 sec ( 55.5%) +Orbital Transformation .... 0.007 sec ( 0.3%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.010 sec ( 0.4%) +SOSCF solution .... 0.035 sec ( 1.4%) +Finished LeanSCF after 4.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 34.0 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000363340 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007024379 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.537969094103 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.026.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.026.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.255970 0.719191 -0.301118 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5446301334197869 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.206694519 0.770819217 -0.362032287 +Nuclear contribution : -0.527580258 -1.238215152 0.667357462 + ----------------------------------------- +Total Dipole Moment : -0.320885738 -0.467395934 0.305325175 + ----------------------------------------- +Magnitude (a.u.) : 0.643933288 +Magnitude (Debye) : 1.636748342 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.979478 0.422359 0.377550 +Rotational constants in MHz : 89322.496932 12662.002557 11318.672801 + +Dipole components along the rotational axes: +x,y,z [a.u.] : 0.419169 0.351638 -0.339556 +x,y,z [Debye]: 1.065442 0.893793 -0.863083 + + + +Dipole moment calculation done in 0.5 sec + +Maximum memory used throughout the entire PROP-calculation: 18.0 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 27 * + * * + * Dihedral ( 2, 1, 0, 3) : 60.00000000 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2869 0.735554 + 2. B(O 2,O 1) 1.3116 0.672672 + 3. B(H 3,N 0) 1.0397 0.391455 + 4. A(O 1,N 0,H 3) 107.0585 0.360719 + 5. A(N 0,O 1,O 2) 120.7312 0.442361 + 6. D(O 2,O 1,N 0,H 3) 60.0000 0.042751 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.082733 -0.729769 -0.402132 + O -0.083291 0.554106 -0.490703 + O 0.606449 1.284397 0.352578 + H -0.459133 -0.970890 0.536549 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.156343 -1.379064 -0.759920 + 1 O 8.0000 0 15.999 -0.157398 1.047109 -0.927294 + 2 O 8.0000 0 15.999 1.146023 2.427159 0.666276 + 3 H 1.0000 0 1.008 -0.867635 -1.834717 1.013931 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.285575792448 0.00000000 0.00000000 + O 2 1 0 1.309902307804 120.93778721 0.00000000 + H 1 2 3 1.037273701931 107.26115677 50.76923102 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.429386172125 0.00000000 0.00000000 + O 2 1 0 2.475356623942 120.93778721 0.00000000 + H 1 2 3 1.960163222568 107.26115677 50.76923102 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.480563629187 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.845e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22298 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.4805636292 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5296548403594556 0.00e+00 4.27e-04 3.36e-03 2.00e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.055) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5307167135097757 -1.06e-03 5.01e-04 4.22e-03 1.58e-02 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.5315975388347169 -8.81e-04 3.75e-04 2.92e-03 1.12e-02 0.700 0.0 + 4 -205.5322051028604164 -6.08e-04 9.31e-04 7.82e-03 7.90e-03 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5336545706496167 -1.45e-03 1.09e-04 1.47e-03 1.70e-03 0.0 + *** Restarting incremental Fock matrix formation *** + 6 -205.5336615280303363 -6.96e-06 3.81e-04 5.03e-03 1.21e-03 0.0 + 7 -205.5334218259161503 2.40e-04 2.85e-04 4.27e-03 6.61e-03 0.0 + 8 -205.5336805110294449 -2.59e-04 5.32e-05 7.65e-04 2.78e-04 0.0 + 9 -205.5336778254380761 2.69e-06 3.12e-05 5.46e-04 7.09e-04 0.0 + 10 -205.5336816870448615 -3.86e-06 8.39e-06 8.66e-05 2.90e-05 0.0 + 11 -205.5336817000655287 -1.30e-08 3.34e-06 3.93e-05 2.36e-05 0.0 + 12 -205.5336817144550423 -1.44e-08 5.74e-07 4.54e-06 3.89e-06 0.1 + 13 -205.5336817147108377 -2.56e-10 1.88e-07 1.74e-06 2.00e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 13 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.53368171471084 Eh -5592.85581 eV + +Components: +Nuclear Repulsion : 69.48056362918709 Eh 1890.66226 eV +Electronic Energy : -275.01424534389798 Eh -7483.51807 eV +One Electron Energy: -418.63907357313025 Eh -11391.74834 eV +Two Electron Energy: 143.62482822923229 Eh 3908.23027 eV + +Virial components: +Potential Energy : -410.37615702399410 Eh -11166.90295 eV +Kinetic Energy : 204.84247530928329 Eh 5574.04713 eV +Virial Ratio : 2.00337433144363 + +DFT components: +N(Alpha) : 11.999998218106 electrons +N(Beta) : 11.999998218106 electrons +N(Total) : 23.999996436212 electrons +E(X) : -23.333588580272 Eh +E(C) : -0.804066048446 Eh +E(XC) : -24.137654628717 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.5580e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.7359e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.8814e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.6988e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.9999e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.4708e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.187361 -522.1146 + 1 2.0000 -19.034358 -517.9512 + 2 2.0000 -14.261820 -388.0838 + 3 2.0000 -1.246881 -33.9293 + 4 2.0000 -0.967920 -26.3384 + 5 2.0000 -0.714549 -19.4439 + 6 2.0000 -0.567230 -15.4351 + 7 2.0000 -0.518699 -14.1145 + 8 2.0000 -0.495192 -13.4749 + 9 2.0000 -0.334497 -9.1021 + 10 2.0000 -0.273269 -7.4360 + 11 2.0000 -0.264720 -7.2034 + 12 0.0000 -0.209050 -5.6885 + 13 0.0000 0.036819 1.0019 + 14 0.0000 0.091546 2.4911 + 15 0.0000 0.136504 3.7145 + 16 0.0000 0.230573 6.2742 + 17 0.0000 0.259273 7.0552 + 18 0.0000 0.313312 8.5257 + 19 0.0000 0.325962 8.8699 + 20 0.0000 0.362679 9.8690 + 21 0.0000 0.382402 10.4057 + 22 0.0000 0.395945 10.7742 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.298078 + 1 O : 0.199861 + 2 O : -0.177192 + 3 H : 0.275409 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.837447 s : 3.837447 + pz : 1.420579 p : 3.405147 + px : 1.121824 + py : 0.862744 + dz2 : 0.015289 d : 0.055484 + dxz : 0.002631 + dyz : 0.010440 + dx2y2 : 0.013524 + dxy : 0.013600 + + 1 O s : 3.742688 s : 3.742688 + pz : 1.470368 p : 3.927279 + px : 1.341640 + py : 1.115271 + dz2 : 0.027234 d : 0.130172 + dxz : 0.012425 + dyz : 0.031034 + dx2y2 : 0.025100 + dxy : 0.034380 + + 2 O s : 3.942711 s : 3.942711 + pz : 1.455401 p : 4.220379 + px : 1.190559 + py : 1.574420 + dz2 : 0.004065 d : 0.014101 + dxz : 0.001490 + dyz : 0.003675 + dx2y2 : 0.000745 + dxy : 0.004126 + + 3 H s : 0.694859 s : 0.694859 + pz : 0.016146 p : 0.029732 + px : 0.008544 + py : 0.005042 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.078624 + 1 O : -0.182401 + 2 O : -0.020217 + 3 H : 0.281243 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.338182 s : 3.338182 + pz : 1.371331 p : 3.429762 + px : 1.041871 + py : 1.016560 + dz2 : 0.050036 d : 0.310680 + dxz : 0.010966 + dyz : 0.099377 + dx2y2 : 0.085842 + dxy : 0.064458 + + 1 O s : 3.369172 s : 3.369172 + pz : 1.460826 p : 4.047711 + px : 1.270860 + py : 1.316026 + dz2 : 0.115181 d : 0.765518 + dxz : 0.073473 + dyz : 0.202747 + dx2y2 : 0.181202 + dxy : 0.192916 + + 2 O s : 3.609990 s : 3.609990 + pz : 1.420295 p : 4.163195 + px : 1.186022 + py : 1.556878 + dz2 : 0.050422 d : 0.247033 + dxz : 0.056806 + dyz : 0.050645 + dx2y2 : 0.047982 + dxy : 0.041178 + + 3 H s : 0.642873 s : 0.642873 + pz : 0.044953 p : 0.075884 + px : 0.020322 + py : 0.010610 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2981 7.0000 -0.2981 2.7649 2.7649 -0.0000 + 1 O 7.8001 8.0000 0.1999 2.5793 2.5793 -0.0000 + 2 O 8.1772 8.0000 -0.1772 1.6749 1.6749 0.0000 + 3 H 0.7246 1.0000 0.2754 0.9142 0.9142 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4007 B( 0-N , 2-O ) : 0.4962 B( 0-N , 3-H ) : 0.8680 +B( 1-O , 2-O ) : 1.1555 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.945 sec +Sum of individual times .... 2.928 sec ( 99.4%) + +SCF preparation .... 0.866 sec ( 29.4%) +Fock matrix formation .... 0.352 sec ( 11.9%) + Startup .... 0.015 sec ( 4.1% of F) + Split-RI-J .... 0.054 sec ( 15.2% of F) + XC integration .... 0.229 sec ( 65.2% of F) + Basis function eval. .... 0.017 sec ( 7.2% of XC) + Density eval. .... 0.026 sec ( 11.4% of XC) + XC-Functional eval. .... 0.014 sec ( 6.3% of XC) + XC-Potential eval. .... 0.024 sec ( 10.5% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.024 sec ( 0.8%) +Total Energy calculation .... 0.030 sec ( 1.0%) +Population analysis .... 1.511 sec ( 51.3%) +Orbital Transformation .... 0.014 sec ( 0.5%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.068 sec ( 2.3%) +SOSCF solution .... 0.063 sec ( 2.1%) +Finished LeanSCF after 4.5 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 34.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000363100 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007006626 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.527038188824 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000002696 -0.000005271 0.000001868 + 2 O : -0.000000168 0.000000652 -0.000000751 + 3 O : 0.000002712 0.000006523 0.000001673 + 4 H : 0.000000151 -0.000001904 -0.000002790 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000101835 +RMS gradient ... 0.0000029397 +MAX gradient ... 0.0000065232 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.059618664 0.004782359 0.003316911 + 2 O : -0.049976170 -0.003314986 0.029244897 + 3 O : 0.026777614 -0.001886887 -0.020451870 + 4 H : -0.036420108 0.000419514 -0.012109939 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000188149 0.0000039706 -0.0000179691 + +Norm of the Cartesian gradient ... 0.0977970319 +RMS gradient ... 0.0282315714 +MAX gradient ... 0.0596186639 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.143 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.006 sec ( 4.0%) +RI-J Coulomb gradient .... 0.063 sec ( 44.0%) +XC gradient .... 0.020 sec ( 13.7%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.527038189 Eh +Current gradient norm .... 0.097797032 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999890672 +Lowest eigenvalues of augmented Hessian: + -0.000103446 0.359913684 0.388018508 0.441481710 0.668588158 +Length of the computed step .... 0.014788224 +The final length of the internal step .... 0.014788224 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0060372670 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0064874624 RMS(Int)= 0.0060362231 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0030236849 0.0001000000 NO + MAX gradient 0.0057836056 0.0003000000 NO + RMS step 0.0060372670 0.0020000000 NO + MAX step 0.0108528526 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0042 Max(Angles) 0.62 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2869 -0.005784 0.0042 1.2911 + 2. B(O 2,O 1) 1.3116 -0.000120 0.0001 1.3117 + 3. B(H 3,N 0) 1.0397 0.002156 -0.0029 1.0367 + 4. A(O 1,N 0,H 3) 107.06 -0.003907 0.62 107.68 + 5. A(N 0,O 1,O 2) 120.73 -0.001217 0.16 120.89 + 6. D(O 2,O 1,N 0,H 3) 60.00 0.071883 0.00 60.00 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.431 %) +Internal coordinates : 0.000 s ( 3.593 %) +B/P matrices and projection : 0.000 s (15.120 %) +Hessian update/contruction : 0.000 s (27.695 %) +Making the step : 0.000 s ( 6.437 %) +Converting the step to Cartesian: 0.000 s ( 5.090 %) +Storing new data : 0.000 s ( 3.743 %) +Checking convergence : 0.000 s ( 0.150 %) +Final printing : 0.000 s (28.443 %) +Total time : 0.001 s + +Time for energy+gradient : 8.705 s +Time for complete geometry iter : 9.631 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.084711 -0.730730 -0.398707 + O -0.081137 0.557104 -0.490530 + O 0.608312 1.290256 0.350652 + H -0.461171 -0.978786 0.534878 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.160080 -1.380879 -0.753447 + 1 O 8.0000 0 15.999 -0.153328 1.052774 -0.926968 + 2 O 8.0000 0 15.999 1.149542 2.438230 0.662635 + 3 H 1.0000 0 1.008 -0.871487 -1.849638 1.010773 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.291108127164 0.00000000 0.00000000 + O 2 1 0 1.311654980118 120.88916554 0.00000000 + H 1 2 3 1.036742788619 107.68037049 59.99999993 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.439840769620 0.00000000 0.00000000 + O 2 1 0 2.478668694618 120.88916554 0.00000000 + H 1 2 3 1.959159941808 107.68037049 59.99999993 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.362591952057 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.850e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22298 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5336715029016261 0.00e+00 1.47e-04 1.26e-03 3.93e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5337056277247996 -3.41e-05 1.28e-04 1.47e-03 6.06e-04 0.0 + 3 -205.5336915661511341 1.41e-05 8.73e-05 1.17e-03 1.39e-03 0.0 + 4 -205.5337085158933235 -1.69e-05 1.56e-04 2.30e-03 7.19e-04 0.0 + 5 -205.5336661337731528 4.24e-05 1.20e-04 1.76e-03 2.30e-03 0.0 + 6 -205.5337127701515954 -4.66e-05 1.23e-05 1.27e-04 4.41e-05 0.0 + 7 -205.5337127788854730 -8.73e-09 5.79e-06 6.48e-05 4.31e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.53371277888547 Eh -5592.85666 eV + +Components: +Nuclear Repulsion : 69.36259195205704 Eh 1887.45208 eV +Electronic Energy : -274.89630473094257 Eh -7480.30874 eV +One Electron Energy: -418.41330612921433 Eh -11385.60489 eV +Two Electron Energy: 143.51700139827179 Eh 3905.29615 eV + +Virial components: +Potential Energy : -410.36689513146592 Eh -11166.65092 eV +Kinetic Energy : 204.83318235258045 Eh 5573.79426 eV +Virial Ratio : 2.00342000460208 + +DFT components: +N(Alpha) : 11.999998199565 electrons +N(Beta) : 11.999998199565 electrons +N(Total) : 23.999996399130 electrons +E(X) : -23.331729459375 Eh +E(C) : -0.803876621309 Eh +E(XC) : -24.135606080684 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 8.7339e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.4804e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 5.7881e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.9933e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.3148e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.4714e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 2.5 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 34.5 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000362952 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006973913 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.527101817796 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000002715 -0.000005335 0.000001858 + 2 O : -0.000000160 0.000000668 -0.000000757 + 3 O : 0.000002754 0.000006624 0.000001665 + 4 H : 0.000000121 -0.000001957 -0.000002765 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000102988 +RMS gradient ... 0.0000029730 +MAX gradient ... 0.0000066243 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.058118990 0.001390664 0.006653950 + 2 O : -0.049660820 0.000268472 0.027327169 + 3 O : 0.027004354 -0.001139744 -0.019821798 + 4 H : -0.035462524 -0.000519392 -0.014159321 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000174246 -0.0000046124 -0.0000200640 + +Norm of the Cartesian gradient ... 0.0960148627 +RMS gradient ... 0.0277171034 +MAX gradient ... 0.0581189901 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.125 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.7%) +RI-J Coulomb gradient .... 0.056 sec ( 45.0%) +XC gradient .... 0.016 sec ( 13.0%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.527101818 Eh +Current gradient norm .... 0.096014863 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999987195 +Lowest eigenvalues of augmented Hessian: + -0.000009425 0.302747654 0.389344446 0.439311076 0.630064872 +Length of the computed step .... 0.005060615 +The final length of the internal step .... 0.005060615 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0020659873 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0021161741 RMS(Int)= 0.0020659325 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000004712 +Previously predicted energy change .... -0.000051734 +Actually observed energy change .... -0.000063629 +Ratio of predicted to observed change .... 1.229918030 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000636290 0.0000050000 NO + RMS gradient 0.0008060497 0.0001000000 NO + MAX gradient 0.0014642099 0.0003000000 NO + RMS step 0.0020659873 0.0020000000 NO + MAX step 0.0037057400 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0015 Max(Angles) 0.21 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2911 -0.001464 0.0015 1.2926 + 2. B(O 2,O 1) 1.3117 0.000843 -0.0009 1.3108 + 3. B(H 3,N 0) 1.0367 0.000252 -0.0005 1.0362 + 4. A(O 1,N 0,H 3) 107.68 -0.000961 0.21 107.89 + 5. A(N 0,O 1,O 2) 120.89 -0.000239 0.04 120.93 + 6. D(O 2,O 1,N 0,H 3) 60.00 0.071270 -0.00 60.00 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 7.457 %) +Internal coordinates : 0.000 s ( 2.812 %) +B/P matrices and projection : 0.000 s (11.614 %) +Hessian update/contruction : 0.000 s (42.054 %) +Making the step : 0.000 s ( 5.379 %) +Converting the step to Cartesian: 0.000 s ( 3.667 %) +Storing new data : 0.000 s ( 3.301 %) +Checking convergence : 0.000 s ( 1.711 %) +Final printing : 0.000 s (21.883 %) +Total time : 0.001 s + +Time for energy+gradient : 7.053 s +Time for complete geometry iter : 7.995 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.085219 -0.730812 -0.397651 + O -0.080245 0.558423 -0.490383 + O 0.608665 1.291731 0.349754 + H -0.461910 -0.981498 0.534571 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.161040 -1.381034 -0.751451 + 1 O 8.0000 0 15.999 -0.151641 1.055267 -0.926689 + 2 O 8.0000 0 15.999 1.150211 2.441017 0.660940 + 3 H 1.0000 0 1.008 -0.872883 -1.854762 1.010194 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.292575318054 0.00000000 0.00000000 + O 2 1 0 1.310789138145 120.93290896 0.00000000 + H 1 2 3 1.036232463915 107.89269376 59.99999993 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.442613358588 0.00000000 0.00000000 + O 2 1 0 2.477032490413 120.93290896 0.00000000 + H 1 2 3 1.958195567877 107.89269376 59.99999993 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.342663226891 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.844e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22299 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5575 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5337030928383797 0.00e+00 5.25e-05 4.17e-04 1.32e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5337074769964261 -4.38e-06 5.60e-05 7.43e-04 1.85e-04 0.0 + 3 -205.5337024734682814 5.00e-06 4.57e-05 6.18e-04 9.60e-04 0.0 + 4 -205.5337078889193663 -5.42e-06 4.14e-05 6.59e-04 2.36e-04 0.0 + 5 -205.5337048960745392 2.99e-06 3.00e-05 4.88e-04 6.94e-04 0.0 + 6 -205.5337083517263181 -3.46e-06 2.88e-06 2.87e-05 9.79e-06 0.0 + 7 -205.5337083522221064 -4.96e-10 1.27e-06 1.45e-05 9.58e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.53370835222211 Eh -5592.85654 eV + +Components: +Nuclear Repulsion : 69.34266322689092 Eh 1886.90980 eV +Electronic Energy : -274.87637157911297 Eh -7479.76633 eV +One Electron Energy: -418.37272155862564 Eh -11384.50053 eV +Two Electron Energy: 143.49634997951264 Eh 3904.73420 eV + +Virial components: +Potential Energy : -410.36497213256519 Eh -11166.59859 eV +Kinetic Energy : 204.83126378034305 Eh 5573.74205 eV +Virial Ratio : 2.00342938162327 + +DFT components: +N(Alpha) : 11.999998182992 electrons +N(Beta) : 11.999998182992 electrons +N(Total) : 23.999996365984 electrons +E(X) : -23.331127352575 Eh +E(C) : -0.803844573209 Eh +E(XC) : -24.134971925784 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 4.9579e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.4493e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.2746e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.2709e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 9.5800e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 7.7259e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 2.5 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 34.7 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000362914 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006964024 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.527107242557 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000002720 -0.000005353 0.000001856 + 2 O : -0.000000156 0.000000676 -0.000000758 + 3 O : 0.000002764 0.000006650 0.000001658 + 4 H : 0.000000112 -0.000001974 -0.000002757 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000103279 +RMS gradient ... 0.0000029814 +MAX gradient ... 0.0000066497 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.057739392 0.000546600 0.007513633 + 2 O : -0.049298150 0.001648052 0.026994546 + 3 O : 0.026806209 -0.001261359 -0.019975042 + 4 H : -0.035247451 -0.000933293 -0.014533137 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000204176 -0.0000004475 -0.0000213837 + +Norm of the Cartesian gradient ... 0.0955298490 +RMS gradient ... 0.0275770920 +MAX gradient ... 0.0577393920 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.128 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.2%) +RI-J Coulomb gradient .... 0.062 sec ( 48.1%) +XC gradient .... 0.018 sec ( 14.4%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.527107243 Eh +Current gradient norm .... 0.095529849 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999178 +Lowest eigenvalues of augmented Hessian: + -0.000000758 0.294508030 0.388757154 0.435997510 0.537505288 +Length of the computed step .... 0.001282190 +The final length of the internal step .... 0.001282190 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0005234518 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0002847879 RMS(Int)= 0.0005234584 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000379 +Previously predicted energy change .... -0.000004712 +Actually observed energy change .... -0.000005425 +Ratio of predicted to observed change .... 1.151168241 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000054248 0.0000050000 NO + RMS gradient 0.0002527187 0.0001000000 NO + MAX gradient 0.0005777441 0.0003000000 NO + RMS step 0.0005234518 0.0020000000 YES + MAX step 0.0011049915 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0006 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2926 -0.000203 0.0003 1.2929 + 2. B(O 2,O 1) 1.3108 0.000578 -0.0006 1.3102 + 3. B(H 3,N 0) 1.0362 -0.000034 -0.0000 1.0362 + 4. A(O 1,N 0,H 3) 107.89 0.000070 0.01 107.90 + 5. A(N 0,O 1,O 2) 120.93 -0.000046 0.01 120.94 + 6. D(O 2,O 1,N 0,H 3) 60.00 0.071065 0.00 60.00 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 8.922 %) +Internal coordinates : 0.000 s ( 2.781 %) +B/P matrices and projection : 0.000 s (19.815 %) +Hessian update/contruction : 0.000 s (29.432 %) +Making the step : 0.000 s ( 5.330 %) +Converting the step to Cartesian: 0.000 s ( 3.708 %) +Storing new data : 0.000 s ( 3.244 %) +Checking convergence : 0.000 s ( 1.275 %) +Final printing : 0.000 s (25.029 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.085244 -0.730854 -0.397580 + O -0.080051 0.558705 -0.490209 + O 0.608567 1.291709 0.349520 + H -0.461980 -0.981716 0.534560 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.161087 -1.381114 -0.751317 + 1 O 8.0000 0 15.999 -0.151275 1.055800 -0.926361 + 2 O 8.0000 0 15.999 1.150025 2.440977 0.660498 + 3 H 1.0000 0 1.008 -0.873016 -1.855175 1.010173 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.292892017501 0.00000000 0.00000000 + O 2 1 0 1.310204401847 120.94453109 0.00000000 + H 1 2 3 1.036217891810 107.90136941 59.99999993 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.443211833810 0.00000000 0.00000000 + O 2 1 0 2.475927498949 120.94453109 0.00000000 + H 1 2 3 1.958168030591 107.90136941 59.99999993 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.348683787383 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.838e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22299 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5575 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.3486837874 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.5 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5337075617707114 0.00e+00 1.68e-05 1.87e-04 2.62e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5337079821234170 -4.20e-07 1.96e-05 2.68e-04 6.56e-05 0.0 + 3 -205.5337072508673373 7.31e-07 1.59e-05 2.34e-04 3.63e-04 0.0 + 4 -205.5337080368391298 -7.86e-07 3.90e-06 6.31e-05 2.45e-05 0.0 + 5 -205.5337080103918765 2.64e-08 2.73e-06 4.60e-05 6.53e-05 0.0 + 6 -205.5337080414902289 -3.11e-08 2.66e-07 1.93e-06 1.50e-06 0.0 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 6 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.53370804149023 Eh -5592.85653 eV + +Components: +Nuclear Repulsion : 69.34868378738281 Eh 1887.07362 eV +Electronic Energy : -274.88239182887298 Eh -7479.93015 eV +One Electron Energy: -418.38355701709361 Eh -11384.79538 eV +Two Electron Energy: 143.50116518822060 Eh 3904.86522 eV + +Virial components: +Potential Energy : -410.36539696544651 Eh -11166.61015 eV +Kinetic Energy : 204.83168892395625 Eh 5573.75362 eV +Virial Ratio : 2.00342729741292 + +DFT components: +N(Alpha) : 11.999998170830 electrons +N(Beta) : 11.999998170830 electrons +N(Total) : 23.999996341660 electrons +E(X) : -23.331208430660 Eh +E(C) : -0.803857176380 Eh +E(XC) : -24.135065607040 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.1098e-08 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.9269e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.6586e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.3472e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.5037e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 5.9351e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.187430 -522.1165 + 1 2.0000 -19.035253 -517.9756 + 2 2.0000 -14.261102 -388.0643 + 3 2.0000 -1.245112 -33.8812 + 4 2.0000 -0.966623 -26.3031 + 5 2.0000 -0.715617 -19.4729 + 6 2.0000 -0.566895 -15.4260 + 7 2.0000 -0.517792 -14.0898 + 8 2.0000 -0.494982 -13.4691 + 9 2.0000 -0.334298 -9.0967 + 10 2.0000 -0.273459 -7.4412 + 11 2.0000 -0.264610 -7.2004 + 12 0.0000 -0.209350 -5.6967 + 13 0.0000 0.036235 0.9860 + 14 0.0000 0.092885 2.5275 + 15 0.0000 0.134372 3.6565 + 16 0.0000 0.229442 6.2434 + 17 0.0000 0.259775 7.0688 + 18 0.0000 0.313493 8.5306 + 19 0.0000 0.325871 8.8674 + 20 0.0000 0.362868 9.8741 + 21 0.0000 0.381867 10.3911 + 22 0.0000 0.395740 10.7686 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.299808 + 1 O : 0.200165 + 2 O : -0.174641 + 3 H : 0.274283 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.836553 s : 3.836553 + pz : 1.424010 p : 3.408697 + px : 1.124387 + py : 0.860300 + dz2 : 0.015038 d : 0.054558 + dxz : 0.002508 + dyz : 0.010322 + dx2y2 : 0.013400 + dxy : 0.013290 + + 1 O s : 3.743331 s : 3.743331 + pz : 1.471773 p : 3.926188 + px : 1.342185 + py : 1.112229 + dz2 : 0.027225 d : 0.130316 + dxz : 0.012421 + dyz : 0.030911 + dx2y2 : 0.025313 + dxy : 0.034446 + + 2 O s : 3.943070 s : 3.943070 + pz : 1.459055 p : 4.217476 + px : 1.189191 + py : 1.569229 + dz2 : 0.004062 d : 0.014095 + dxz : 0.001479 + dyz : 0.003649 + dx2y2 : 0.000698 + dxy : 0.004206 + + 3 H s : 0.695716 s : 0.695716 + pz : 0.016213 p : 0.030001 + px : 0.008668 + py : 0.005120 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.079495 + 1 O : -0.180566 + 2 O : -0.019023 + 3 H : 0.279085 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.338465 s : 3.338465 + pz : 1.376763 p : 3.433111 + px : 1.044935 + py : 1.011413 + dz2 : 0.049402 d : 0.307919 + dxz : 0.010886 + dyz : 0.098675 + dx2y2 : 0.085372 + dxy : 0.063584 + + 1 O s : 3.371311 s : 3.371311 + pz : 1.462329 p : 4.045974 + px : 1.271493 + py : 1.312151 + dz2 : 0.115482 d : 0.763281 + dxz : 0.073136 + dyz : 0.200596 + dx2y2 : 0.181578 + dxy : 0.192489 + + 2 O s : 3.609571 s : 3.609571 + pz : 1.423628 p : 4.161624 + px : 1.184713 + py : 1.553283 + dz2 : 0.050610 d : 0.247829 + dxz : 0.056735 + dyz : 0.050828 + dx2y2 : 0.048140 + dxy : 0.041517 + + 3 H s : 0.644081 s : 0.644081 + pz : 0.045191 p : 0.076834 + px : 0.020677 + py : 0.010966 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2998 7.0000 -0.2998 2.7650 2.7650 0.0000 + 1 O 7.7998 8.0000 0.2002 2.5785 2.5785 0.0000 + 2 O 8.1746 8.0000 -0.1746 1.6787 1.6787 0.0000 + 3 H 0.7257 1.0000 0.2743 0.9145 0.9145 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3981 B( 0-N , 2-O ) : 0.4987 B( 0-N , 3-H ) : 0.8681 +B( 1-O , 2-O ) : 1.1570 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.419 sec +Sum of individual times .... 2.403 sec ( 99.3%) + +SCF preparation .... 0.854 sec ( 35.3%) +Fock matrix formation .... 0.157 sec ( 6.5%) + Startup .... 0.009 sec ( 5.4% of F) + Split-RI-J .... 0.022 sec ( 14.1% of F) + XC integration .... 0.104 sec ( 66.2% of F) + Basis function eval. .... 0.006 sec ( 6.1% of XC) + Density eval. .... 0.009 sec ( 8.8% of XC) + XC-Functional eval. .... 0.005 sec ( 5.2% of XC) + XC-Potential eval. .... 0.008 sec ( 8.1% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.010 sec ( 0.4%) +Total Energy calculation .... 0.012 sec ( 0.5%) +Population analysis .... 1.321 sec ( 54.6%) +Orbital Transformation .... 0.006 sec ( 0.3%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.010 sec ( 0.4%) +SOSCF solution .... 0.033 sec ( 1.3%) +Finished LeanSCF after 3.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 35.0 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000362914 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006963172 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.527107783325 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.027.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.027.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.273172 0.738724 -0.292663 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5337080414902289 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.226078959 0.837602910 -0.317383356 +Nuclear contribution : -0.566763326 -1.278145113 0.647971669 + ----------------------------------------- +Total Dipole Moment : -0.340684367 -0.440542203 0.330588313 + ----------------------------------------- +Magnitude (a.u.) : 0.647635625 +Magnitude (Debye) : 1.646158937 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.995853 0.416693 0.375411 +Rotational constants in MHz : 89813.414987 12492.156109 11254.549546 + +Dipole components along the rotational axes: +x,y,z [a.u.] : 0.403385 0.315378 -0.396546 +x,y,z [Debye]: 1.025323 0.801628 -1.007941 + + + +Dipole moment calculation done in 0.5 sec + +Maximum memory used throughout the entire PROP-calculation: 18.5 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 28 * + * * + * Dihedral ( 2, 1, 0, 3) : 69.23076923 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2940 0.716048 + 2. B(O 2,O 1) 1.3120 0.671926 + 3. B(H 3,N 0) 1.0388 0.392976 + 4. A(O 1,N 0,H 3) 107.7149 0.359309 + 5. A(N 0,O 1,O 2) 120.7521 0.440130 + 6. D(O 2,O 1,N 0,H 3) 69.2308 0.040267 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.054659 -0.728798 -0.383439 + O -0.102461 0.561866 -0.463655 + O 0.630188 1.310694 0.326154 + H -0.491776 -1.005918 0.517231 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.103291 -1.377229 -0.724595 + 1 O 8.0000 0 15.999 -0.193623 1.061773 -0.876180 + 2 O 8.0000 0 15.999 1.190883 2.476853 0.616343 + 3 H 1.0000 0 1.008 -0.929322 -1.900910 0.977425 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.292892017501 0.00000000 0.00000000 + O 2 1 0 1.310204401847 120.94453109 0.00000000 + H 1 2 3 1.036217891810 107.90136941 59.99999993 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.443211833810 0.00000000 0.00000000 + O 2 1 0 2.475927498949 120.94453109 0.00000000 + H 1 2 3 1.958168030591 107.90136941 59.99999993 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1676 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.241296123497 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.833e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22303 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.2412961235 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.5 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5177026539203098 0.00e+00 4.53e-04 3.62e-03 2.02e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.040) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5187479465533329 -1.05e-03 5.31e-04 4.66e-03 1.59e-02 0.700 0.1 + ***Turning on AO-DIIS*** + 3 -205.5196213494298831 -8.73e-04 3.96e-04 3.23e-03 1.13e-02 0.700 0.1 + 4 -205.5202219993040558 -6.01e-04 9.89e-04 8.70e-03 7.98e-03 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5216617853818093 -1.44e-03 1.13e-04 1.42e-03 1.71e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -205.5216711261334126 -9.34e-06 3.60e-04 4.62e-03 1.15e-03 0.0 + 7 -205.5214933125256493 1.78e-04 2.46e-04 3.55e-03 6.26e-03 0.0 + 8 -205.5216910538596835 -1.98e-04 5.91e-05 7.51e-04 1.90e-04 0.0 + 9 -205.5216902092831788 8.45e-07 3.13e-05 4.68e-04 5.10e-04 0.0 + 10 -205.5216925604166249 -2.35e-06 1.08e-05 1.33e-04 5.44e-05 0.1 + 11 -205.5216925821162590 -2.17e-08 4.96e-06 5.76e-05 3.56e-05 0.0 + 12 -205.5216926147613776 -3.26e-08 8.21e-07 6.42e-06 4.55e-06 0.0 + 13 -205.5216926152828592 -5.21e-10 2.51e-07 2.15e-06 2.88e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 13 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.52169261528286 Eh -5592.52957 eV + +Components: +Nuclear Repulsion : 69.24129612349726 Eh 1884.15146 eV +Electronic Energy : -274.76298873878011 Eh -7476.68103 eV +One Electron Energy: -418.16973291107263 Eh -11378.97693 eV +Two Electron Energy: 143.40674417229252 Eh 3902.29590 eV + +Virial components: +Potential Energy : -410.35071610812736 Eh -11166.21066 eV +Kinetic Energy : 204.82902349284450 Eh 5573.68109 eV +Virial Ratio : 2.00338169420830 + +DFT components: +N(Alpha) : 11.999995909803 electrons +N(Beta) : 11.999995909803 electrons +N(Total) : 23.999991819605 electrons +E(X) : -23.326573476158 Eh +E(C) : -0.803831570930 Eh +E(XC) : -24.130405047088 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 5.2148e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.1513e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.5090e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.7135e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.8800e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.8264e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.186972 -522.1041 + 1 2.0000 -19.040334 -518.1138 + 2 2.0000 -14.255216 -387.9041 + 3 2.0000 -1.243893 -33.8481 + 4 2.0000 -0.966334 -26.2953 + 5 2.0000 -0.712997 -19.4016 + 6 2.0000 -0.567375 -15.4391 + 7 2.0000 -0.518107 -14.0984 + 8 2.0000 -0.494487 -13.4557 + 9 2.0000 -0.335125 -9.1192 + 10 2.0000 -0.275825 -7.5056 + 11 2.0000 -0.255619 -6.9557 + 12 0.0000 -0.216512 -5.8916 + 13 0.0000 0.035212 0.9582 + 14 0.0000 0.092072 2.5054 + 15 0.0000 0.135173 3.6782 + 16 0.0000 0.230958 6.2847 + 17 0.0000 0.257920 7.0183 + 18 0.0000 0.315834 8.5943 + 19 0.0000 0.326091 8.8734 + 20 0.0000 0.365815 9.9543 + 21 0.0000 0.376042 10.2326 + 22 0.0000 0.394766 10.7421 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.324325 + 1 O : 0.197502 + 2 O : -0.153571 + 3 H : 0.280394 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.835361 s : 3.835361 + pz : 1.448833 p : 3.434660 + px : 1.135617 + py : 0.850209 + dz2 : 0.014242 d : 0.054305 + dxz : 0.003493 + dyz : 0.010901 + dx2y2 : 0.013477 + dxy : 0.012191 + + 1 O s : 3.746602 s : 3.746602 + pz : 1.475002 p : 3.929229 + px : 1.341026 + py : 1.113201 + dz2 : 0.024639 d : 0.126667 + dxz : 0.012544 + dyz : 0.032020 + dx2y2 : 0.026565 + dxy : 0.030898 + + 2 O s : 3.941991 s : 3.941991 + pz : 1.465510 p : 4.198151 + px : 1.173480 + py : 1.559160 + dz2 : 0.004955 d : 0.013429 + dxz : 0.000646 + dyz : 0.002773 + dx2y2 : 0.000059 + dxy : 0.004996 + + 3 H s : 0.689254 s : 0.689254 + pz : 0.015553 p : 0.030352 + px : 0.009525 + py : 0.005275 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.096399 + 1 O : -0.179259 + 2 O : -0.007481 + 3 H : 0.283139 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.333202 s : 3.333202 + pz : 1.395445 p : 3.455382 + px : 1.057898 + py : 1.002039 + dz2 : 0.045800 d : 0.307815 + dxz : 0.012610 + dyz : 0.099387 + dx2y2 : 0.084472 + dxy : 0.065546 + + 1 O s : 3.372956 s : 3.372956 + pz : 1.458113 p : 4.044967 + px : 1.273613 + py : 1.313241 + dz2 : 0.104311 d : 0.761336 + dxz : 0.072511 + dyz : 0.200238 + dx2y2 : 0.183870 + dxy : 0.200407 + + 2 O s : 3.611961 s : 3.611961 + pz : 1.422005 p : 4.148299 + px : 1.177710 + py : 1.548583 + dz2 : 0.044824 d : 0.247221 + dxz : 0.057517 + dyz : 0.048196 + dx2y2 : 0.051849 + dxy : 0.044835 + + 3 H s : 0.639812 s : 0.639812 + pz : 0.043085 p : 0.077049 + px : 0.022797 + py : 0.011167 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3243 7.0000 -0.3243 2.7391 2.7391 -0.0000 + 1 O 7.8025 8.0000 0.1975 2.5646 2.5646 -0.0000 + 2 O 8.1536 8.0000 -0.1536 1.6771 1.6771 0.0000 + 3 H 0.7196 1.0000 0.2804 0.9095 0.9095 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3864 B( 0-N , 2-O ) : 0.4943 B( 0-N , 3-H ) : 0.8584 +B( 1-O , 2-O ) : 1.1549 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 3 sec + +Total time .... 3.045 sec +Sum of individual times .... 3.028 sec ( 99.4%) + +SCF preparation .... 1.009 sec ( 33.1%) +Fock matrix formation .... 0.352 sec ( 11.6%) + Startup .... 0.016 sec ( 4.4% of F) + Split-RI-J .... 0.054 sec ( 15.3% of F) + XC integration .... 0.223 sec ( 63.3% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.016 sec ( 7.0% of XC) + Density eval. .... 0.022 sec ( 10.0% of XC) + XC-Functional eval. .... 0.013 sec ( 5.7% of XC) + XC-Potential eval. .... 0.022 sec ( 9.9% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.040 sec ( 1.3%) +Total Energy calculation .... 0.033 sec ( 1.1%) +Population analysis .... 1.446 sec ( 47.5%) +Orbital Transformation .... 0.015 sec ( 0.5%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.072 sec ( 2.4%) +SOSCF solution .... 0.061 sec ( 2.0%) +Finished LeanSCF after 4.5 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 35.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000362609 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006950101 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.515105122713 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000002885 -0.000005476 0.000001796 + 2 O : -0.000000194 0.000000682 -0.000000714 + 3 O : 0.000002929 0.000006961 0.000001535 + 4 H : 0.000000150 -0.000002167 -0.000002617 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000106539 +RMS gradient ... 0.0000030755 +MAX gradient ... 0.0000069608 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.062195572 0.007067651 0.006238378 + 2 O : -0.051240138 -0.005544853 0.033734479 + 3 O : 0.027353554 -0.000591636 -0.023925045 + 4 H : -0.038308988 -0.000931162 -0.016047812 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000109857 -0.0000014946 -0.0000053559 + +Norm of the Cartesian gradient ... 0.1039154609 +RMS gradient ... 0.0299978097 +MAX gradient ... 0.0621955720 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.123 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.006 sec ( 4.5%) +RI-J Coulomb gradient .... 0.057 sec ( 46.3%) +XC gradient .... 0.018 sec ( 15.0%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.515105123 Eh +Current gradient norm .... 0.103915461 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999860951 +Lowest eigenvalues of augmented Hessian: + -0.000125521 0.358534413 0.389303649 0.439278234 0.667533806 +Length of the computed step .... 0.016678026 +The final length of the internal step .... 0.016678026 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0068087754 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0068693214 RMS(Int)= 0.0068075183 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0032363281 0.0001000000 NO + MAX gradient 0.0058458591 0.0003000000 NO + RMS step 0.0068087754 0.0020000000 NO + MAX step 0.0128077815 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0043 Max(Angles) 0.73 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2940 -0.005846 0.0043 1.2984 + 2. B(O 2,O 1) 1.3120 0.000534 -0.0004 1.3116 + 3. B(H 3,N 0) 1.0388 0.002455 -0.0033 1.0354 + 4. A(O 1,N 0,H 3) 107.71 -0.004593 0.73 108.45 + 5. A(N 0,O 1,O 2) 120.75 -0.001123 0.15 120.90 + 6. D(O 2,O 1,N 0,H 3) 69.23 0.077426 0.00 69.23 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.344 %) +Internal coordinates : 0.000 s ( 3.347 %) +B/P matrices and projection : 0.000 s (15.900 %) +Hessian update/contruction : 0.000 s (26.778 %) +Making the step : 0.000 s ( 7.671 %) +Converting the step to Cartesian: 0.000 s ( 4.881 %) +Storing new data : 0.000 s ( 3.905 %) +Checking convergence : 0.000 s ( 0.139 %) +Final printing : 0.000 s (27.755 %) +Total time : 0.001 s + +Time for energy+gradient : 8.984 s +Time for complete geometry iter : 9.856 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.057025 -0.729537 -0.379350 + O -0.100012 0.565383 -0.463696 + O 0.631982 1.316303 0.324029 + H -0.493653 -1.014305 0.515309 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.107762 -1.378625 -0.716868 + 1 O 8.0000 0 15.999 -0.188996 1.068418 -0.876258 + 2 O 8.0000 0 15.999 1.194273 2.487452 0.612326 + 3 H 1.0000 0 1.008 -0.932868 -1.916758 0.973794 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.298375360381 0.00000000 0.00000000 + O 2 1 0 1.311566724226 120.89850016 0.00000000 + H 1 2 3 1.035447770162 108.44869798 69.23076942 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.453573850152 0.00000000 0.00000000 + O 2 1 0 2.478501915152 120.89850016 0.00000000 + H 1 2 3 1.956712711586 108.44869798 69.23076942 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.135035317889 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.832e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22302 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5216890544623993 0.00e+00 1.62e-04 1.52e-03 4.61e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5217296024647453 -4.05e-05 1.40e-04 1.60e-03 6.05e-04 0.0 + 3 -205.5217117277103966 1.79e-05 1.02e-04 1.35e-03 1.68e-03 0.0 + 4 -205.5217337249141565 -2.20e-05 1.55e-04 2.14e-03 7.45e-04 0.0 + 5 -205.5216947382036210 3.90e-05 1.15e-04 1.55e-03 2.21e-03 0.0 + 6 -205.5217389652274278 -4.42e-05 1.25e-05 1.17e-04 4.07e-05 0.0 + 7 -205.5217389874101173 -2.22e-08 5.30e-06 5.81e-05 3.83e-05 0.0 + 8 -205.5217390283883105 -4.10e-08 1.12e-06 9.24e-06 3.80e-06 0.0 + 9 -205.5217390291999209 -8.12e-10 6.09e-07 5.19e-06 1.59e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.52173902919992 Eh -5592.53084 eV + +Components: +Nuclear Repulsion : 69.13503531788881 Eh 1881.25995 eV +Electronic Energy : -274.65677434708869 Eh -7473.79079 eV +One Electron Energy: -417.96369894118232 Eh -11373.37046 eV +Two Electron Energy: 143.30692459409360 Eh 3899.57967 eV + +Virial components: +Potential Energy : -410.34247675608651 Eh -11165.98646 eV +Kinetic Energy : 204.82073772688656 Eh 5573.45562 eV +Virial Ratio : 2.00342251136332 + +DFT components: +N(Alpha) : 11.999995864758 electrons +N(Beta) : 11.999995864758 electrons +N(Total) : 23.999991729516 electrons +E(X) : -23.324829351577 Eh +E(C) : -0.803658733333 Eh +E(XC) : -24.128488084911 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 8.1161e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.1861e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 6.0943e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.2064e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.5889e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.3625e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 2.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 35.5 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000362449 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006916415 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.515185062839 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000002904 -0.000005541 0.000001786 + 2 O : -0.000000185 0.000000703 -0.000000721 + 3 O : 0.000002971 0.000007062 0.000001523 + 4 H : 0.000000117 -0.000002224 -0.000002588 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000107728 +RMS gradient ... 0.0000031098 +MAX gradient ... 0.0000070623 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.060457723 0.003565949 0.009945855 + 2 O : -0.050915439 -0.001638680 0.031728633 + 3 O : 0.027463063 -0.000111649 -0.023389098 + 4 H : -0.037005347 -0.001815620 -0.018285390 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000140719 -0.0000009070 -0.0000100142 + +Norm of the Cartesian gradient ... 0.1018669503 +RMS gradient ... 0.0294064556 +MAX gradient ... 0.0604577235 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.146 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.006 sec ( 4.4%) +RI-J Coulomb gradient .... 0.066 sec ( 45.1%) +XC gradient .... 0.019 sec ( 12.7%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.515185063 Eh +Current gradient norm .... 0.101866950 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999972234 +Lowest eigenvalues of augmented Hessian: + -0.000017360 0.275249895 0.393250192 0.436884402 0.622103255 +Length of the computed step .... 0.007452146 +The final length of the internal step .... 0.007452146 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0030423258 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0030353771 RMS(Int)= 0.0030422340 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000008681 +Previously predicted energy change .... -0.000062778 +Actually observed energy change .... -0.000079940 +Ratio of predicted to observed change .... 1.273378959 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000799401 0.0000050000 NO + RMS gradient 0.0010047687 0.0001000000 NO + MAX gradient 0.0015103189 0.0003000000 NO + RMS step 0.0030423258 0.0020000000 NO + MAX step 0.0059798061 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0017 Max(Angles) 0.34 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2984 -0.001510 0.0017 1.3001 + 2. B(O 2,O 1) 1.3116 0.001215 -0.0013 1.3102 + 3. B(H 3,N 0) 1.0354 0.000306 -0.0007 1.0348 + 4. A(O 1,N 0,H 3) 108.45 -0.001443 0.34 108.79 + 5. A(N 0,O 1,O 2) 120.90 -0.000356 0.07 120.97 + 6. D(O 2,O 1,N 0,H 3) 69.23 0.076673 -0.00 69.23 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 7.187 %) +Internal coordinates : 0.000 s ( 3.098 %) +B/P matrices and projection : 0.000 s (13.879 %) +Hessian update/contruction : 0.000 s (40.149 %) +Making the step : 0.000 s ( 5.204 %) +Converting the step to Cartesian: 0.000 s ( 3.965 %) +Storing new data : 0.000 s ( 3.222 %) +Checking convergence : 0.000 s ( 1.363 %) +Final printing : 0.000 s (21.809 %) +Total time : 0.001 s + +Time for energy+gradient : 7.093 s +Time for complete geometry iter : 7.948 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.057878 -0.729375 -0.377700 + O -0.098627 0.567214 -0.463544 + O 0.632417 1.318230 0.322735 + H -0.494621 -1.018225 0.514801 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.109374 -1.378319 -0.713750 + 1 O 8.0000 0 15.999 -0.186377 1.071879 -0.875971 + 2 O 8.0000 0 15.999 1.195096 2.491093 0.609880 + 3 H 1.0000 0 1.008 -0.934697 -1.924167 0.972834 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.300066445160 0.00000000 0.00000000 + O 2 1 0 1.310222734090 120.96740321 0.00000000 + H 1 2 3 1.034764471091 108.79131563 69.23076942 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.456769537254 0.00000000 0.00000000 + O 2 1 0 2.475962141868 120.96740321 0.00000000 + H 1 2 3 1.955421463474 108.79131563 69.23076942 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1674 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.118553312291 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.820e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5217238389485033 0.00e+00 7.64e-05 5.94e-04 1.95e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5217325439104457 -8.70e-06 7.93e-05 9.94e-04 2.80e-04 0.0 + 3 -205.5217230595125102 9.48e-06 6.33e-05 8.26e-04 1.45e-03 0.0 + 4 -205.5217339006940733 -1.08e-05 4.71e-05 7.42e-04 2.63e-04 0.0 + 5 -205.5217301797513301 3.72e-06 3.37e-05 5.31e-04 7.31e-04 0.0 + 6 -205.5217345616687226 -4.38e-06 4.06e-06 3.00e-05 1.31e-05 0.0 + 7 -205.5217345660292949 -4.36e-09 1.59e-06 1.48e-05 9.46e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.52173456602929 Eh -5592.53072 eV + +Components: +Nuclear Repulsion : 69.11855331229089 Eh 1880.81145 eV +Electronic Energy : -274.64028787832012 Eh -7473.34217 eV +One Electron Energy: -417.93172306118083 Eh -11372.50035 eV +Two Electron Energy: 143.29143518286068 Eh 3899.15818 eV + +Virial components: +Potential Energy : -410.34066282557887 Eh -11165.93710 eV +Kinetic Energy : 204.81892825954961 Eh 5573.40638 eV +Virial Ratio : 2.00343135428181 + +DFT components: +N(Alpha) : 11.999995823946 electrons +N(Beta) : 11.999995823946 electrons +N(Total) : 23.999991647892 electrons +E(X) : -23.324628660866 Eh +E(C) : -0.803642984027 Eh +E(XC) : -24.128271644893 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 4.3606e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.4758e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.5949e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.1787e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 9.4591e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.5963e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 2.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 35.7 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000362395 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006902239 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.515194721895 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000002910 -0.000005565 0.000001784 + 2 O : -0.000000178 0.000000715 -0.000000722 + 3 O : 0.000002985 0.000007096 0.000001512 + 4 H : 0.000000103 -0.000002247 -0.000002574 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000108127 +RMS gradient ... 0.0000031213 +MAX gradient ... 0.0000070965 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.059931728 0.002593371 0.011129271 + 2 O : -0.050409786 0.000161792 0.031280910 + 3 O : 0.027126914 -0.000384598 -0.023625758 + 4 H : -0.036648856 -0.002370566 -0.018784423 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000135370 -0.0000032599 -0.0000136086 + +Norm of the Cartesian gradient ... 0.1011823743 +RMS gradient ... 0.0292088355 +MAX gradient ... 0.0599317283 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.137 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.006 sec ( 4.5%) +RI-J Coulomb gradient .... 0.062 sec ( 45.3%) +XC gradient .... 0.021 sec ( 15.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.515194722 Eh +Current gradient norm .... 0.101182374 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999998732 +Lowest eigenvalues of augmented Hessian: + -0.000001097 0.255196542 0.393494161 0.435040079 0.567609196 +Length of the computed step .... 0.001592278 +The final length of the internal step .... 0.001592278 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0006500448 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0004180747 RMS(Int)= 0.0006500513 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000548 +Previously predicted energy change .... -0.000008681 +Actually observed energy change .... -0.000009659 +Ratio of predicted to observed change .... 1.112710171 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000096591 0.0000050000 NO + RMS gradient 0.0003074750 0.0001000000 NO + MAX gradient 0.0007355216 0.0003000000 NO + RMS step 0.0006500448 0.0020000000 YES + MAX step 0.0013909513 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0007 Max(Angles) 0.03 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3001 0.000003 0.0002 1.3002 + 2. B(O 2,O 1) 1.3102 0.000736 -0.0007 1.3095 + 3. B(H 3,N 0) 1.0348 -0.000071 0.0000 1.0348 + 4. A(O 1,N 0,H 3) 108.79 -0.000004 0.03 108.82 + 5. A(N 0,O 1,O 2) 120.97 -0.000146 0.03 120.99 + 6. D(O 2,O 1,N 0,H 3) 69.23 0.076359 0.00 69.23 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 8.249 %) +Internal coordinates : 0.000 s ( 2.825 %) +B/P matrices and projection : 0.000 s (12.881 %) +Hessian update/contruction : 0.000 s (32.203 %) +Making the step : 0.000 s ( 6.102 %) +Converting the step to Cartesian: 0.000 s ( 3.955 %) +Storing new data : 0.000 s ( 3.277 %) +Checking convergence : 0.000 s ( 1.356 %) +Final printing : 0.000 s (28.927 %) +Total time : 0.001 s + +Time for energy+gradient : 7.025 s +Time for complete geometry iter : 7.981 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 4 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.057954 -0.729284 -0.377577 + O -0.098301 0.567483 -0.463290 + O 0.632290 1.318276 0.322396 + H -0.494744 -1.018631 0.514763 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.109516 -1.378146 -0.713517 + 1 O 8.0000 0 15.999 -0.185761 1.072387 -0.875491 + 2 O 8.0000 0 15.999 1.194856 2.491181 0.609239 + 3 H 1.0000 0 1.008 -0.934931 -1.924934 0.972761 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.300222341007 0.00000000 0.00000000 + O 2 1 0 1.309486674340 120.99478932 0.00000000 + H 1 2 3 1.034784557382 108.82184471 69.23076942 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.457064137710 0.00000000 0.00000000 + O 2 1 0 2.474571190522 120.99478932 0.00000000 + H 1 2 3 1.955459421062 108.82184471 69.23076942 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1674 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.130563950951 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.813e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22303 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5217327385430508 0.00e+00 2.22e-05 2.40e-04 3.10e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5217333448969157 -6.06e-07 2.27e-05 3.06e-04 7.48e-05 0.0 + 3 -205.5217324982255604 8.47e-07 1.74e-05 2.50e-04 4.28e-04 0.0 + 4 -205.5217334404716780 -9.42e-07 3.10e-06 2.83e-05 1.22e-05 0.0 + 5 -205.5217334369439754 3.53e-09 1.52e-06 2.20e-05 2.97e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.52173343694398 Eh -5592.53069 eV + +Components: +Nuclear Repulsion : 69.13056395095147 Eh 1881.13828 eV +Electronic Energy : -274.65229738789537 Eh -7473.66897 eV +One Electron Energy: -417.95391713327211 Eh -11373.10428 eV +Two Electron Energy: 143.30161974537671 Eh 3899.43532 eV + +Virial components: +Potential Energy : -410.34183663535464 Eh -11165.96904 eV +Kinetic Energy : 204.82010319841066 Eh 5573.43836 eV +Virial Ratio : 2.00342559264241 + +DFT components: +N(Alpha) : 11.999995801629 electrons +N(Beta) : 11.999995801629 electrons +N(Total) : 23.999991603258 electrons +E(X) : -23.324884200063 Eh +E(C) : -0.803668685998 Eh +E(XC) : -24.128552886061 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -3.5277e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.2014e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.5213e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.8187e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.9697e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.5508e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 2.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 35.9 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000362394 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006900366 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.515195465105 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000002909 -0.000005565 0.000001784 + 2 O : -0.000000176 0.000000717 -0.000000721 + 3 O : 0.000002984 0.000007096 0.000001509 + 4 H : 0.000000102 -0.000002248 -0.000002573 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000108122 +RMS gradient ... 0.0000031212 +MAX gradient ... 0.0000070962 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.059898256 0.002648311 0.011134755 + 2 O : -0.050139776 0.000390877 0.031541959 + 3 O : 0.026885989 -0.000609804 -0.023903829 + 4 H : -0.036644470 -0.002429384 -0.018772884 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000342255 -0.0000188638 -0.0000181999 + +Norm of the Cartesian gradient ... 0.1011118392 +RMS gradient ... 0.0291884738 +MAX gradient ... 0.0598982564 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.129 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.8%) +RI-J Coulomb gradient .... 0.059 sec ( 45.7%) +XC gradient .... 0.021 sec ( 16.2%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.515195465 Eh +Current gradient norm .... 0.101111839 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999474 +Lowest eigenvalues of augmented Hessian: + -0.000000338 0.262861434 0.351732553 0.394662324 0.468594151 +Length of the computed step .... 0.001025510 +The final length of the internal step .... 0.001025510 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0004186628 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0002050002 RMS(Int)= 0.0004186651 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000169 +Previously predicted energy change .... -0.000000548 +Actually observed energy change .... -0.000000743 +Ratio of predicted to observed change .... 1.355578994 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000007432 0.0000050000 YES + RMS gradient 0.0001379857 0.0001000000 NO + MAX gradient 0.0003051835 0.0003000000 NO + RMS step 0.0004186628 0.0020000000 YES + MAX step 0.0009191709 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0005 Max(Angles) 0.02 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3002 0.000001 0.0001 1.3003 + 2. B(O 2,O 1) 1.3095 0.000305 -0.0005 1.3090 + 3. B(H 3,N 0) 1.0348 -0.000039 0.0000 1.0348 + 4. A(O 1,N 0,H 3) 108.82 0.000126 -0.02 108.81 + 5. A(N 0,O 1,O 2) 120.99 -0.000061 0.02 121.01 + 6. D(O 2,O 1,N 0,H 3) 69.23 0.076328 -0.00 69.23 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.233 %) +Internal coordinates : 0.000 s ( 2.758 %) +B/P matrices and projection : 0.000 s (13.669 %) +Hessian update/contruction : 0.000 s (35.372 %) +Making the step : 0.000 s ( 5.156 %) +Converting the step to Cartesian: 0.000 s ( 3.597 %) +Storing new data : 0.000 s ( 3.118 %) +Checking convergence : 0.000 s ( 1.319 %) +Final printing : 0.000 s (25.540 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 4 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.057939 -0.729312 -0.377653 + O -0.098169 0.567556 -0.463071 + O 0.632147 1.318153 0.322247 + H -0.494747 -1.018553 0.514769 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.109490 -1.378201 -0.713660 + 1 O 8.0000 0 15.999 -0.185512 1.072526 -0.875077 + 2 O 8.0000 0 15.999 1.194585 2.490948 0.608959 + 3 H 1.0000 0 1.008 -0.934936 -1.924786 0.972772 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.300301065461 0.00000000 0.00000000 + O 2 1 0 1.309000270029 121.01261098 0.00000000 + H 1 2 3 1.034831523626 108.80563528 69.23076942 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.457212905367 0.00000000 0.00000000 + O 2 1 0 2.473652019584 121.01261098 0.00000000 + H 1 2 3 1.955548174402 108.80563528 69.23076942 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1674 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.139769883336 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.809e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22303 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.1397698833 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5217332256012810 0.00e+00 1.43e-05 1.44e-04 1.96e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5217334686975619 -2.43e-07 1.29e-05 1.73e-04 4.37e-05 0.0 + 3 -205.5217331959792659 2.73e-07 9.80e-06 1.42e-04 2.42e-04 0.0 + 4 -205.5217334964781344 -3.00e-07 1.45e-06 1.25e-05 5.95e-06 0.0 + 5 -205.5217334960121320 4.66e-10 6.84e-07 1.06e-05 1.42e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.52173349601213 Eh -5592.53069 eV + +Components: +Nuclear Repulsion : 69.13976988333609 Eh 1881.38879 eV +Electronic Energy : -274.66150337934823 Eh -7473.91947 eV +One Electron Energy: -417.97133689232970 Eh -11373.57830 eV +Two Electron Energy: 143.30983351298147 Eh 3899.65882 eV + +Virial components: +Potential Energy : -410.34251240822243 Eh -11165.98743 eV +Kinetic Energy : 204.82077891221030 Eh 5573.45674 eV +Virial Ratio : 2.00342228258053 + +DFT components: +N(Alpha) : 11.999995785981 electrons +N(Beta) : 11.999995785981 electrons +N(Total) : 23.999991571963 electrons +E(X) : -23.325099152360 Eh +E(C) : -0.803687520961 Eh +E(XC) : -24.128786673321 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -4.6600e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.0613e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 6.8420e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.7308e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.4210e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.1901e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.187360 -522.1146 + 1 2.0000 -19.041245 -518.1386 + 2 2.0000 -14.254144 -387.8750 + 3 2.0000 -1.242989 -33.8235 + 4 2.0000 -0.965134 -26.2626 + 5 2.0000 -0.714076 -19.4310 + 6 2.0000 -0.567248 -15.4356 + 7 2.0000 -0.517525 -14.0826 + 8 2.0000 -0.494723 -13.4621 + 9 2.0000 -0.334765 -9.1094 + 10 2.0000 -0.275930 -7.5084 + 11 2.0000 -0.255352 -6.9485 + 12 0.0000 -0.216485 -5.8909 + 13 0.0000 0.035183 0.9574 + 14 0.0000 0.094222 2.5639 + 15 0.0000 0.133101 3.6219 + 16 0.0000 0.229840 6.2543 + 17 0.0000 0.258532 7.0350 + 18 0.0000 0.315821 8.5939 + 19 0.0000 0.326349 8.8804 + 20 0.0000 0.365544 9.9470 + 21 0.0000 0.375601 10.2206 + 22 0.0000 0.394616 10.7380 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.326338 + 1 O : 0.198773 + 2 O : -0.151364 + 3 H : 0.278928 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.833183 s : 3.833183 + pz : 1.453694 p : 3.439902 + px : 1.139121 + py : 0.847086 + dz2 : 0.013962 d : 0.053253 + dxz : 0.003288 + dyz : 0.010838 + dx2y2 : 0.013315 + dxy : 0.011850 + + 1 O s : 3.746719 s : 3.746719 + pz : 1.476761 p : 3.927411 + px : 1.341012 + py : 1.109639 + dz2 : 0.024691 d : 0.127097 + dxz : 0.012576 + dyz : 0.031964 + dx2y2 : 0.026800 + dxy : 0.031065 + + 2 O s : 3.942338 s : 3.942338 + pz : 1.469567 p : 4.195458 + px : 1.171969 + py : 1.553923 + dz2 : 0.004988 d : 0.013567 + dxz : 0.000652 + dyz : 0.002805 + dx2y2 : 0.000019 + dxy : 0.005104 + + 3 H s : 0.690393 s : 0.690393 + pz : 0.015635 p : 0.030678 + px : 0.009664 + py : 0.005379 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.097478 + 1 O : -0.177150 + 2 O : -0.005992 + 3 H : 0.280620 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.332695 s : 3.332695 + pz : 1.402134 p : 3.460129 + px : 1.061819 + py : 0.996176 + dz2 : 0.045061 d : 0.304654 + dxz : 0.012438 + dyz : 0.098676 + dx2y2 : 0.083994 + dxy : 0.064485 + + 1 O s : 3.374497 s : 3.374497 + pz : 1.460342 p : 4.042887 + px : 1.273761 + py : 1.308784 + dz2 : 0.105032 d : 0.759766 + dxz : 0.072308 + dyz : 0.197994 + dx2y2 : 0.184515 + dxy : 0.199917 + + 2 O s : 3.610516 s : 3.610516 + pz : 1.425705 p : 4.146823 + px : 1.176197 + py : 1.544920 + dz2 : 0.045230 d : 0.248653 + dxz : 0.057524 + dyz : 0.048458 + dx2y2 : 0.052130 + dxy : 0.045310 + + 3 H s : 0.641212 s : 0.641212 + pz : 0.043354 p : 0.078168 + px : 0.023194 + py : 0.011620 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3263 7.0000 -0.3263 2.7388 2.7388 -0.0000 + 1 O 7.8012 8.0000 0.1988 2.5646 2.5646 -0.0000 + 2 O 8.1514 8.0000 -0.1514 1.6814 1.6814 -0.0000 + 3 H 0.7211 1.0000 0.2789 0.9100 0.9100 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3836 B( 0-N , 2-O ) : 0.4966 B( 0-N , 3-H ) : 0.8586 +B( 1-O , 2-O ) : 1.1571 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.667 sec +Sum of individual times .... 2.653 sec ( 99.5%) + +SCF preparation .... 0.920 sec ( 34.5%) +Fock matrix formation .... 0.126 sec ( 4.7%) + Startup .... 0.007 sec ( 5.7% of F) + Split-RI-J .... 0.021 sec ( 16.5% of F) + XC integration .... 0.079 sec ( 62.9% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.005 sec ( 6.7% of XC) + Density eval. .... 0.007 sec ( 9.0% of XC) + XC-Functional eval. .... 0.004 sec ( 5.6% of XC) + XC-Potential eval. .... 0.007 sec ( 8.5% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.008 sec ( 0.3%) +Total Energy calculation .... 0.011 sec ( 0.4%) +Population analysis .... 1.543 sec ( 57.9%) +Orbital Transformation .... 0.007 sec ( 0.3%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.010 sec ( 0.4%) +SOSCF solution .... 0.028 sec ( 1.0%) +Finished LeanSCF after 4.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 36.2 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000362398 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006900223 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.515195670390 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.028.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.028.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.290731 0.760798 -0.282333 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5217334960121320 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.248697255 0.917911711 -0.269554399 +Nuclear contribution : -0.606316000 -1.323542078 0.624190741 + ----------------------------------------- +Total Dipole Moment : -0.357618745 -0.405630367 0.354636341 + ----------------------------------------- +Magnitude (a.u.) : 0.646679284 +Magnitude (Debye) : 1.643728110 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.029949 0.411153 0.373253 +Rotational constants in MHz : 90835.582623 12326.069350 11189.843303 + +Dipole components along the rotational axes: +x,y,z [a.u.] : -0.381741 0.267031 0.448511 +x,y,z [Debye]: -0.970308 0.678740 1.140025 + + + +Dipole moment calculation done in 0.5 sec + +Maximum memory used throughout the entire PROP-calculation: 19.1 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 29 * + * * + * Dihedral ( 2, 1, 0, 3) : 78.46153846 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.3013 0.696821 + 2. B(O 2,O 1) 1.3109 0.674904 + 3. B(H 3,N 0) 1.0375 0.394982 + 4. A(O 1,N 0,H 3) 108.6352 0.357958 + 5. A(N 0,O 1,O 2) 120.8348 0.438323 + 6. D(O 2,O 1,N 0,H 3) 78.4615 0.037908 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.029514 -0.726217 -0.360516 + O -0.117986 0.569945 -0.433946 + O 0.652877 1.338502 0.296499 + H -0.524085 -1.044385 0.494256 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.055774 -1.372351 -0.681277 + 1 O 8.0000 0 15.999 -0.222961 1.077039 -0.820040 + 2 O 8.0000 0 15.999 1.233759 2.529401 0.560301 + 3 H 1.0000 0 1.008 -0.990377 -1.973602 0.934009 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.300301065461 0.00000000 0.00000000 + O 2 1 0 1.309000270029 121.01261098 0.00000000 + H 1 2 3 1.034831523626 108.80563528 69.23076942 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.457212905367 0.00000000 0.00000000 + O 2 1 0 2.473652019584 121.01261098 0.00000000 + H 1 2 3 1.955548174402 108.80563528 69.23076942 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1673 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.033640639894 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.831e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22303 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.0336406399 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5050394274869632 0.00e+00 4.69e-04 3.81e-03 2.05e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.023) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5060854618404846 -1.05e-03 5.61e-04 5.10e-03 1.61e-02 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.5069783681265676 -8.93e-04 4.25e-04 3.57e-03 1.15e-02 0.700 0.1 + 4 -205.5075941810798099 -6.16e-04 1.09e-03 9.70e-03 8.12e-03 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5090820575377393 -1.49e-03 1.36e-04 1.40e-03 1.78e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -205.5091003429043326 -1.83e-05 3.84e-04 4.66e-03 1.31e-03 0.1 + 7 -205.5089780620600095 1.22e-04 2.13e-04 2.65e-03 5.97e-03 0.0 + 8 -205.5091344728015201 -1.56e-04 9.34e-05 7.20e-04 2.36e-04 0.0 + 9 -205.5091371821681037 -2.71e-06 8.66e-05 6.47e-04 2.12e-04 0.1 + 10 -205.5091366996989564 4.82e-07 3.46e-05 3.19e-04 3.24e-04 0.1 + 11 -205.5091379957403888 -1.30e-06 1.49e-05 1.26e-04 5.35e-05 0.0 + 12 -205.5091380264580607 -3.07e-08 6.61e-06 5.57e-05 3.85e-05 0.0 + 13 -205.5091380517515063 -2.53e-08 8.46e-07 6.11e-06 3.93e-06 0.0 + 14 -205.5091380523968496 -6.45e-10 3.50e-07 2.81e-06 2.59e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 14 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50913805239685 Eh -5592.18795 eV + +Components: +Nuclear Repulsion : 69.03364063989430 Eh 1878.50086 eV +Electronic Energy : -274.54277869229111 Eh -7470.68881 eV +One Electron Energy: -417.75558626493989 Eh -11367.70743 eV +Two Electron Energy: 143.21280757264876 Eh 3897.01861 eV + +Virial components: +Potential Energy : -410.31922226442384 Eh -11165.35367 eV +Kinetic Energy : 204.81008421202696 Eh 5573.16573 eV +Virial Ratio : 2.00341318076724 + +DFT components: +N(Alpha) : 11.999995369247 electrons +N(Beta) : 11.999995369247 electrons +N(Total) : 23.999990738495 electrons +E(X) : -23.319180204136 Eh +E(C) : -0.803715228077 Eh +E(XC) : -24.122895432214 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 6.4534e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.8147e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.4964e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.7770e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.5912e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.2681e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.188736 -522.1521 + 1 2.0000 -19.047427 -518.3068 + 2 2.0000 -14.246087 -387.6557 + 3 2.0000 -1.242384 -33.8070 + 4 2.0000 -0.964939 -26.2573 + 5 2.0000 -0.711289 -19.3552 + 6 2.0000 -0.567419 -15.4402 + 7 2.0000 -0.518577 -14.1112 + 8 2.0000 -0.495032 -13.4705 + 9 2.0000 -0.335649 -9.1335 + 10 2.0000 -0.278984 -7.5915 + 11 2.0000 -0.245162 -6.6712 + 12 0.0000 -0.223822 -6.0905 + 13 0.0000 0.032673 0.8891 + 14 0.0000 0.094986 2.5847 + 15 0.0000 0.133992 3.6461 + 16 0.0000 0.230384 6.2691 + 17 0.0000 0.258237 7.0270 + 18 0.0000 0.317804 8.6479 + 19 0.0000 0.327353 8.9077 + 20 0.0000 0.364760 9.9256 + 21 0.0000 0.371926 10.1206 + 22 0.0000 0.393522 10.7083 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.358448 + 1 O : 0.196618 + 2 O : -0.125056 + 3 H : 0.286887 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.827864 s : 3.827864 + pz : 1.483329 p : 3.478502 + px : 1.162728 + py : 0.832444 + dz2 : 0.012596 d : 0.052082 + dxz : 0.004091 + dyz : 0.011456 + dx2y2 : 0.013286 + dxy : 0.010653 + + 1 O s : 3.751689 s : 3.751689 + pz : 1.474343 p : 3.927437 + px : 1.339159 + py : 1.113935 + dz2 : 0.022033 d : 0.124256 + dxz : 0.013079 + dyz : 0.033405 + dx2y2 : 0.028983 + dxy : 0.026755 + + 2 O s : 3.939707 s : 3.939707 + pz : 1.461083 p : 4.171835 + px : 1.168189 + py : 1.542562 + dz2 : 0.005806 d : 0.013515 + dxz : 0.000011 + dyz : 0.002221 + dx2y2 : -0.000388 + dxy : 0.005864 + + 3 H s : 0.681911 s : 0.681911 + pz : 0.015072 p : 0.031202 + px : 0.010606 + py : 0.005525 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.119786 + 1 O : -0.174025 + 2 O : 0.007586 + 3 H : 0.286224 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.323399 s : 3.323399 + pz : 1.423645 p : 3.493379 + px : 1.086969 + py : 0.982765 + dz2 : 0.041311 d : 0.303007 + dxz : 0.013886 + dyz : 0.097917 + dx2y2 : 0.082820 + dxy : 0.067073 + + 1 O s : 3.376673 s : 3.376673 + pz : 1.450048 p : 4.037539 + px : 1.276194 + py : 1.311296 + dz2 : 0.093592 d : 0.759813 + dxz : 0.070895 + dyz : 0.199125 + dx2y2 : 0.187229 + dxy : 0.208973 + + 2 O s : 3.613354 s : 3.613354 + pz : 1.411638 p : 4.131240 + px : 1.179577 + py : 1.540025 + dz2 : 0.039753 d : 0.247819 + dxz : 0.057666 + dyz : 0.045779 + dx2y2 : 0.055712 + dxy : 0.048910 + + 3 H s : 0.635276 s : 0.635276 + pz : 0.041271 p : 0.078500 + px : 0.025492 + py : 0.011737 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3584 7.0000 -0.3584 2.7000 2.7000 -0.0000 + 1 O 7.8034 8.0000 0.1966 2.5617 2.5617 -0.0000 + 2 O 8.1251 8.0000 -0.1251 1.6837 1.6837 -0.0000 + 3 H 0.7131 1.0000 0.2869 0.9048 0.9048 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3734 B( 0-N , 2-O ) : 0.4837 B( 0-N , 3-H ) : 0.8429 +B( 1-O , 2-O ) : 1.1632 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 3 sec + +Total time .... 3.153 sec +Sum of individual times .... 3.134 sec ( 99.4%) + +SCF preparation .... 0.928 sec ( 29.4%) +Fock matrix formation .... 0.422 sec ( 13.4%) + Startup .... 0.016 sec ( 3.9% of F) + Split-RI-J .... 0.059 sec ( 13.9% of F) + XC integration .... 0.269 sec ( 63.7% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.017 sec ( 6.5% of XC) + Density eval. .... 0.024 sec ( 8.8% of XC) + XC-Functional eval. .... 0.014 sec ( 5.0% of XC) + XC-Potential eval. .... 0.024 sec ( 8.8% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.036 sec ( 1.1%) +Total Energy calculation .... 0.037 sec ( 1.2%) +Population analysis .... 1.562 sec ( 49.6%) +Orbital Transformation .... 0.015 sec ( 0.5%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.073 sec ( 2.3%) +SOSCF solution .... 0.061 sec ( 1.9%) +Finished LeanSCF after 4.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 36.5 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000362028 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006892381 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502607698885 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003063 -0.000005694 0.000001710 + 2 O : -0.000000211 0.000000721 -0.000000673 + 3 O : 0.000003162 0.000007429 0.000001373 + 4 H : 0.000000111 -0.000002456 -0.000002409 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000111651 +RMS gradient ... 0.0000032231 +MAX gradient ... 0.0000074287 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.061728631 0.007203603 0.008448600 + 2 O : -0.049933326 -0.006311580 0.036469006 + 3 O : 0.026399363 0.000787452 -0.026025542 + 4 H : -0.038194667 -0.001679475 -0.018892065 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000001889 0.0000118059 -0.0000218234 + +Norm of the Cartesian gradient ... 0.1048346064 +RMS gradient ... 0.0302631441 +MAX gradient ... 0.0617286306 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.129 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 4.0%) +RI-J Coulomb gradient .... 0.061 sec ( 47.7%) +XC gradient .... 0.018 sec ( 14.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.502607699 Eh +Current gradient norm .... 0.104834606 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999791482 +Lowest eigenvalues of augmented Hessian: + -0.000167208 0.357251531 0.391112796 0.437498003 0.670213499 +Length of the computed step .... 0.020424668 +The final length of the internal step .... 0.020424668 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0083383359 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0076328340 RMS(Int)= 0.0083343924 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0034535953 0.0001000000 NO + MAX gradient 0.0062041786 0.0003000000 NO + RMS step 0.0083383359 0.0020000000 NO + MAX step 0.0173635202 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0043 Max(Angles) 0.99 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3013 -0.004490 0.0034 1.3047 + 2. B(O 2,O 1) 1.3109 0.001483 -0.0012 1.3097 + 3. B(H 3,N 0) 1.0375 0.003157 -0.0043 1.0333 + 4. A(O 1,N 0,H 3) 108.64 -0.006204 0.99 109.63 + 5. A(N 0,O 1,O 2) 120.83 -0.000863 0.11 120.95 + 6. D(O 2,O 1,N 0,H 3) 78.46 0.078793 0.00 78.46 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.644 %) +Internal coordinates : 0.000 s ( 3.709 %) +B/P matrices and projection : 0.000 s (16.914 %) +Hessian update/contruction : 0.000 s (27.745 %) +Making the step : 0.000 s ( 6.825 %) +Converting the step to Cartesian: 0.000 s ( 5.045 %) +Storing new data : 0.000 s ( 4.006 %) +Checking convergence : 0.000 s ( 0.148 %) +Final printing : 0.000 s (25.519 %) +Total time : 0.001 s + +Time for energy+gradient : 9.228 s +Time for complete geometry iter : 10.092 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.032543 -0.725755 -0.354977 + O -0.115117 0.573872 -0.434471 + O 0.654565 1.343486 0.294005 + H -0.525613 -1.053759 0.491735 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.061497 -1.371479 -0.670809 + 1 O 8.0000 0 15.999 -0.217539 1.084461 -0.821031 + 2 O 8.0000 0 15.999 1.236948 2.538821 0.555589 + 3 H 1.0000 0 1.008 -0.993265 -1.991316 0.929244 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.304672173014 0.00000000 0.00000000 + O 2 1 0 1.309729576076 120.94783758 0.00000000 + H 1 2 3 1.033259861107 109.63002540 78.46153833 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.465473101544 0.00000000 0.00000000 + O 2 1 0 2.475030208280 120.94783758 0.00000000 + H 1 2 3 1.952578162667 109.63002540 78.46153833 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1673 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.971784234391 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.820e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22303 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5091497743406990 0.00e+00 1.87e-04 2.20e-03 5.16e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5092013393576167 -5.16e-05 1.41e-04 1.56e-03 6.56e-04 0.0 + 3 -205.5091896087652685 1.17e-05 1.08e-04 1.46e-03 1.65e-03 0.0 + 4 -205.5092089982056791 -1.94e-05 1.38e-04 1.85e-03 7.87e-04 0.0 + 5 -205.5091825303853170 2.65e-05 9.67e-05 1.26e-03 1.76e-03 0.0 + 6 -205.5092141801039247 -3.16e-05 1.45e-05 1.09e-04 4.73e-05 0.0 + 7 -205.5092142434501739 -6.33e-08 6.00e-06 5.22e-05 3.21e-05 0.0 + 8 -205.5092142826612189 -3.92e-08 2.24e-06 1.56e-05 7.80e-06 0.0 + 9 -205.5092142852989241 -2.64e-09 7.17e-07 5.49e-06 2.54e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50921428529892 Eh -5592.19002 eV + +Components: +Nuclear Repulsion : 68.97178423439101 Eh 1876.81766 eV +Electronic Energy : -274.48099851968993 Eh -7469.00769 eV +One Electron Energy: -417.63455972153696 Eh -11364.41413 eV +Two Electron Energy: 143.15356120184703 Eh 3895.40644 eV + +Virial components: +Potential Energy : -410.31470784600378 Eh -11165.23083 eV +Kinetic Energy : 204.80549356070489 Eh 5573.04081 eV +Virial Ratio : 2.00343604418202 + +DFT components: +N(Alpha) : 11.999995419083 electrons +N(Beta) : 11.999995419083 electrons +N(Total) : 23.999990838166 electrons +E(X) : -23.318734477735 Eh +E(C) : -0.803632065604 Eh +E(XC) : -24.122366543339 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.6377e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.4946e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 7.1734e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.6343e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.5372e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.1887e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 3.1 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 36.7 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361863 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006854830 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502721317904 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003078 -0.000005755 0.000001701 + 2 O : -0.000000198 0.000000746 -0.000000680 + 3 O : 0.000003202 0.000007520 0.000001353 + 4 H : 0.000000074 -0.000002511 -0.000002374 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000112750 +RMS gradient ... 0.0000032548 +MAX gradient ... 0.0000075199 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.059559676 0.003988991 0.012893719 + 2 O : -0.049442571 -0.002271667 0.034301854 + 3 O : 0.026206410 0.000710588 -0.025643403 + 4 H : -0.036323515 -0.002427912 -0.021552170 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000008196 0.0000146983 -0.0000221863 + +Norm of the Cartesian gradient ... 0.1024232111 +RMS gradient ... 0.0295670343 +MAX gradient ... 0.0595596764 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.144 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.006 sec ( 4.0%) +RI-J Coulomb gradient .... 0.066 sec ( 46.1%) +XC gradient .... 0.021 sec ( 14.6%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.502721318 Eh +Current gradient norm .... 0.102423211 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999894946 +Lowest eigenvalues of augmented Hessian: + -0.000046767 0.215695643 0.402952359 0.436735848 0.647895980 +Length of the computed step .... 0.014496241 +The final length of the internal step .... 0.014496241 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0059180655 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0055633939 RMS(Int)= 0.0059168264 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000023389 +Previously predicted energy change .... -0.000083639 +Actually observed energy change .... -0.000113619 +Ratio of predicted to observed change .... 1.358445783 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0001136190 0.0000050000 NO + RMS gradient 0.0013547813 0.0001000000 NO + MAX gradient 0.0027829187 0.0003000000 NO + RMS step 0.0059180655 0.0020000000 NO + MAX step 0.0135040717 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0020 Max(Angles) 0.77 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3047 -0.000611 0.0010 1.3057 + 2. B(O 2,O 1) 1.3097 0.001554 -0.0020 1.3077 + 3. B(H 3,N 0) 1.0333 0.000443 -0.0013 1.0320 + 4. A(O 1,N 0,H 3) 109.63 -0.002783 0.77 110.40 + 5. A(N 0,O 1,O 2) 120.95 -0.000533 0.12 121.07 + 6. D(O 2,O 1,N 0,H 3) 78.46 0.077760 -0.00 78.46 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 7.893 %) +Internal coordinates : 0.000 s ( 2.526 %) +B/P matrices and projection : 0.000 s (13.102 %) +Hessian update/contruction : 0.001 s (39.542 %) +Making the step : 0.000 s ( 4.341 %) +Converting the step to Cartesian: 0.000 s ( 3.394 %) +Storing new data : 0.000 s ( 2.605 %) +Checking convergence : 0.000 s ( 1.184 %) +Final printing : 0.000 s (22.573 %) +Total time : 0.001 s + +Time for energy+gradient : 7.559 s +Time for complete geometry iter : 8.432 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.034450 -0.724144 -0.351405 + O -0.112535 0.576520 -0.434619 + O 0.655337 1.346492 0.291777 + H -0.527060 -1.061023 0.490539 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.065101 -1.368434 -0.664059 + 1 O 8.0000 0 15.999 -0.212660 1.089464 -0.821310 + 2 O 8.0000 0 15.999 1.238408 2.544500 0.551378 + 3 H 1.0000 0 1.008 -0.996000 -2.005043 0.926985 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.305659731245 0.00000000 0.00000000 + O 2 1 0 1.307721159298 121.06553083 0.00000000 + H 1 2 3 1.031999343769 110.40375172 78.46153833 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.467339316142 0.00000000 0.00000000 + O 2 1 0 2.471234850608 121.06553083 0.00000000 + H 1 2 3 1.950196130111 110.40375172 78.46153833 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1672 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.980136523498 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.800e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5091821141216712 0.00e+00 1.36e-04 1.35e-03 3.70e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5092074251106453 -2.53e-05 1.15e-04 1.26e-03 4.08e-04 0.0 + 3 -205.5091956559846551 1.18e-05 9.04e-05 1.09e-03 1.96e-03 0.0 + 4 -205.5092130968062918 -1.74e-05 5.79e-05 8.38e-04 3.13e-04 0.0 + 5 -205.5092089166663811 4.18e-06 3.66e-05 5.74e-04 7.69e-04 0.0 + 6 -205.5092144234423870 -5.51e-06 8.95e-06 6.75e-05 3.10e-05 0.0 + 7 -205.5092144575062036 -3.41e-08 4.26e-06 2.98e-05 1.50e-05 0.0 + 8 -205.5092144667005698 -9.19e-09 1.20e-06 8.97e-06 4.80e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50921446670057 Eh -5592.19003 eV + +Components: +Nuclear Repulsion : 68.98013652349786 Eh 1877.04494 eV +Electronic Energy : -274.48935099019843 Eh -7469.23497 eV +One Electron Energy: -417.64967328578871 Eh -11364.82539 eV +Two Electron Energy: 143.16032229559028 Eh 3895.59042 eV + +Virial components: +Potential Energy : -410.31450414910796 Eh -11165.22529 eV +Kinetic Energy : 204.80528968240736 Eh 5573.03526 eV +Virial Ratio : 2.00343704396202 + +DFT components: +N(Alpha) : 11.999995435094 electrons +N(Beta) : 11.999995435094 electrons +N(Total) : 23.999990870188 electrons +E(X) : -23.319236133927 Eh +E(C) : -0.803681159575 Eh +E(XC) : -24.122917293502 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 9.1944e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.9683e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.2017e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.8052e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.8006e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.7610e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 2.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 36.9 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361773 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006828433 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502747806482 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003085 -0.000005790 0.000001697 + 2 O : -0.000000186 0.000000766 -0.000000684 + 3 O : 0.000003224 0.000007572 0.000001333 + 4 H : 0.000000047 -0.000002548 -0.000002346 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000113364 +RMS gradient ... 0.0000032725 +MAX gradient ... 0.0000075718 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.058593256 0.003177279 0.014867561 + 2 O : -0.048517244 0.000064423 0.033453993 + 3 O : 0.025492781 0.000051131 -0.025975039 + 4 H : -0.035568793 -0.003292833 -0.022346516 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000009212 0.0000155420 -0.0000221418 + +Norm of the Cartesian gradient ... 0.1011797486 +RMS gradient ... 0.0292080775 +MAX gradient ... 0.0585932558 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.139 sec + +Densities .... 0.001 sec ( 0.4%) +One electron gradient .... 0.006 sec ( 4.5%) +RI-J Coulomb gradient .... 0.064 sec ( 45.9%) +XC gradient .... 0.022 sec ( 15.6%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.502747806 Eh +Current gradient norm .... 0.101179749 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999993222 +Lowest eigenvalues of augmented Hessian: + -0.000003744 0.176748243 0.403580077 0.436592163 0.645733677 +Length of the computed step .... 0.003681892 +The final length of the internal step .... 0.003681892 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0015031261 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0011729983 RMS(Int)= 0.0015031532 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000001872 +Previously predicted energy change .... -0.000023389 +Actually observed energy change .... -0.000026489 +Ratio of predicted to observed change .... 1.132541184 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000264886 0.0000050000 NO + RMS gradient 0.0005290046 0.0001000000 NO + MAX gradient 0.0010168346 0.0003000000 NO + RMS step 0.0015031261 0.0020000000 YES + MAX step 0.0029901093 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0007 Max(Angles) 0.17 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3057 0.001017 -0.0007 1.3050 + 2. B(O 2,O 1) 1.3077 0.000570 -0.0007 1.3070 + 3. B(H 3,N 0) 1.0320 -0.000179 0.0000 1.0320 + 4. A(O 1,N 0,H 3) 110.40 -0.000435 0.17 110.58 + 5. A(N 0,O 1,O 2) 121.07 -0.000315 0.06 121.13 + 6. D(O 2,O 1,N 0,H 3) 78.46 0.077018 0.00 78.46 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.049 %) +Internal coordinates : 0.000 s ( 3.153 %) +B/P matrices and projection : 0.000 s (12.118 %) +Hessian update/contruction : 0.000 s (31.429 %) +Making the step : 0.000 s ( 5.517 %) +Converting the step to Cartesian: 0.000 s ( 4.039 %) +Storing new data : 0.000 s ( 3.251 %) +Checking convergence : 0.000 s ( 2.167 %) +Final printing : 0.000 s (27.980 %) +Total time : 0.001 s + +Time for energy+gradient : 7.424 s +Time for complete geometry iter : 8.357 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 4 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.034838 -0.723326 -0.350789 + O -0.111816 0.576674 -0.434404 + O 0.655328 1.346963 0.291160 + H -0.527382 -1.062467 0.490325 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.065834 -1.366889 -0.662896 + 1 O 8.0000 0 15.999 -0.211301 1.089757 -0.820905 + 2 O 8.0000 0 15.999 1.238390 2.545391 0.550213 + 3 H 1.0000 0 1.008 -0.996608 -2.007772 0.926580 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.304959490593 0.00000000 0.00000000 + O 2 1 0 1.307018732947 121.12559231 0.00000000 + H 1 2 3 1.032031553985 110.57507236 78.46153833 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.466016053082 0.00000000 0.00000000 + O 2 1 0 2.469907457175 121.12559231 0.00000000 + H 1 2 3 1.950256998597 110.57507236 78.46153833 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1672 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.006588244826 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.792e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22303 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5092085477351986 0.00e+00 3.98e-05 3.05e-04 9.09e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5092105212688978 -1.97e-06 2.85e-05 3.02e-04 8.32e-05 0.1 + 3 -205.5092103723603998 1.49e-07 2.67e-05 2.44e-04 3.38e-04 0.0 + 4 -205.5092108371078723 -4.65e-07 1.66e-05 1.67e-04 1.12e-04 0.0 + 5 -205.5092108386133134 -1.51e-09 8.25e-06 1.33e-04 1.24e-04 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50921083861331 Eh -5592.18993 eV + +Components: +Nuclear Repulsion : 69.00658824482596 Eh 1877.76473 eV +Electronic Energy : -274.51579908343928 Eh -7469.95466 eV +One Electron Energy: -417.70298315145914 Eh -11366.27602 eV +Two Electron Energy: 143.18718406801986 Eh 3896.32136 eV + +Virial components: +Potential Energy : -410.31744380435850 Eh -11165.30528 eV +Kinetic Energy : 204.80823296574519 Eh 5573.11535 eV +Virial Ratio : 2.00342260593101 + +DFT components: +N(Alpha) : 11.999995439549 electrons +N(Beta) : 11.999995439549 electrons +N(Total) : 23.999990879098 electrons +E(X) : -23.320173306694 Eh +E(C) : -0.803747443502 Eh +E(XC) : -24.123920750196 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.5054e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.3266e-04 Tolerance : 1.0000e-07 + Last RMS-Density change ... 8.2495e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 4.3421e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.2367e-04 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.4504e-04 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 2.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 37.1 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361765 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006822380 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502750224186 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003085 -0.000005793 0.000001697 + 2 O : -0.000000183 0.000000770 -0.000000684 + 3 O : 0.000003226 0.000007577 0.000001327 + 4 H : 0.000000042 -0.000002553 -0.000002340 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000113414 +RMS gradient ... 0.0000032740 +MAX gradient ... 0.0000075769 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.058466156 0.003549792 0.014934684 + 2 O : -0.048095453 0.000073911 0.033704476 + 3 O : 0.025165852 -0.000155870 -0.026321641 + 4 H : -0.035536556 -0.003467833 -0.022317519 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0001619681 0.0001036227 -0.0000634162 + +Norm of the Cartesian gradient ... 0.1010060617 +RMS gradient ... 0.0291579385 +MAX gradient ... 0.0584661562 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.138 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.0%) +RI-J Coulomb gradient .... 0.066 sec ( 47.6%) +XC gradient .... 0.021 sec ( 15.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.502750224 Eh +Current gradient norm .... 0.101006062 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999996907 +Lowest eigenvalues of augmented Hessian: + -0.000001707 0.156548645 0.398583128 0.442698446 0.533041117 +Length of the computed step .... 0.002487016 +The final length of the internal step .... 0.002487016 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0010153201 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0005523308 RMS(Int)= 0.0010153521 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000854 +Previously predicted energy change .... -0.000001872 +Actually observed energy change .... -0.000002418 +Ratio of predicted to observed change .... 1.291416627 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000024177 0.0000050000 YES + RMS gradient 0.0003327571 0.0001000000 NO + MAX gradient 0.0008021892 0.0003000000 NO + RMS step 0.0010153201 0.0020000000 YES + MAX step 0.0019500723 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0010 Max(Angles) 0.08 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3050 0.000802 -0.0010 1.3039 + 2. B(O 2,O 1) 1.3070 0.000075 -0.0003 1.3067 + 3. B(H 3,N 0) 1.0320 -0.000105 0.0001 1.0322 + 4. A(O 1,N 0,H 3) 110.58 -0.000058 0.08 110.66 + 5. A(N 0,O 1,O 2) 121.13 0.000028 0.01 121.14 + 6. D(O 2,O 1,N 0,H 3) 78.46 0.076917 0.00 78.46 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.216 %) +Internal coordinates : 0.000 s ( 2.838 %) +B/P matrices and projection : 0.000 s (17.253 %) +Hessian update/contruction : 0.000 s (32.009 %) +Making the step : 0.000 s ( 5.108 %) +Converting the step to Cartesian: 0.000 s ( 3.859 %) +Storing new data : 0.000 s ( 3.065 %) +Checking convergence : 0.000 s ( 1.816 %) +Final printing : 0.000 s (23.723 %) +Total time : 0.001 s + +Time for energy+gradient : 7.633 s +Time for complete geometry iter : 8.613 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 5 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.034908 -0.722539 -0.350547 + O -0.111590 0.576430 -0.434379 + O 0.655215 1.346784 0.290943 + H -0.527425 -1.062832 0.490275 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.065967 -1.365400 -0.662437 + 1 O 8.0000 0 15.999 -0.210875 1.089294 -0.820858 + 2 O 8.0000 0 15.999 1.238178 2.545054 0.549802 + 3 H 1.0000 0 1.008 -0.996689 -2.008460 0.926485 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.303927556757 0.00000000 0.00000000 + O 2 1 0 1.306724371381 121.13744181 0.00000000 + H 1 2 3 1.032159479170 110.65552812 78.46153833 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.464065980744 0.00000000 0.00000000 + O 2 1 0 2.469351194431 121.13744181 0.00000000 + H 1 2 3 1.950498742162 110.65552812 78.46153833 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1672 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.035580859963 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.788e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22303 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5092088610354608 0.00e+00 2.96e-05 2.52e-04 5.94e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5092098900046835 -1.03e-06 2.98e-05 3.64e-04 1.38e-04 0.0 + 3 -205.5092091856429306 7.04e-07 1.44e-05 2.47e-04 3.25e-04 0.0 + 4 -205.5092102167797066 -1.03e-06 4.94e-06 3.63e-05 1.96e-05 0.0 + 5 -205.5092102178081177 -1.03e-09 8.79e-06 8.66e-05 5.06e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50921021780812 Eh -5592.18991 eV + +Components: +Nuclear Repulsion : 69.03558085996303 Eh 1878.55366 eV +Electronic Energy : -274.54479107777115 Eh -7470.74357 eV +One Electron Energy: -417.75709554697573 Eh -11367.74849 eV +Two Electron Energy: 143.21230446920461 Eh 3897.00492 eV + +Virial components: +Potential Energy : -410.31918654428085 Eh -11165.35270 eV +Kinetic Energy : 204.80997632647274 Eh 5573.16279 eV +Virial Ratio : 2.00341406167745 + +DFT components: +N(Alpha) : 11.999995437121 electrons +N(Beta) : 11.999995437121 electrons +N(Total) : 23.999990874241 electrons +E(X) : -23.320708356016 Eh +E(C) : -0.803807756386 Eh +E(XC) : -24.124516112402 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.0284e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.6575e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 8.7941e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.3906e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 5.0636e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.0239e-04 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 2.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 37.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361775 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006820769 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502751223892 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003083 -0.000005789 0.000001698 + 2 O : -0.000000182 0.000000769 -0.000000684 + 3 O : 0.000003224 0.000007571 0.000001324 + 4 H : 0.000000041 -0.000002551 -0.000002338 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000113329 +RMS gradient ... 0.0000032715 +MAX gradient ... 0.0000075705 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.058593691 0.004298927 0.014831528 + 2 O : -0.047949524 -0.000305052 0.033841647 + 3 O : 0.024931977 -0.000480850 -0.026462949 + 4 H : -0.035576145 -0.003513026 -0.022210225 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000122128 0.0000358374 0.0000152456 + +Norm of the Cartesian gradient ... 0.1010425773 +RMS gradient ... 0.0291684796 +MAX gradient ... 0.0585936911 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.133 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.7%) +RI-J Coulomb gradient .... 0.058 sec ( 43.6%) +XC gradient .... 0.018 sec ( 13.6%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.502751224 Eh +Current gradient norm .... 0.101042577 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999342 +Lowest eigenvalues of augmented Hessian: + -0.000000355 0.127716535 0.383617284 0.410800168 0.568548181 +Length of the computed step .... 0.001147380 +The final length of the internal step .... 0.001147380 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0004684160 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0003620699 RMS(Int)= 0.0004684353 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000178 +Previously predicted energy change .... -0.000000854 +Actually observed energy change .... -0.000001000 +Ratio of predicted to observed change .... 1.171105256 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000009997 0.0000050000 YES + RMS gradient 0.0001688448 0.0001000000 NO + MAX gradient 0.0003401406 0.0003000000 NO + RMS step 0.0004684160 0.0020000000 YES + MAX step 0.0006770925 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0003 Max(Angles) 0.04 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3039 0.000095 -0.0003 1.3036 + 2. B(O 2,O 1) 1.3067 -0.000340 0.0002 1.3069 + 3. B(H 3,N 0) 1.0322 0.000041 -0.0000 1.0321 + 4. A(O 1,N 0,H 3) 110.66 -0.000081 0.04 110.69 + 5. A(N 0,O 1,O 2) 121.14 -0.000195 0.03 121.17 + 6. D(O 2,O 1,N 0,H 3) 78.46 0.076834 -0.00 78.46 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.486 %) +Internal coordinates : 0.000 s ( 2.759 %) +B/P matrices and projection : 0.000 s (11.148 %) +Hessian update/contruction : 0.000 s (33.996 %) +Making the step : 0.000 s ( 5.298 %) +Converting the step to Cartesian: 0.000 s ( 3.642 %) +Storing new data : 0.000 s ( 3.091 %) +Checking convergence : 0.000 s ( 1.214 %) +Final printing : 0.000 s (28.146 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 5 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.035076 -0.722391 -0.350444 + O -0.111437 0.576261 -0.434292 + O 0.655325 1.347169 0.290850 + H -0.527520 -1.063196 0.490177 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.066284 -1.365121 -0.662243 + 1 O 8.0000 0 15.999 -0.210585 1.088976 -0.820693 + 2 O 8.0000 0 15.999 1.238384 2.545781 0.549627 + 3 H 1.0000 0 1.008 -0.996869 -2.009149 0.926301 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.303594500109 0.00000000 0.00000000 + O 2 1 0 1.306925150139 121.16959574 0.00000000 + H 1 2 3 1.032130462857 110.69432266 78.46153833 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.463436594892 0.00000000 0.00000000 + O 2 1 0 2.469730611296 121.16959574 0.00000000 + H 1 2 3 1.950443909277 110.69432266 78.46153833 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1672 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.035509202256 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.789e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.0355092023 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5092081169769358 0.00e+00 1.40e-05 1.08e-04 3.41e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5092084233676815 -3.06e-07 7.81e-06 7.26e-05 4.44e-05 0.0 + 3 -205.5092084129699401 1.04e-08 8.81e-06 1.06e-04 1.02e-04 0.0 + 4 -205.5092084418770355 -2.89e-08 5.82e-06 6.76e-05 4.90e-05 0.0 + 5 -205.5092084374207388 4.46e-09 4.13e-06 5.37e-05 5.83e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50920843742074 Eh -5592.18986 eV + +Components: +Nuclear Repulsion : 69.03550920225625 Eh 1878.55171 eV +Electronic Energy : -274.54471763967706 Eh -7470.74157 eV +One Electron Energy: -417.75584921157605 Eh -11367.71458 eV +Two Electron Energy: 143.21113157189902 Eh 3896.97301 eV + +Virial components: +Potential Energy : -410.31865125065389 Eh -11165.33814 eV +Kinetic Energy : 204.80944281323315 Eh 5573.14827 eV +Virial Ratio : 2.00341666680294 + +DFT components: +N(Alpha) : 11.999995456629 electrons +N(Beta) : 11.999995456629 electrons +N(Total) : 23.999990913257 electrons +E(X) : -23.320652127343 Eh +E(C) : -0.803812303625 Eh +E(XC) : -24.124464430968 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -4.4563e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.3689e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.1319e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.8409e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 5.8340e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 6.0540e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.190124 -522.1898 + 1 2.0000 -19.047490 -518.3086 + 2 2.0000 -14.244258 -387.6060 + 3 2.0000 -1.243270 -33.8311 + 4 2.0000 -0.964612 -26.2484 + 5 2.0000 -0.712320 -19.3832 + 6 2.0000 -0.568522 -15.4703 + 7 2.0000 -0.518758 -14.1161 + 8 2.0000 -0.496412 -13.5081 + 9 2.0000 -0.334227 -9.0948 + 10 2.0000 -0.278708 -7.5840 + 11 2.0000 -0.244389 -6.6502 + 12 0.0000 -0.222883 -6.0650 + 13 0.0000 0.033695 0.9169 + 14 0.0000 0.098688 2.6854 + 15 0.0000 0.133050 3.6205 + 16 0.0000 0.230694 6.2775 + 17 0.0000 0.258713 7.0400 + 18 0.0000 0.317629 8.6431 + 19 0.0000 0.327853 8.9213 + 20 0.0000 0.362728 9.8703 + 21 0.0000 0.372632 10.1398 + 22 0.0000 0.393708 10.7134 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.359827 + 1 O : 0.199512 + 2 O : -0.125046 + 3 H : 0.285361 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.818702 s : 3.818702 + pz : 1.491549 p : 3.490145 + px : 1.169326 + py : 0.829269 + dz2 : 0.012177 d : 0.050980 + dxz : 0.003661 + dyz : 0.011676 + dx2y2 : 0.013058 + dxy : 0.010408 + + 1 O s : 3.750391 s : 3.750391 + pz : 1.477636 p : 3.924667 + px : 1.337842 + py : 1.109190 + dz2 : 0.022178 d : 0.125431 + dxz : 0.013204 + dyz : 0.033554 + dx2y2 : 0.029345 + dxy : 0.027150 + + 2 O s : 3.939776 s : 3.939776 + pz : 1.468945 p : 4.171461 + px : 1.165817 + py : 1.536699 + dz2 : 0.005821 d : 0.013808 + dxz : 0.000039 + dyz : 0.002337 + dx2y2 : -0.000354 + dxy : 0.005965 + + 3 H s : 0.682919 s : 0.682919 + pz : 0.015202 p : 0.031720 + px : 0.010776 + py : 0.005742 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.120982 + 1 O : -0.171236 + 2 O : 0.008782 + 3 H : 0.283436 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.316631 s : 3.316631 + pz : 1.431849 p : 3.503459 + px : 1.093284 + py : 0.978326 + dz2 : 0.040291 d : 0.300892 + dxz : 0.013429 + dyz : 0.098316 + dx2y2 : 0.082520 + dxy : 0.066338 + + 1 O s : 3.376114 s : 3.376114 + pz : 1.453579 p : 4.034394 + px : 1.274899 + py : 1.305916 + dz2 : 0.094828 d : 0.760728 + dxz : 0.070753 + dyz : 0.197761 + dx2y2 : 0.188381 + dxy : 0.209005 + + 2 O s : 3.611154 s : 3.611154 + pz : 1.418320 p : 4.130785 + px : 1.176740 + py : 1.535725 + dz2 : 0.040293 d : 0.249279 + dxz : 0.057556 + dyz : 0.046081 + dx2y2 : 0.055891 + dxy : 0.049459 + + 3 H s : 0.636485 s : 0.636485 + pz : 0.041574 p : 0.080079 + px : 0.025962 + py : 0.012544 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3598 7.0000 -0.3598 2.7029 2.7029 0.0000 + 1 O 7.8005 8.0000 0.1995 2.5667 2.5667 -0.0000 + 2 O 8.1250 8.0000 -0.1250 1.6878 1.6878 0.0000 + 3 H 0.7146 1.0000 0.2854 0.9055 0.9055 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3752 B( 0-N , 2-O ) : 0.4854 B( 0-N , 3-H ) : 0.8423 +B( 1-O , 2-O ) : 1.1654 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 2 sec + +Total time .... 2.998 sec +Sum of individual times .... 2.983 sec ( 99.5%) + +SCF preparation .... 1.029 sec ( 34.3%) +Fock matrix formation .... 0.136 sec ( 4.5%) + Startup .... 0.008 sec ( 5.5% of F) + Split-RI-J .... 0.020 sec ( 14.4% of F) + XC integration .... 0.090 sec ( 66.2% of F) + Basis function eval. .... 0.007 sec ( 8.3% of XC) + Density eval. .... 0.009 sec ( 10.1% of XC) + XC-Functional eval. .... 0.007 sec ( 7.6% of XC) + XC-Potential eval. .... 0.010 sec ( 10.7% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.008 sec ( 0.3%) +Total Energy calculation .... 0.011 sec ( 0.4%) +Population analysis .... 1.749 sec ( 58.3%) +Orbital Transformation .... 0.006 sec ( 0.2%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.015 sec ( 0.5%) +SOSCF solution .... 0.029 sec ( 1.0%) +Finished LeanSCF after 4.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 37.6 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000361767 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006818737 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502751467397 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.029.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.029.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.308648 0.787144 -0.269693 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5092084374207388 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.271332861 1.010306763 -0.222725268 +Nuclear contribution : -0.646018977 -1.378398412 0.594721343 + ----------------------------------------- +Total Dipole Moment : -0.374686116 -0.368091649 0.371996075 + ----------------------------------------- +Magnitude (a.u.) : 0.643632059 +Magnitude (Debye) : 1.635982681 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.095204 0.406683 0.371628 +Rotational constants in MHz : 92791.877168 12192.043056 11141.115558 + +Dipole components along the rotational axes: +x,y,z [a.u.] : -0.362190 0.206039 -0.490539 +x,y,z [Debye]: -0.920614 0.523708 -1.246851 + + + +Dipole moment calculation done in 0.6 sec + +Maximum memory used throughout the entire PROP-calculation: 19.8 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 30 * + * * + * Dihedral ( 2, 1, 0, 3) : 87.69230769 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.3044 0.688441 + 2. B(O 2,O 1) 1.3089 0.680069 + 3. B(H 3,N 0) 1.0349 0.398921 + 4. A(O 1,N 0,H 3) 110.5360 0.357826 + 5. A(N 0,O 1,O 2) 121.0091 0.437969 + 6. D(O 2,O 1,N 0,H 3) 87.6923 0.036908 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.008999 -0.718729 -0.330187 + O -0.128652 0.578076 -0.403220 + O 0.674609 1.367955 0.263160 + H -0.555666 -1.089458 0.466539 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.017006 -1.358201 -0.623962 + 1 O 8.0000 0 15.999 -0.243117 1.092405 -0.761975 + 2 O 8.0000 0 15.999 1.274826 2.585060 0.497300 + 3 H 1.0000 0 1.008 -1.050056 -2.058777 0.881630 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.303594500109 0.00000000 0.00000000 + O 2 1 0 1.306925150139 121.16959574 0.00000000 + H 1 2 3 1.032130462857 110.69432266 78.46153833 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.463436594892 0.00000000 0.00000000 + O 2 1 0 2.469730611296 121.16959574 0.00000000 + H 1 2 3 1.950443909277 110.69432266 78.46153833 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1672 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 68.932951874721 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.831e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22305 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 68.9329518747 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.4926226352459082 0.00e+00 4.79e-04 3.93e-03 2.07e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.006) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.4936911364420951 -1.07e-03 6.15e-04 5.58e-03 1.63e-02 0.700 0.1 + ***Turning on AO-DIIS*** + 3 -205.4946660229067277 -9.75e-04 4.94e-04 4.03e-03 1.17e-02 0.700 0.1 + 4 -205.4953577118380679 -6.92e-04 1.36e-03 1.12e-02 8.26e-03 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.4970706387278199 -1.71e-03 2.36e-04 1.59e-03 2.12e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -205.4971372552146534 -6.66e-05 5.78e-04 6.11e-03 2.11e-03 0.0 + 7 -205.4971230754916576 1.42e-05 7.11e-04 4.99e-03 6.14e-03 0.0 + 8 -205.4973419288351408 -2.19e-04 3.99e-04 2.87e-03 6.76e-04 0.1 + 9 -205.4973559913431984 -1.41e-05 2.13e-04 1.96e-03 9.21e-04 0.0 + 10 -205.4973614647375655 -5.47e-06 1.18e-04 1.03e-03 6.91e-04 0.0 + 11 -205.4973683093629404 -6.84e-06 2.89e-05 2.74e-04 1.55e-04 0.0 + 12 -205.4973689634282721 -6.54e-07 1.90e-05 1.66e-04 7.81e-05 0.1 + 13 -205.4973691052489642 -1.42e-07 8.22e-06 6.00e-05 2.53e-05 0.0 + 14 -205.4973691339784239 -2.87e-08 3.76e-06 3.77e-05 9.16e-06 0.0 + 15 -205.4973691376241334 -3.65e-09 2.75e-07 3.25e-06 2.91e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 15 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49736913762413 Eh -5591.86770 eV + +Components: +Nuclear Repulsion : 68.93295187472123 Eh 1875.76098 eV +Electronic Energy : -274.43032101234536 Eh -7467.62868 eV +One Electron Energy: -417.54164566441256 Eh -11361.88581 eV +Two Electron Energy: 143.11132465206720 Eh 3894.25712 eV + +Virial components: +Potential Energy : -410.27053539140883 Eh -11164.02884 eV +Kinetic Energy : 204.77316625378469 Eh 5572.16114 eV +Virial Ratio : 2.00353661027511 + +DFT components: +N(Alpha) : 11.999997354878 electrons +N(Beta) : 11.999997354878 electrons +N(Total) : 23.999994709757 electrons +E(X) : -23.311332670221 Eh +E(C) : -0.803996235752 Eh +E(XC) : -24.115328905974 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.6457e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.2532e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.7491e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.1205e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.9073e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.2110e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.196451 -522.3620 + 1 2.0000 -19.055240 -518.5194 + 2 2.0000 -14.231475 -387.2581 + 3 2.0000 -1.243960 -33.8499 + 4 2.0000 -0.964357 -26.2415 + 5 2.0000 -0.708944 -19.2914 + 6 2.0000 -0.568394 -15.4668 + 7 2.0000 -0.520796 -14.1716 + 8 2.0000 -0.498835 -13.5740 + 9 2.0000 -0.335295 -9.1238 + 10 2.0000 -0.282664 -7.6917 + 11 2.0000 -0.232582 -6.3289 + 12 0.0000 -0.229987 -6.2583 + 13 0.0000 0.029616 0.8059 + 14 0.0000 0.101832 2.7710 + 15 0.0000 0.134041 3.6474 + 16 0.0000 0.230304 6.2669 + 17 0.0000 0.260302 7.0832 + 18 0.0000 0.319606 8.6969 + 19 0.0000 0.329277 8.9601 + 20 0.0000 0.355832 9.6827 + 21 0.0000 0.375305 10.2126 + 22 0.0000 0.392488 10.6802 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.407257 + 1 O : 0.196278 + 2 O : -0.089086 + 3 H : 0.300065 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.797484 s : 3.797484 + pz : 1.506587 p : 3.561431 + px : 1.252694 + py : 0.802150 + dz2 : 0.009789 d : 0.048341 + dxz : 0.004283 + dyz : 0.012445 + dx2y2 : 0.012674 + dxy : 0.009151 + + 1 O s : 3.760000 s : 3.760000 + pz : 1.457632 p : 3.919195 + px : 1.337749 + py : 1.123815 + dz2 : 0.019383 d : 0.124526 + dxz : 0.013817 + dyz : 0.035907 + dx2y2 : 0.033049 + dxy : 0.022371 + + 2 O s : 3.934552 s : 3.934552 + pz : 1.428369 p : 4.140455 + px : 1.187816 + py : 1.524270 + dz2 : 0.006133 d : 0.014080 + dxz : -0.000274 + dyz : 0.002305 + dx2y2 : -0.000360 + dxy : 0.006276 + + 3 H s : 0.667217 s : 0.667217 + pz : 0.014931 p : 0.032719 + px : 0.011992 + py : 0.005796 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.154614 + 1 O : -0.164763 + 2 O : 0.026420 + 3 H : 0.292957 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.296595 s : 3.296595 + pz : 1.436815 p : 3.563412 + px : 1.171697 + py : 0.954900 + dz2 : 0.036184 d : 0.294607 + dxz : 0.014333 + dyz : 0.092673 + dx2y2 : 0.081144 + dxy : 0.070272 + + 1 O s : 3.380069 s : 3.380069 + pz : 1.422335 p : 4.017252 + px : 1.281549 + py : 1.313368 + dz2 : 0.081394 d : 0.767441 + dxz : 0.068553 + dyz : 0.202970 + dx2y2 : 0.192195 + dxy : 0.222329 + + 2 O s : 3.615214 s : 3.615214 + pz : 1.378075 p : 4.110802 + px : 1.201300 + py : 1.531426 + dz2 : 0.035419 d : 0.247565 + dxz : 0.056873 + dyz : 0.043208 + dx2y2 : 0.058816 + dxy : 0.053248 + + 3 H s : 0.626251 s : 0.626251 + pz : 0.039643 p : 0.080792 + px : 0.028805 + py : 0.012344 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.4073 7.0000 -0.4073 2.6385 2.6385 0.0000 + 1 O 7.8037 8.0000 0.1963 2.5982 2.5982 0.0000 + 2 O 8.0891 8.0000 -0.0891 1.6951 1.6951 -0.0000 + 3 H 0.6999 1.0000 0.3001 0.8987 0.8987 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3764 B( 0-N , 2-O ) : 0.4500 B( 0-N , 3-H ) : 0.8121 +B( 1-O , 2-O ) : 1.1901 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 3 sec + +Total time .... 3.389 sec +Sum of individual times .... 3.370 sec ( 99.4%) + +SCF preparation .... 0.978 sec ( 28.8%) +Fock matrix formation .... 0.425 sec ( 12.5%) + Startup .... 0.017 sec ( 4.0% of F) + Split-RI-J .... 0.063 sec ( 14.8% of F) + XC integration .... 0.269 sec ( 63.3% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.018 sec ( 6.6% of XC) + Density eval. .... 0.024 sec ( 8.9% of XC) + XC-Functional eval. .... 0.015 sec ( 5.4% of XC) + XC-Potential eval. .... 0.025 sec ( 9.2% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.063 sec ( 1.8%) +Total Energy calculation .... 0.034 sec ( 1.0%) +Population analysis .... 1.723 sec ( 50.9%) +Orbital Transformation .... 0.014 sec ( 0.4%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.070 sec ( 2.1%) +SOSCF solution .... 0.064 sec ( 1.9%) +Finished LeanSCF after 5.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 37.9 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000361339 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006815955 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.490914522441 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003222 -0.000005920 0.000001608 + 2 O : -0.000000212 0.000000772 -0.000000635 + 3 O : 0.000003412 0.000007919 0.000001179 + 4 H : 0.000000023 -0.000002771 -0.000002152 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000117096 +RMS gradient ... 0.0000033803 +MAX gradient ... 0.0000079191 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.052985570 -0.000450461 0.006040462 + 2 O : -0.041943624 -0.002200534 0.032151132 + 3 O : 0.021579102 0.003185962 -0.022068986 + 4 H : -0.032621048 -0.000534967 -0.016122608 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000094568 -0.0000057457 0.0000076556 + +Norm of the Cartesian gradient ... 0.0890458956 +RMS gradient ... 0.0257053359 +MAX gradient ... 0.0529855702 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.156 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.2%) +RI-J Coulomb gradient .... 0.060 sec ( 38.6%) +XC gradient .... 0.019 sec ( 12.2%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.490914522 Eh +Current gradient norm .... 0.089045896 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999446841 +Lowest eigenvalues of augmented Hessian: + -0.000416816 0.357352366 0.394920809 0.437180683 0.675195635 +Length of the computed step .... 0.033275156 +The final length of the internal step .... 0.033275156 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0135845256 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0097755410 RMS(Int)= 0.0135627761 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000006 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0051866693 0.0001000000 NO + MAX gradient 0.0106926155 0.0003000000 NO + RMS step 0.0135845256 0.0020000000 NO + MAX step 0.0299136051 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0067 Max(Angles) 1.71 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3044 0.002283 -0.0018 1.3026 + 2. B(O 2,O 1) 1.3089 0.003931 -0.0031 1.3058 + 3. B(H 3,N 0) 1.0349 0.005010 -0.0067 1.0282 + 4. A(O 1,N 0,H 3) 110.54 -0.010693 1.71 112.25 + 5. A(N 0,O 1,O 2) 121.01 0.001145 -0.15 120.86 + 6. D(O 2,O 1,N 0,H 3) 87.69 0.065248 0.00 87.69 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.771 %) +Internal coordinates : 0.000 s ( 3.664 %) +B/P matrices and projection : 0.000 s (16.183 %) +Hessian update/contruction : 0.000 s (26.107 %) +Making the step : 0.000 s ( 7.939 %) +Converting the step to Cartesian: 0.000 s ( 5.496 %) +Storing new data : 0.000 s ( 3.969 %) +Checking convergence : 0.000 s ( 0.000 %) +Final printing : 0.000 s (26.718 %) +Total time : 0.001 s + +Time for energy+gradient : 9.585 s +Time for complete geometry iter : 10.404 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.013204 -0.713011 -0.320549 + O -0.125588 0.581928 -0.405824 + O 0.675666 1.369076 0.260163 + H -0.555582 -1.100148 0.462502 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.024953 -1.347396 -0.605749 + 1 O 8.0000 0 15.999 -0.237326 1.099684 -0.766897 + 2 O 8.0000 0 15.999 1.276824 2.587178 0.491637 + 3 H 1.0000 0 1.008 -1.049898 -2.078979 0.874002 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.302600681458 0.00000000 0.00000000 + O 2 1 0 1.305813093551 120.85913759 0.00000000 + H 1 2 3 1.028210649265 112.24989693 87.69230781 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.461558549814 0.00000000 0.00000000 + O 2 1 0 2.467629128899 120.85913759 0.00000000 + H 1 2 3 1.943036535092 112.24989693 87.69230781 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1672 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.061527434228 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.799e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22303 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.4975121188407456 0.00e+00 8.70e-05 1.24e-03 3.54e-03 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.004) - skipping pre-diagonalization + Will do a full diagonalization + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 2 -205.4975490218753293 -3.69e-05 3.19e-04 4.16e-03 2.76e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 3 -205.4976552582435829 -1.06e-04 9.90e-05 7.73e-04 3.81e-04 0.0 + 4 -205.4976608589104785 -5.60e-06 2.54e-04 2.21e-03 5.77e-04 0.0 + 5 -205.4976593214558420 1.54e-06 7.66e-05 9.78e-04 1.13e-03 0.0 + 6 -205.4976653002432840 -5.98e-06 1.13e-04 8.84e-04 4.23e-04 0.0 + 7 -205.4976645056859752 7.95e-07 6.87e-05 5.78e-04 5.10e-04 0.0 + 8 -205.4976683931970456 -3.89e-06 1.86e-05 1.70e-04 5.22e-05 0.0 + 9 -205.4976685041648921 -1.11e-07 2.50e-05 1.88e-04 2.46e-05 0.0 + 10 -205.4976685759573911 -7.18e-08 5.38e-06 3.94e-05 2.34e-05 0.0 + 11 -205.4976685820669786 -6.11e-09 9.29e-07 1.11e-05 4.63e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49766858206698 Eh -5591.87585 eV + +Components: +Nuclear Repulsion : 69.06152743422814 Eh 1879.25970 eV +Electronic Energy : -274.55919601629512 Eh -7471.13555 eV +One Electron Energy: -417.78909528247527 Eh -11368.61925 eV +Two Electron Energy: 143.22989926618018 Eh 3897.48370 eV + +Virial components: +Potential Energy : -410.27924011260120 Eh -11164.26570 eV +Kinetic Energy : 204.78157153053419 Eh 5572.38986 eV +Virial Ratio : 2.00349688229356 + +DFT components: +N(Alpha) : 11.999997295135 electrons +N(Beta) : 11.999997295135 electrons +N(Total) : 23.999994590269 electrons +E(X) : -23.315585030163 Eh +E(C) : -0.804319145821 Eh +E(XC) : -24.119904175984 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 6.1096e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.1127e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 9.2907e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.7584e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.6342e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.7278e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 3.3 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 38.1 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361251 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006774169 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.491255664720 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003221 -0.000005941 0.000001610 + 2 O : -0.000000194 0.000000802 -0.000000643 + 3 O : 0.000003425 0.000007929 0.000001138 + 4 H : -0.000000010 -0.000002789 -0.000002105 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000117245 +RMS gradient ... 0.0000033846 +MAX gradient ... 0.0000079286 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.048797008 -0.002373652 0.011323552 + 2 O : -0.039654475 0.001652555 0.028890930 + 3 O : 0.019732648 0.001211243 -0.021387142 + 4 H : -0.028875181 -0.000490145 -0.018827340 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000147035 -0.0000035894 0.0000016846 + +Norm of the Cartesian gradient ... 0.0834364351 +RMS gradient ... 0.0240860241 +MAX gradient ... 0.0487970084 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.122 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.9%) +RI-J Coulomb gradient .... 0.057 sec ( 46.9%) +XC gradient .... 0.021 sec ( 16.8%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.491255665 Eh +Current gradient norm .... 0.083436435 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.997022314 +Lowest eigenvalues of augmented Hessian: + -0.000668430 0.110198520 0.420792832 0.457406197 0.654598636 +Length of the computed step .... 0.077343891 +The final length of the internal step .... 0.077343891 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0315755114 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0238411378 RMS(Int)= 0.0315001010 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000003 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000336214 +Previously predicted energy change .... -0.000208639 +Actually observed energy change .... -0.000341142 +Ratio of predicted to observed change .... 1.635084000 +New trust radius .... 0.200000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0003411423 0.0000050000 NO + RMS gradient 0.0036523345 0.0001000000 NO + MAX gradient 0.0076471539 0.0003000000 NO + RMS step 0.0315755114 0.0020000000 NO + MAX step 0.0732306702 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0095 Max(Angles) 4.20 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3026 0.004075 -0.0095 1.2931 + 2. B(O 2,O 1) 1.3058 0.001931 -0.0056 1.3002 + 3. B(H 3,N 0) 1.0282 0.001077 -0.0072 1.0210 + 4. A(O 1,N 0,H 3) 112.25 -0.007647 4.20 116.45 + 5. A(N 0,O 1,O 2) 120.86 -0.000260 0.02 120.88 + 6. D(O 2,O 1,N 0,H 3) 87.69 0.061560 -0.00 87.69 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 7.326 %) +Internal coordinates : 0.000 s ( 2.907 %) +B/P matrices and projection : 0.000 s (11.279 %) +Hessian update/contruction : 0.000 s (41.977 %) +Making the step : 0.000 s ( 4.535 %) +Converting the step to Cartesian: 0.000 s ( 3.721 %) +Storing new data : 0.000 s ( 3.605 %) +Checking convergence : 0.000 s ( 1.628 %) +Final printing : 0.000 s (22.791 %) +Total time : 0.001 s + +Time for energy+gradient : 7.634 s +Time for complete geometry iter : 8.443 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.023243 -0.696731 -0.300570 + O -0.116507 0.588270 -0.410925 + O 0.678438 1.374497 0.252668 + H -0.557396 -1.128191 0.455119 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.043922 -1.316631 -0.567995 + 1 O 8.0000 0 15.999 -0.220167 1.111668 -0.776536 + 2 O 8.0000 0 15.999 1.282061 2.597423 0.477474 + 3 H 1.0000 0 1.008 -1.053326 -2.131973 0.860050 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.293098330662 0.00000000 0.00000000 + O 2 1 0 1.300172063086 120.88174115 0.00000000 + H 1 2 3 1.021049985434 116.44570560 87.69230781 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.443601709183 0.00000000 0.00000000 + O 2 1 0 2.456969126208 120.88174115 0.00000000 + H 1 2 3 1.929504841514 116.44570560 87.69230781 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1674 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.389253377113 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.734e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22296 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.4970903438670575 0.00e+00 2.02e-04 2.51e-03 8.34e-03 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.006) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.4972948855851769 -2.05e-04 2.26e-04 2.62e-03 6.48e-03 0.700 0.1 + ***Turning on AO-DIIS*** + 3 -205.4974777437645344 -1.83e-04 1.82e-04 1.78e-03 4.62e-03 0.700 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 4 -205.4976109596577771 -1.33e-04 4.93e-04 4.71e-03 3.25e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 5 -205.4979353040207002 -3.24e-04 2.21e-04 2.46e-03 7.50e-04 0.0 + 6 -205.4979369881553453 -1.68e-06 3.30e-04 2.63e-03 2.51e-03 0.0 + 7 -205.4979768427305089 -3.99e-05 1.25e-04 9.58e-04 2.01e-04 0.0 + 8 -205.4979793798684682 -2.54e-06 9.11e-05 6.52e-04 2.74e-04 0.0 + 9 -205.4979802240210347 -8.44e-07 3.03e-05 2.94e-04 2.32e-04 0.0 + 10 -205.4979812865099689 -1.06e-06 1.77e-05 1.88e-04 7.27e-05 0.0 + 11 -205.4979814303252965 -1.44e-07 9.42e-06 6.98e-05 4.47e-05 0.0 + 12 -205.4979814581013784 -2.78e-08 2.95e-06 2.50e-05 6.16e-06 0.0 + 13 -205.4979814598537473 -1.75e-09 5.31e-07 5.32e-06 3.43e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 13 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49798145985375 Eh -5591.88436 eV + +Components: +Nuclear Repulsion : 69.38925337711346 Eh 1888.17758 eV +Electronic Energy : -274.88723483696720 Eh -7480.06194 eV +One Electron Energy: -418.42838439919126 Eh -11386.01519 eV +Two Electron Energy: 143.54114956222404 Eh 3905.95325 eV + +Virial components: +Potential Energy : -410.29697038043093 Eh -11164.74817 eV +Kinetic Energy : 204.79898892057722 Eh 5572.86381 eV +Virial Ratio : 2.00341306635819 + +DFT components: +N(Alpha) : 11.999997361907 electrons +N(Beta) : 11.999997361907 electrons +N(Total) : 23.999994723814 electrons +E(X) : -23.324628085349 Eh +E(C) : -0.805203523394 Eh +E(XC) : -24.129831608743 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.7524e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.3164e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 5.3124e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.2496e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.4279e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.3135e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 3.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 38.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361038 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006676973 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.491665524341 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003214 -0.000006004 0.000001601 + 2 O : -0.000000152 0.000000865 -0.000000666 + 3 O : 0.000003479 0.000007999 0.000001048 + 4 H : -0.000000113 -0.000002860 -0.000001982 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000118098 +RMS gradient ... 0.0000034092 +MAX gradient ... 0.0000079993 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.040490564 -0.002084188 0.016516048 + 2 O : -0.031900387 0.006281231 0.023391669 + 3 O : 0.014296924 -0.002552088 -0.020230101 + 4 H : -0.022887101 -0.001644955 -0.019677617 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000086591 0.0000005059 0.0000133160 + +Norm of the Cartesian gradient ... 0.0710969349 +RMS gradient ... 0.0205239173 +MAX gradient ... 0.0404905636 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.128 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.9%) +RI-J Coulomb gradient .... 0.059 sec ( 46.4%) +XC gradient .... 0.020 sec ( 15.4%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.491665524 Eh +Current gradient norm .... 0.071096935 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.200 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999433045 +Lowest eigenvalues of augmented Hessian: + -0.000127143 0.078561923 0.422453699 0.458875575 0.658891087 +Length of the computed step .... 0.033687919 +The final length of the internal step .... 0.033687919 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0137530354 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0098039451 RMS(Int)= 0.0137483181 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000002 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000063644 +Previously predicted energy change .... -0.000336214 +Actually observed energy change .... -0.000409860 +Ratio of predicted to observed change .... 1.219042753 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0004098596 0.0000050000 NO + RMS gradient 0.0025602693 0.0001000000 NO + MAX gradient 0.0047046292 0.0003000000 NO + RMS step 0.0137530354 0.0020000000 NO + MAX step 0.0307145038 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0072 Max(Angles) 1.76 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2931 0.004705 -0.0072 1.2859 + 2. B(O 2,O 1) 1.3002 -0.003126 0.0011 1.3013 + 3. B(H 3,N 0) 1.0210 -0.001895 -0.0002 1.0208 + 4. A(O 1,N 0,H 3) 116.45 -0.001835 1.76 118.21 + 5. A(N 0,O 1,O 2) 120.88 -0.000682 0.07 120.96 + 6. D(O 2,O 1,N 0,H 3) 87.69 0.052095 0.00 87.69 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.486 %) +Internal coordinates : 0.000 s ( 3.495 %) +B/P matrices and projection : 0.000 s (17.933 %) +Hessian update/contruction : 0.000 s (27.964 %) +Making the step : 0.000 s ( 5.319 %) +Converting the step to Cartesian: 0.000 s ( 4.255 %) +Storing new data : 0.000 s ( 3.343 %) +Checking convergence : 0.000 s ( 1.520 %) +Final printing : 0.000 s (25.684 %) +Total time : 0.001 s + +Time for energy+gradient : 7.535 s +Time for complete geometry iter : 8.434 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 4 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.027428 -0.688800 -0.293306 + O -0.113158 0.588606 -0.413378 + O 0.680369 1.378051 0.250299 + H -0.558491 -1.140013 0.452676 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.051831 -1.301643 -0.554268 + 1 O 8.0000 0 15.999 -0.213837 1.112305 -0.781171 + 2 O 8.0000 0 15.999 1.285711 2.604138 0.472997 + 3 H 1.0000 0 1.008 -1.055396 -2.154312 0.855434 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.285897940154 0.00000000 0.00000000 + O 2 1 0 1.301297414820 120.95574043 0.00000000 + H 1 2 3 1.020837943238 118.20551692 87.69230781 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.429994943065 0.00000000 0.00000000 + O 2 1 0 2.459095732790 120.95574043 0.00000000 + H 1 2 3 1.929104139836 118.20551692 87.69230781 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1674 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.501130739394 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.738e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22295 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.5 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.4978507542285797 0.00e+00 8.79e-05 9.11e-04 4.54e-03 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.007) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.4978954822692003 -4.47e-05 1.00e-04 1.02e-03 3.38e-03 0.700 0.0 + ***Turning on AO-DIIS*** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 3 -205.4979336446794491 -3.82e-05 2.66e-04 2.50e-03 2.49e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 4 -205.4980220847062924 -8.84e-05 1.42e-04 1.47e-03 7.46e-04 0.0 + 5 -205.4979944901391491 2.76e-05 1.19e-04 1.50e-03 2.98e-03 0.0 + 6 -205.4980301006367540 -3.56e-05 8.45e-05 8.95e-04 2.65e-04 0.0 + 7 -205.4980284683089735 1.63e-06 4.91e-05 4.96e-04 6.83e-04 0.0 + 8 -205.4980336570997110 -5.19e-06 5.18e-05 4.00e-04 7.66e-05 0.0 + 9 -205.4980342632486554 -6.06e-07 4.65e-05 3.29e-04 4.24e-05 0.0 + 10 -205.4980344334279607 -1.70e-07 8.07e-06 7.43e-05 3.01e-05 0.0 + 11 -205.4980344647203765 -3.13e-08 3.44e-06 2.55e-05 1.34e-05 0.0 + 12 -205.4980344706674487 -5.95e-09 1.72e-06 1.84e-05 4.71e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49803447066745 Eh -5591.88580 eV + +Components: +Nuclear Repulsion : 69.50113073939377 Eh 1891.22192 eV +Electronic Energy : -274.99916521006128 Eh -7483.10772 eV +One Electron Energy: -418.65368790015685 Eh -11392.14601 eV +Two Electron Energy: 143.65452269009560 Eh 3909.03829 eV + +Virial components: +Potential Energy : -410.30228243171905 Eh -11164.89272 eV +Kinetic Energy : 204.80424796105163 Eh 5573.00691 eV +Virial Ratio : 2.00338755917674 + +DFT components: +N(Alpha) : 11.999997533662 electrons +N(Beta) : 11.999997533662 electrons +N(Total) : 23.999995067323 electrons +E(X) : -23.327459685355 Eh +E(C) : -0.805563700276 Eh +E(XC) : -24.133023385631 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 5.9471e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.8408e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.7178e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.4858e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.7134e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 6.4830e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 3.5 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 38.5 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360942 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006640701 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.491754711367 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003209 -0.000006033 0.000001588 + 2 O : -0.000000141 0.000000879 -0.000000680 + 3 O : 0.000003516 0.000008051 0.000001020 + 4 H : -0.000000166 -0.000002897 -0.000001928 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000118671 +RMS gradient ... 0.0000034257 +MAX gradient ... 0.0000080510 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.037910568 0.000694307 0.016181412 + 2 O : -0.028980339 0.004995902 0.021374725 + 3 O : 0.012625207 -0.003053372 -0.019252018 + 4 H : -0.021555436 -0.002636837 -0.018304120 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000019954 0.0000023041 0.0000189311 + +Norm of the Cartesian gradient ... 0.0660849373 +RMS gradient ... 0.0190770782 +MAX gradient ... 0.0379105680 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.128 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.9%) +RI-J Coulomb gradient .... 0.061 sec ( 47.7%) +XC gradient .... 0.019 sec ( 14.9%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.491754711 Eh +Current gradient norm .... 0.066084937 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999692439 +Lowest eigenvalues of augmented Hessian: + -0.000073889 0.062655625 0.418113844 0.460127332 0.570428620 +Length of the computed step .... 0.024807396 +The final length of the internal step .... 0.024807396 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0101275770 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0063617994 RMS(Int)= 0.0101263352 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000036967 +Previously predicted energy change .... -0.000063644 +Actually observed energy change .... -0.000089187 +Ratio of predicted to observed change .... 1.401352155 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000891870 0.0000050000 NO + RMS gradient 0.0020307963 0.0001000000 NO + MAX gradient 0.0039713325 0.0003000000 NO + RMS step 0.0101275770 0.0020000000 NO + MAX step 0.0194569292 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0066 Max(Angles) 1.11 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2859 0.002820 -0.0066 1.2793 + 2. B(O 2,O 1) 1.3013 -0.003971 0.0047 1.3060 + 3. B(H 3,N 0) 1.0208 -0.000996 0.0005 1.0213 + 4. A(O 1,N 0,H 3) 118.21 -0.000126 1.11 119.32 + 5. A(N 0,O 1,O 2) 120.96 -0.000104 0.01 120.97 + 6. D(O 2,O 1,N 0,H 3) 87.69 0.048257 0.00 87.69 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.548 %) +Internal coordinates : 0.000 s ( 3.151 %) +B/P matrices and projection : 0.000 s (12.466 %) +Hessian update/contruction : 0.000 s (33.425 %) +Making the step : 0.000 s ( 5.068 %) +Converting the step to Cartesian: 0.000 s ( 4.110 %) +Storing new data : 0.000 s ( 3.151 %) +Checking convergence : 0.000 s ( 1.370 %) +Final printing : 0.000 s (26.301 %) +Total time : 0.001 s + +Time for energy+gradient : 7.945 s +Time for complete geometry iter : 8.767 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 5 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.030181 -0.683332 -0.289069 + O -0.112042 0.586994 -0.415789 + O 0.682599 1.381374 0.249863 + H -0.559085 -1.147193 0.451287 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.057033 -1.291310 -0.546261 + 1 O 8.0000 0 15.999 -0.211728 1.109258 -0.785727 + 2 O 8.0000 0 15.999 1.289926 2.610419 0.472172 + 3 H 1.0000 0 1.008 -1.056518 -2.167881 0.852809 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.279252502728 0.00000000 0.00000000 + O 2 1 0 1.305981001420 120.97024309 0.00000000 + H 1 2 3 1.021290419390 119.32031683 87.69230781 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.417436886288 0.00000000 0.00000000 + O 2 1 0 2.467946428787 120.97024309 0.00000000 + H 1 2 3 1.929959195844 119.32031683 87.69230781 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.523069393893 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.777e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22295 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.6 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.4979372912423230 0.00e+00 7.42e-05 6.18e-04 4.23e-03 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.009) - skipping pre-diagonalization + Will do a full diagonalization + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 2 -205.4979701109486143 -3.28e-05 2.65e-04 2.41e-03 3.07e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 3 -205.4980543379713538 -8.42e-05 1.68e-04 1.90e-03 7.92e-04 0.0 + 4 -205.4980197795973993 3.46e-05 1.11e-04 1.23e-03 3.37e-03 0.0 + 5 -205.4980595710938189 -3.98e-05 4.44e-05 4.73e-04 1.81e-04 0.0 + 6 -205.4980591729185733 3.98e-07 3.73e-05 3.54e-04 3.94e-04 0.0 + 7 -205.4980611458940132 -1.97e-06 3.70e-05 2.76e-04 7.13e-05 0.0 + 8 -205.4980614573730975 -3.11e-07 3.25e-05 2.91e-04 3.87e-05 0.0 + 9 -205.4980615785516136 -1.21e-07 5.06e-06 5.66e-05 2.61e-05 0.0 + 10 -205.4980615954982852 -1.69e-08 3.20e-06 2.95e-05 1.03e-05 0.0 + 11 -205.4980615990274089 -3.53e-09 1.11e-06 9.71e-06 3.83e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49806159902741 Eh -5591.88654 eV + +Components: +Nuclear Repulsion : 69.52306939389288 Eh 1891.81890 eV +Electronic Energy : -275.02113099292029 Eh -7483.70544 eV +One Electron Energy: -418.70643276466848 Eh -11393.58127 eV +Two Electron Energy: 143.68530177174819 Eh 3909.87584 eV + +Virial components: +Potential Energy : -410.30288193653388 Eh -11164.90903 eV +Kinetic Energy : 204.80482033750647 Eh 5573.02249 eV +Virial Ratio : 2.00338488742784 + +DFT components: +N(Alpha) : 11.999997749694 electrons +N(Beta) : 11.999997749694 electrons +N(Total) : 23.999995499387 electrons +E(X) : -23.328071017769 Eh +E(C) : -0.805724779337 Eh +E(XC) : -24.133795797106 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.5291e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 9.7099e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.1057e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.0723e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.8331e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.4801e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 3.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 38.6 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360866 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006620578 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.491801886778 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003206 -0.000006056 0.000001574 + 2 O : -0.000000142 0.000000876 -0.000000694 + 3 O : 0.000003553 0.000008103 0.000001014 + 4 H : -0.000000205 -0.000002924 -0.000001895 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000119248 +RMS gradient ... 0.0000034424 +MAX gradient ... 0.0000081034 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.036656004 0.003589389 0.015378672 + 2 O : -0.028272714 0.002015660 0.019445717 + 3 O : 0.012650064 -0.002277318 -0.017718415 + 4 H : -0.021033354 -0.003327731 -0.017105975 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000006279 0.0000034566 0.0000229734 + +Norm of the Cartesian gradient ... 0.0632442703 +RMS gradient ... 0.0182570482 +MAX gradient ... 0.0366560038 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.138 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.006 sec ( 4.0%) +RI-J Coulomb gradient .... 0.066 sec ( 47.9%) +XC gradient .... 0.019 sec ( 13.9%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.491801887 Eh +Current gradient norm .... 0.063244270 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999961624 +Lowest eigenvalues of augmented Hessian: + -0.000022123 0.070067341 0.351716350 0.430109139 0.466561986 +Length of the computed step .... 0.008761068 +The final length of the internal step .... 0.008761068 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0035766909 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0016504668 RMS(Int)= 0.0035766459 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000011062 +Previously predicted energy change .... -0.000036967 +Actually observed energy change .... -0.000047175 +Ratio of predicted to observed change .... 1.276144504 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000471754 0.0000050000 NO + RMS gradient 0.0011615563 0.0001000000 NO + MAX gradient 0.0027181185 0.0003000000 NO + RMS step 0.0035766909 0.0020000000 NO + MAX step 0.0075973056 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0040 Max(Angles) 0.09 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2793 0.000567 -0.0021 1.2771 + 2. B(O 2,O 1) 1.3060 -0.002718 0.0040 1.3100 + 3. B(H 3,N 0) 1.0213 0.000005 0.0003 1.0216 + 4. A(O 1,N 0,H 3) 119.32 0.000575 0.09 119.41 + 5. A(N 0,O 1,O 2) 120.97 0.000234 -0.03 120.94 + 6. D(O 2,O 1,N 0,H 3) 87.69 0.045965 0.00 87.69 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (11.053 %) +Internal coordinates : 0.000 s ( 2.991 %) +B/P matrices and projection : 0.000 s (11.704 %) +Hessian update/contruction : 0.000 s (27.828 %) +Making the step : 0.000 s ( 6.112 %) +Converting the step to Cartesian: 0.000 s ( 3.771 %) +Storing new data : 0.000 s ( 3.121 %) +Checking convergence : 0.000 s ( 1.300 %) +Final printing : 0.000 s (31.860 %) +Total time : 0.001 s + +Time for energy+gradient : 7.919 s +Time for complete geometry iter : 8.890 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 6 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.030514 -0.682657 -0.288978 + O -0.112887 0.585401 -0.416824 + O 0.683765 1.382729 0.250797 + H -0.559072 -1.147629 0.451297 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.057664 -1.290035 -0.546090 + 1 O 8.0000 0 15.999 -0.213325 1.106248 -0.787684 + 2 O 8.0000 0 15.999 1.292128 2.612978 0.473938 + 3 H 1.0000 0 1.008 -1.056492 -2.168704 0.852829 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.277145926471 0.00000000 0.00000000 + O 2 1 0 1.310001322383 120.93575297 0.00000000 + H 1 2 3 1.021557438066 119.41222425 87.69230781 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.413456034084 0.00000000 0.00000000 + O 2 1 0 2.475543734379 120.93575297 0.00000000 + H 1 2 3 1.930463788014 119.41222425 87.69230781 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.472843826986 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.814e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22295 +Total number of batches ... 349 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.6 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.4980525376528249 0.00e+00 1.25e-04 1.72e-03 2.31e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.4980730422275315 -2.05e-05 1.09e-04 1.15e-03 5.31e-04 0.0 + 3 -205.4980555622624365 1.75e-05 7.81e-05 9.02e-04 2.36e-03 0.0 + 4 -205.4980756870465939 -2.01e-05 1.46e-05 2.07e-04 5.61e-05 0.1 + 5 -205.4980755747504872 1.12e-07 7.16e-06 1.09e-04 1.34e-04 0.1 + 6 -205.4980757497149284 -1.75e-07 3.39e-06 2.25e-05 1.06e-05 0.1 + 7 -205.4980757549715804 -5.26e-09 3.93e-06 2.88e-05 6.68e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49807575497158 Eh -5591.88693 eV + +Components: +Nuclear Repulsion : 69.47284382698597 Eh 1890.45219 eV +Electronic Energy : -274.97091958195756 Eh -7482.33912 eV +One Electron Energy: -418.61387937391544 Eh -11391.06277 eV +Two Electron Energy: 143.64295979195788 Eh 3908.72365 eV + +Virial components: +Potential Energy : -410.29966898875523 Eh -11164.82160 eV +Kinetic Energy : 204.80159323378365 Eh 5572.93467 eV +Virial Ratio : 2.00340076710435 + +DFT components: +N(Alpha) : 11.999997854442 electrons +N(Beta) : 11.999997854442 electrons +N(Total) : 23.999995708884 electrons +E(X) : -23.326886417706 Eh +E(C) : -0.805660688353 Eh +E(XC) : -24.132547106059 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 5.2567e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.8849e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.9253e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.5402e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 6.6823e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.3236e-04 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 3.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 38.8 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360839 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006620576 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.491816018198 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003209 -0.000006064 0.000001569 + 2 O : -0.000000151 0.000000865 -0.000000700 + 3 O : 0.000003571 0.000008128 0.000001024 + 4 H : -0.000000212 -0.000002930 -0.000001893 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000119528 +RMS gradient ... 0.0000034505 +MAX gradient ... 0.0000081283 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.036805973 0.004299926 0.015088119 + 2 O : -0.029333815 0.000299979 0.018488725 + 3 O : 0.013665795 -0.001237676 -0.016697603 + 4 H : -0.021137953 -0.003362228 -0.016879241 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000029353 0.0000129041 0.0000220656 + +Norm of the Cartesian gradient ... 0.0633509124 +RMS gradient ... 0.0182878332 +MAX gradient ... 0.0368059727 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.124 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 4.0%) +RI-J Coulomb gradient .... 0.058 sec ( 47.2%) +XC gradient .... 0.018 sec ( 14.6%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.491816018 Eh +Current gradient norm .... 0.063350912 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999989746 +Lowest eigenvalues of augmented Hessian: + -0.000004264 0.077240455 0.243032884 0.422576783 0.464691806 +Length of the computed step .... 0.004528638 +The final length of the internal step .... 0.004528638 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0018488088 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0012465621 RMS(Int)= 0.0018487728 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000002132 +Previously predicted energy change .... -0.000011062 +Actually observed energy change .... -0.000014131 +Ratio of predicted to observed change .... 1.277432501 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000141314 0.0000050000 NO + RMS gradient 0.0004335284 0.0001000000 NO + MAX gradient 0.0009516132 0.0003000000 NO + RMS step 0.0018488088 0.0020000000 YES + MAX step 0.0032351839 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0017 Max(Angles) 0.19 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2771 -0.000102 0.0000 1.2772 + 2. B(O 2,O 1) 1.3100 -0.000952 0.0017 1.3117 + 3. B(H 3,N 0) 1.0216 0.000237 -0.0001 1.0215 + 4. A(O 1,N 0,H 3) 119.41 0.000368 -0.19 119.23 + 5. A(N 0,O 1,O 2) 120.94 0.000143 -0.02 120.91 + 6. D(O 2,O 1,N 0,H 3) 87.69 0.045845 -0.00 87.69 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (11.842 %) +Internal coordinates : 0.000 s ( 2.871 %) +B/P matrices and projection : 0.000 s (12.440 %) +Hessian update/contruction : 0.000 s (32.895 %) +Making the step : 0.000 s ( 4.665 %) +Converting the step to Cartesian: 0.000 s ( 3.708 %) +Storing new data : 0.000 s ( 2.990 %) +Checking convergence : 0.000 s ( 1.316 %) +Final printing : 0.000 s (27.153 %) +Total time : 0.001 s + +Time for energy+gradient : 7.795 s +Time for complete geometry iter : 8.706 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 7 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.030148 -0.683424 -0.289825 + O -0.113705 0.584653 -0.416961 + O 0.684048 1.382895 0.251514 + H -0.558903 -1.146281 0.451564 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.056972 -1.291484 -0.547690 + 1 O 8.0000 0 15.999 -0.214872 1.104834 -0.787942 + 2 O 8.0000 0 15.999 1.292663 2.613293 0.475293 + 3 H 1.0000 0 1.008 -1.056173 -2.166156 0.853332 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.277170559599 0.00000000 0.00000000 + O 2 1 0 1.311662542217 120.91173569 0.00000000 + H 1 2 3 1.021506200395 119.22686187 87.69230781 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.413502583950 0.00000000 0.00000000 + O 2 1 0 2.478682984913 120.91173569 0.00000000 + H 1 2 3 1.930366962849 119.22686187 87.69230781 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.435346537875 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.830e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22295 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.5 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.4980781109387067 0.00e+00 5.59e-05 7.75e-04 8.97e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.4980815533363625 -3.44e-06 4.75e-05 4.71e-04 2.06e-04 0.0 + 3 -205.4980792682647461 2.29e-06 3.00e-05 3.57e-04 9.14e-04 0.0 + 4 -205.4980821974830860 -2.93e-06 9.66e-06 9.20e-05 3.42e-05 0.0 + 5 -205.4980822006457402 -3.16e-09 7.89e-06 7.25e-05 6.70e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49808220064574 Eh -5591.88710 eV + +Components: +Nuclear Repulsion : 69.43534653787493 Eh 1889.43184 eV +Electronic Energy : -274.93342873852066 Eh -7481.31894 eV +One Electron Energy: -418.54090543739818 Eh -11389.07705 eV +Two Electron Energy: 143.60747669887749 Eh 3907.75811 eV + +Virial components: +Potential Energy : -410.29665232881189 Eh -11164.73951 eV +Kinetic Energy : 204.79857012816615 Eh 5572.85241 eV +Virial Ratio : 2.00341561013850 + +DFT components: +N(Alpha) : 11.999997875764 electrons +N(Beta) : 11.999997875764 electrons +N(Total) : 23.999995751529 electrons +E(X) : -23.325878548615 Eh +E(C) : -0.805584933866 Eh +E(XC) : -24.131463482481 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.1627e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.2511e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 7.8886e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.6403e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 6.6984e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.0689e-04 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 3.1 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 39.0 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360839 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006624817 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.491818221837 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003211 -0.000006064 0.000001569 + 2 O : -0.000000156 0.000000858 -0.000000701 + 3 O : 0.000003574 0.000008133 0.000001032 + 4 H : -0.000000208 -0.000002927 -0.000001900 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000119585 +RMS gradient ... 0.0000034521 +MAX gradient ... 0.0000081331 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.037073239 0.004051628 0.015078228 + 2 O : -0.030100422 -0.000152038 0.018221042 + 3 O : 0.014271842 -0.000733504 -0.016290311 + 4 H : -0.021244659 -0.003166086 -0.017008959 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000802390 -0.0000650011 0.0000173109 + +Norm of the Cartesian gradient ... 0.0638476362 +RMS gradient ... 0.0184312250 +MAX gradient ... 0.0370732388 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.121 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.8%) +RI-J Coulomb gradient .... 0.059 sec ( 48.4%) +XC gradient .... 0.018 sec ( 14.6%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.491818222 Eh +Current gradient norm .... 0.063847636 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999882 +Lowest eigenvalues of augmented Hessian: + -0.000000049 0.075735228 0.234693464 0.418160333 0.462982195 +Length of the computed step .... 0.000486633 +The final length of the internal step .... 0.000486633 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0001986673 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001418087 RMS(Int)= 0.0001986640 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000025 +Previously predicted energy change .... -0.000002132 +Actually observed energy change .... -0.000002204 +Ratio of predicted to observed change .... 1.033552354 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000022036 0.0000050000 YES + RMS gradient 0.0000523059 0.0001000000 YES + MAX gradient 0.0000923441 0.0003000000 YES + RMS step 0.0001986673 0.0020000000 YES + MAX step 0.0003841503 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.02 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2772 -0.000036 0.0000 1.2772 + 2. B(O 2,O 1) 1.3117 -0.000073 0.0001 1.3118 + 3. B(H 3,N 0) 1.0215 0.000092 -0.0001 1.0214 + 4. A(O 1,N 0,H 3) 119.23 0.000034 -0.02 119.20 + 5. A(N 0,O 1,O 2) 120.91 -0.000011 0.00 120.91 + 6. D(O 2,O 1,N 0,H 3) 87.69 0.046129 -0.00 87.69 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (12.987 %) +Internal coordinates : 0.000 s ( 3.319 %) +B/P matrices and projection : 0.000 s (13.709 %) +Hessian update/contruction : 0.000 s (26.840 %) +Making the step : 0.000 s ( 5.195 %) +Converting the step to Cartesian: 0.000 s ( 4.040 %) +Storing new data : 0.000 s ( 3.463 %) +Checking convergence : 0.000 s ( 1.587 %) +Final printing : 0.000 s (28.571 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 7 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.030127 -0.683550 -0.289899 + O -0.113771 0.584582 -0.416929 + O 0.684060 1.382917 0.251565 + H -0.558870 -1.146105 0.451554 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.056932 -1.291722 -0.547829 + 1 O 8.0000 0 15.999 -0.214996 1.104699 -0.787881 + 2 O 8.0000 0 15.999 1.292687 2.613334 0.475390 + 3 H 1.0000 0 1.008 -1.056112 -2.165824 0.853314 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.277219785936 0.00000000 0.00000000 + O 2 1 0 1.311776592966 120.91357731 0.00000000 + H 1 2 3 1.021409920468 119.20485168 87.69230781 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.413595608245 0.00000000 0.00000000 + O 2 1 0 2.478898509593 120.91357731 0.00000000 + H 1 2 3 1.930185020154 119.20485168 87.69230781 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.431952796960 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.831e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22295 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.4319527970 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.4980824668514572 0.00e+00 6.92e-06 1.05e-04 1.31e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.4980825012461594 -3.44e-08 6.23e-06 8.01e-05 1.85e-05 0.0 + 3 -205.4980824939808883 7.27e-09 4.05e-06 3.36e-05 5.59e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 3 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49808249398089 Eh -5591.88711 eV + +Components: +Nuclear Repulsion : 69.43195279696013 Eh 1889.33949 eV +Electronic Energy : -274.93003529094102 Eh -7481.22660 eV +One Electron Energy: -418.53571246086756 Eh -11388.93574 eV +Two Electron Energy: 143.60567716992654 Eh 3907.70914 eV + +Virial components: +Potential Energy : -410.29690471899460 Eh -11164.74638 eV +Kinetic Energy : 204.79882222501368 Eh 5572.85927 eV +Virial Ratio : 2.00341437641765 + +DFT components: +N(Alpha) : 11.999997877299 electrons +N(Beta) : 11.999997877299 electrons +N(Total) : 23.999995754598 electrons +E(X) : -23.325948113587 Eh +E(C) : -0.805579158552 Eh +E(XC) : -24.131527272139 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -7.2653e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.3593e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.0457e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.5021e-05 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 5.5857e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.0133e-04 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.201123 -522.4891 + 1 2.0000 -19.045682 -518.2593 + 2 2.0000 -14.227513 -387.1503 + 3 2.0000 -1.248283 -33.9675 + 4 2.0000 -0.967428 -26.3250 + 5 2.0000 -0.710206 -19.3257 + 6 2.0000 -0.575342 -15.6559 + 7 2.0000 -0.521617 -14.1939 + 8 2.0000 -0.504837 -13.7373 + 9 2.0000 -0.325961 -8.8699 + 10 2.0000 -0.278554 -7.5798 + 11 2.0000 -0.230892 -6.2829 + 12 0.0000 -0.222248 -6.0477 + 13 0.0000 0.032881 0.8947 + 14 0.0000 0.110649 3.0109 + 15 0.0000 0.137850 3.7511 + 16 0.0000 0.243416 6.6237 + 17 0.0000 0.260648 7.0926 + 18 0.0000 0.318424 8.6648 + 19 0.0000 0.329538 8.9672 + 20 0.0000 0.352116 9.5816 + 21 0.0000 0.376883 10.2555 + 22 0.0000 0.394557 10.7364 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.396247 + 1 O : 0.196554 + 2 O : -0.104911 + 3 H : 0.304604 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.730922 s : 3.730922 + pz : 1.494965 p : 3.617057 + px : 1.317044 + py : 0.805048 + dz2 : 0.008123 d : 0.048268 + dxz : 0.002960 + dyz : 0.014838 + dx2y2 : 0.012078 + dxy : 0.010269 + + 1 O s : 3.758591 s : 3.758591 + pz : 1.461549 p : 3.916318 + px : 1.336654 + py : 1.118115 + dz2 : 0.019932 d : 0.128537 + dxz : 0.014423 + dyz : 0.036251 + dx2y2 : 0.034336 + dxy : 0.023594 + + 2 O s : 3.931328 s : 3.931328 + pz : 1.446741 p : 4.159262 + px : 1.199060 + py : 1.513462 + dz2 : 0.005552 d : 0.014321 + dxz : -0.000255 + dyz : 0.002925 + dx2y2 : 0.000510 + dxy : 0.005589 + + 3 H s : 0.660708 s : 0.660708 + pz : 0.015290 p : 0.034687 + px : 0.012419 + py : 0.006979 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.152758 + 1 O : -0.157742 + 2 O : 0.018620 + 3 H : 0.291880 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.243505 s : 3.243505 + pz : 1.415296 p : 3.607826 + px : 1.225746 + py : 0.966784 + dz2 : 0.033310 d : 0.301427 + dxz : 0.012302 + dyz : 0.098503 + dx2y2 : 0.081670 + dxy : 0.075641 + + 1 O s : 3.370768 s : 3.370768 + pz : 1.421402 p : 4.005665 + px : 1.281251 + py : 1.303012 + dz2 : 0.082250 d : 0.781309 + dxz : 0.068532 + dyz : 0.207728 + dx2y2 : 0.194790 + dxy : 0.228010 + + 2 O s : 3.616627 s : 3.616627 + pz : 1.393748 p : 4.120140 + px : 1.205378 + py : 1.521013 + dz2 : 0.036181 d : 0.244613 + dxz : 0.055637 + dyz : 0.043233 + dx2y2 : 0.056666 + dxy : 0.052896 + + 3 H s : 0.622885 s : 0.622885 + pz : 0.039556 p : 0.085236 + px : 0.029822 + py : 0.015858 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3962 7.0000 -0.3962 2.6925 2.6925 -0.0000 + 1 O 7.8034 8.0000 0.1966 2.6529 2.6529 -0.0000 + 2 O 8.1049 8.0000 -0.1049 1.6981 1.6981 0.0000 + 3 H 0.6954 1.0000 0.3046 0.8980 0.8980 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4345 B( 0-N , 2-O ) : 0.4533 B( 0-N , 3-H ) : 0.8047 +B( 1-O , 2-O ) : 1.1850 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 3 sec + +Total time .... 3.132 sec +Sum of individual times .... 3.119 sec ( 99.6%) + +SCF preparation .... 1.059 sec ( 33.8%) +Fock matrix formation .... 0.092 sec ( 2.9%) + Startup .... 0.006 sec ( 6.5% of F) + Split-RI-J .... 0.013 sec ( 13.9% of F) + XC integration .... 0.061 sec ( 66.8% of F) + Basis function eval. .... 0.003 sec ( 5.6% of XC) + Density eval. .... 0.005 sec ( 8.4% of XC) + XC-Functional eval. .... 0.003 sec ( 4.8% of XC) + XC-Potential eval. .... 0.005 sec ( 8.0% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.005 sec ( 0.2%) +Total Energy calculation .... 0.007 sec ( 0.2%) +Population analysis .... 1.921 sec ( 61.3%) +Orbital Transformation .... 0.007 sec ( 0.2%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.010 sec ( 0.3%) +SOSCF solution .... 0.018 sec ( 0.6%) +Finished LeanSCF after 5.1 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 39.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360838 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006625052 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.491818280347 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.030.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.030.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.327143 0.833993 -0.251268 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.4980824939808883 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.247295619 1.062245758 -0.221302024 +Nuclear contribution : -0.684538481 -1.479444017 0.549005330 + ----------------------------------------- +Total Dipole Moment : -0.437242862 -0.417198259 0.327703306 + ----------------------------------------- +Magnitude (a.u.) : 0.687477392 +Magnitude (Debye) : 1.747428659 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.222249 0.409297 0.374201 +Rotational constants in MHz : 96600.591461 12270.406063 11218.272679 + +Dipole components along the rotational axes: +x,y,z [a.u.] : 0.460924 0.124401 0.494670 +x,y,z [Debye]: 1.171575 0.316202 1.257352 + + + +Dipole moment calculation done in 0.7 sec + +Maximum memory used throughout the entire PROP-calculation: 20.6 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 31 * + * * + * Dihedral ( 2, 1, 0, 3) : 96.92307692 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2778 0.758483 + 2. B(O 2,O 1) 1.3135 0.668056 + 3. B(H 3,N 0) 1.0242 0.414946 + 4. A(O 1,N 0,H 3) 119.0237 0.366247 + 5. A(N 0,O 1,O 2) 120.7973 0.444271 + 6. D(O 2,O 1,N 0,H 3) 96.9231 0.045790 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.006954 -0.680290 -0.265103 + O -0.127750 0.585877 -0.387281 + O 0.699913 1.402481 0.223793 + H -0.583917 -1.170225 0.424882 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.013141 -1.285561 -0.500972 + 1 O 8.0000 0 15.999 -0.241412 1.107148 -0.731854 + 2 O 8.0000 0 15.999 1.322644 2.650305 0.422908 + 3 H 1.0000 0 1.008 -1.103444 -2.211404 0.802911 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.277219785936 0.00000000 0.00000000 + O 2 1 0 1.311776592966 120.91357731 0.00000000 + H 1 2 3 1.021409920468 119.20485168 87.69230781 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.413595608245 0.00000000 0.00000000 + O 2 1 0 2.478898509593 120.91357731 0.00000000 + H 1 2 3 1.930185020154 119.20485168 87.69230781 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1668 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.343378871338 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.872e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22308 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.3433788713 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.4871863921949000 0.00e+00 5.27e-04 4.50e-03 1.95e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.000) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.4882829560730499 -1.10e-03 8.15e-04 6.37e-03 1.55e-02 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.4895673797826419 -1.28e-03 7.51e-04 5.81e-03 1.11e-02 0.700 0.0 + 4 -205.4905980820356319 -1.03e-03 2.30e-03 1.80e-02 7.93e-03 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.4933302033730627 -2.73e-03 5.45e-04 4.59e-03 3.17e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -205.4936645120336891 -3.34e-04 1.30e-03 1.18e-02 4.57e-03 0.0 + 7 -205.4941119189824406 -4.47e-04 4.72e-03 3.42e-02 9.12e-03 0.1 + 8 -205.4952033909231943 -1.09e-03 1.05e-03 7.60e-03 9.50e-03 0.0 + 9 -205.4956166635834904 -4.13e-04 6.96e-04 5.50e-03 1.01e-03 0.0 + 10 -205.4956778388973646 -6.12e-05 5.67e-04 4.38e-03 8.87e-04 0.0 + 11 -205.4956699770714010 7.86e-06 2.34e-04 1.72e-03 1.72e-03 0.0 + 12 -205.4956980795796824 -2.81e-05 3.24e-05 2.61e-04 2.46e-04 0.0 + 13 -205.4956985310037965 -4.51e-07 1.29e-05 1.24e-04 6.95e-05 0.0 + 14 -205.4956985843866448 -5.34e-08 2.78e-06 3.35e-05 2.07e-05 0.0 + 15 -205.4956985895508126 -5.16e-09 1.32e-06 1.39e-05 8.11e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 15 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49569858955081 Eh -5591.82224 eV + +Components: +Nuclear Repulsion : 69.34337887133782 Eh 1886.92927 eV +Electronic Energy : -274.83907746088857 Eh -7478.75151 eV +One Electron Energy: -418.37440742299202 Eh -11384.54641 eV +Two Electron Energy: 143.53532996210342 Eh 3905.79490 eV + +Virial components: +Potential Energy : -410.24837889661478 Eh -11163.42593 eV +Kinetic Energy : 204.75268030706400 Eh 5571.60369 eV +Virial Ratio : 2.00362885741653 + +DFT components: +N(Alpha) : 11.999998832037 electrons +N(Beta) : 11.999998832037 electrons +N(Total) : 23.999997664075 electrons +E(X) : -23.319215884443 Eh +E(C) : -0.805498217127 Eh +E(XC) : -24.124714101570 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 5.1642e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.3892e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.3231e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.1715e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 8.1061e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.9630e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.202623 -522.5299 + 1 2.0000 -19.049008 -518.3499 + 2 2.0000 -14.222440 -387.0123 + 3 2.0000 -1.247037 -33.9336 + 4 2.0000 -0.967663 -26.3315 + 5 2.0000 -0.707325 -19.2473 + 6 2.0000 -0.573107 -15.5950 + 7 2.0000 -0.518615 -14.1122 + 8 2.0000 -0.509148 -13.8546 + 9 2.0000 -0.325725 -8.8634 + 10 2.0000 -0.279778 -7.6131 + 11 2.0000 -0.226963 -6.1760 + 12 0.0000 -0.222894 -6.0653 + 13 0.0000 0.029893 0.8134 + 14 0.0000 0.112490 3.0610 + 15 0.0000 0.138663 3.7732 + 16 0.0000 0.242819 6.6074 + 17 0.0000 0.261989 7.1291 + 18 0.0000 0.319823 8.7028 + 19 0.0000 0.330048 8.9811 + 20 0.0000 0.346496 9.4286 + 21 0.0000 0.380761 10.3610 + 22 0.0000 0.394098 10.7239 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.429882 + 1 O : 0.194400 + 2 O : -0.080672 + 3 H : 0.316154 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.729975 s : 3.729975 + pz : 1.283338 p : 3.654202 + px : 1.587555 + py : 0.783309 + dz2 : 0.005047 d : 0.045705 + dxz : 0.003890 + dyz : 0.014598 + dx2y2 : 0.012201 + dxy : 0.009969 + + 1 O s : 3.766335 s : 3.766335 + pz : 1.413939 p : 3.917293 + px : 1.372647 + py : 1.130706 + dz2 : 0.016275 d : 0.121972 + dxz : 0.014663 + dyz : 0.036741 + dx2y2 : 0.039444 + dxy : 0.014849 + + 2 O s : 3.927634 s : 3.927634 + pz : 1.346809 p : 4.136680 + px : 1.320059 + py : 1.469812 + dz2 : 0.004996 d : 0.016358 + dxz : 0.000193 + dyz : 0.004572 + dx2y2 : 0.001890 + dxy : 0.004707 + + 3 H s : 0.648831 s : 0.648831 + pz : 0.014378 p : 0.035015 + px : 0.013587 + py : 0.007050 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.168124 + 1 O : -0.162893 + 2 O : 0.031619 + 3 H : 0.299398 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.235331 s : 3.235331 + pz : 1.213861 p : 3.635305 + px : 1.472070 + py : 0.949375 + dz2 : 0.029765 d : 0.297487 + dxz : 0.013776 + dyz : 0.080722 + dx2y2 : 0.080332 + dxy : 0.092893 + + 1 O s : 3.371138 s : 3.371138 + pz : 1.349516 p : 4.000819 + px : 1.340574 + py : 1.310729 + dz2 : 0.066351 d : 0.790936 + dxz : 0.065720 + dyz : 0.206115 + dx2y2 : 0.202846 + dxy : 0.249904 + + 2 O s : 3.620079 s : 3.620079 + pz : 1.308068 p : 4.105324 + px : 1.310335 + py : 1.486921 + dz2 : 0.035236 d : 0.242978 + dxz : 0.052868 + dyz : 0.040697 + dx2y2 : 0.057547 + dxy : 0.056630 + + 3 H s : 0.615473 s : 0.615473 + pz : 0.035690 p : 0.085129 + px : 0.033528 + py : 0.015911 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.4299 7.0000 -0.4299 2.6140 2.6140 0.0000 + 1 O 7.8056 8.0000 0.1944 2.6838 2.6838 -0.0000 + 2 O 8.0807 8.0000 -0.0807 1.6856 1.6856 -0.0000 + 3 H 0.6838 1.0000 0.3162 0.8919 0.8919 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4358 B( 0-N , 2-O ) : 0.3955 B( 0-N , 3-H ) : 0.7827 +B( 1-O , 2-O ) : 1.2145 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 3 sec + +Total time .... 3.515 sec +Sum of individual times .... 3.493 sec ( 99.4%) + +SCF preparation .... 1.006 sec ( 28.6%) +Fock matrix formation .... 0.401 sec ( 11.4%) + Startup .... 0.016 sec ( 4.1% of F) + Split-RI-J .... 0.057 sec ( 14.3% of F) + XC integration .... 0.259 sec ( 64.6% of F) + Basis function eval. .... 0.017 sec ( 6.6% of XC) + Density eval. .... 0.021 sec ( 8.0% of XC) + XC-Functional eval. .... 0.013 sec ( 5.2% of XC) + XC-Potential eval. .... 0.023 sec ( 9.0% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.025 sec ( 0.7%) +Total Energy calculation .... 0.038 sec ( 1.1%) +Population analysis .... 1.878 sec ( 53.4%) +Orbital Transformation .... 0.014 sec ( 0.4%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.070 sec ( 2.0%) +SOSCF solution .... 0.061 sec ( 1.7%) +Finished LeanSCF after 5.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 39.7 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360374 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006627187 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.489431776801 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003324 -0.000006172 0.000001461 + 2 O : -0.000000179 0.000000862 -0.000000652 + 3 O : 0.000003739 0.000008447 0.000000889 + 4 H : -0.000000236 -0.000003137 -0.000001699 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000123035 +RMS gradient ... 0.0000035517 +MAX gradient ... 0.0000084466 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.019888709 -0.008019464 -0.016231245 + 2 O : 0.018972180 -0.002696435 -0.005148583 + 3 O : -0.005847799 0.011202858 0.008730261 + 4 H : 0.006764328 -0.000486959 0.012649567 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000071453 -0.0000082913 -0.0000049815 + +Norm of the Cartesian gradient ... 0.0394838091 +RMS gradient ... 0.0113979939 +MAX gradient ... 0.0198887086 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.154 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.008 sec ( 5.0%) +RI-J Coulomb gradient .... 0.058 sec ( 37.3%) +XC gradient .... 0.021 sec ( 13.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.489431777 Eh +Current gradient norm .... 0.039483809 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.998776486 +Lowest eigenvalues of augmented Hessian: + -0.001137941 0.365475938 0.410759814 0.444536817 0.663924529 +Length of the computed step .... 0.049512893 +The final length of the internal step .... 0.049512893 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0202135539 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0216943838 RMS(Int)= 0.0201878699 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0094987471 0.0001000000 NO + MAX gradient 0.0203991452 0.0003000000 NO + RMS step 0.0202135539 0.0020000000 NO + MAX step 0.0458677827 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0064 Max(Angles) 2.63 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2778 0.006847 -0.0048 1.2730 + 2. B(O 2,O 1) 1.3135 0.007342 -0.0058 1.3077 + 3. B(H 3,N 0) 1.0242 0.004943 -0.0064 1.0179 + 4. A(O 1,N 0,H 3) 119.02 -0.000143 0.02 119.05 + 5. A(N 0,O 1,O 2) 120.80 0.020399 -2.63 118.17 + 6. D(O 2,O 1,N 0,H 3) 96.92 -0.022808 0.00 96.92 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.014 %) +Internal coordinates : 0.000 s ( 3.239 %) +B/P matrices and projection : 0.000 s (12.958 %) +Hessian update/contruction : 0.000 s (26.056 %) +Making the step : 0.000 s ( 5.352 %) +Converting the step to Cartesian: 0.000 s ( 4.507 %) +Storing new data : 0.000 s ( 5.211 %) +Checking convergence : 0.000 s ( 0.141 %) +Final printing : 0.000 s (33.099 %) +Total time : 0.001 s + +Time for energy+gradient : 10.076 s +Time for complete geometry iter : 10.929 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.000711 -0.669401 -0.259600 + O -0.138340 0.588301 -0.400141 + O 0.694974 1.374725 0.230008 + H -0.574631 -1.155781 0.426025 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.001343 -1.264985 -0.490573 + 1 O 8.0000 0 15.999 -0.261425 1.111727 -0.756157 + 2 O 8.0000 0 15.999 1.313311 2.597854 0.434652 + 3 H 1.0000 0 1.008 -1.085895 -2.184110 0.805071 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.272991565358 0.00000000 0.00000000 + O 2 1 0 1.307656158235 118.16924885 0.00000000 + H 1 2 3 1.017856549842 119.04613716 96.92307672 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.405605429319 0.00000000 0.00000000 + O 2 1 0 2.471112016399 118.16924885 0.00000000 + H 1 2 3 1.923470122819 119.04613716 96.92307672 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1669 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.833173808082 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.853e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22307 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.4954264031732691 0.00e+00 2.32e-04 1.37e-03 9.23e-03 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.005) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.4956821492529571 -2.56e-04 2.72e-04 1.91e-03 6.43e-03 0.700 0.1 + ***Turning on AO-DIIS*** + 3 -205.4958850522553462 -2.03e-04 2.01e-04 1.47e-03 4.43e-03 0.700 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 4 -205.4960220111195213 -1.37e-04 4.99e-04 3.61e-03 3.12e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 5 -205.4963467427982096 -3.25e-04 1.20e-04 1.26e-03 5.02e-04 0.0 + 6 -205.4963301938533391 1.65e-05 8.25e-05 8.65e-04 2.43e-03 0.1 + 7 -205.4963508928699980 -2.07e-05 5.18e-05 4.81e-04 1.38e-04 0.0 + 8 -205.4963520072902270 -1.11e-06 1.41e-04 1.19e-03 1.09e-04 0.0 + 9 -205.4963528368440961 -8.30e-07 3.53e-05 3.11e-04 1.82e-04 0.0 + 10 -205.4963530008512862 -1.64e-07 3.65e-05 2.87e-04 1.40e-04 0.0 + 11 -205.4963532539632070 -2.53e-07 5.05e-06 5.14e-05 1.49e-05 0.0 + 12 -205.4963532621957256 -8.23e-09 3.27e-06 2.62e-05 7.85e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49635326219573 Eh -5591.84006 eV + +Components: +Nuclear Repulsion : 69.83317380808165 Eh 1900.25727 eV +Electronic Energy : -275.32952707027738 Eh -7492.09732 eV +One Electron Energy: -419.32951958475672 Eh -11410.53633 eV +Two Electron Energy: 143.99999251447935 Eh 3918.43901 eV + +Virial components: +Potential Energy : -410.29445061736942 Eh -11164.67960 eV +Kinetic Energy : 204.79809735517370 Eh 5572.83955 eV +Virial Ratio : 2.00340948434599 + +DFT components: +N(Alpha) : 11.999998752738 electrons +N(Beta) : 11.999998752738 electrons +N(Total) : 23.999997505475 electrons +E(X) : -23.330721797363 Eh +E(C) : -0.806165759487 Eh +E(XC) : -24.136887556850 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 8.2325e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.6212e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.2703e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.1248e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 7.8450e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 9.6139e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 3.6 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 39.8 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361042 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006725114 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.489989189535 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003264 -0.000005960 0.000001521 + 2 O : -0.000000189 0.000000864 -0.000000655 + 3 O : 0.000003556 0.000007975 0.000000874 + 4 H : -0.000000103 -0.000002879 -0.000001740 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000117486 +RMS gradient ... 0.0000033915 +MAX gradient ... 0.0000079749 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.020938749 -0.001785548 -0.011377220 + 2 O : 0.015558533 -0.001991904 -0.012023709 + 3 O : -0.006937570 0.001019906 0.011530956 + 4 H : 0.012317786 0.002757546 0.011869972 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000098854 -0.0000042173 0.0000103309 + +Norm of the Cartesian gradient ... 0.0380003540 +RMS gradient ... 0.0109697573 +MAX gradient ... 0.0209387491 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.131 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.9%) +RI-J Coulomb gradient .... 0.061 sec ( 46.8%) +XC gradient .... 0.019 sec ( 14.8%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.489989190 Eh +Current gradient norm .... 0.038000354 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999992348 +Lowest eigenvalues of augmented Hessian: + -0.000010564 0.365468234 0.411481869 0.456494690 0.647700320 +Length of the computed step .... 0.003912006 +The final length of the internal step .... 0.003912006 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0015970699 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0010024465 RMS(Int)= 0.0015971734 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000005282 +Previously predicted energy change .... -0.000570365 +Actually observed energy change .... -0.000557413 +Ratio of predicted to observed change .... 0.977290943 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0005574127 0.0000050000 NO + RMS gradient 0.0011133892 0.0001000000 NO + MAX gradient 0.0018387588 0.0003000000 NO + RMS step 0.0015970699 0.0020000000 YES + MAX step 0.0026224881 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0014 Max(Angles) 0.10 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2730 -0.001839 0.0012 1.2742 + 2. B(O 2,O 1) 1.3077 0.001749 -0.0014 1.3063 + 3. B(H 3,N 0) 1.0179 -0.000266 0.0003 1.0181 + 4. A(O 1,N 0,H 3) 119.05 0.000102 -0.02 119.03 + 5. A(N 0,O 1,O 2) 118.17 -0.000957 0.10 118.27 + 6. D(O 2,O 1,N 0,H 3) 96.92 -0.029134 -0.00 96.92 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 8.097 %) +Internal coordinates : 0.000 s ( 3.104 %) +B/P matrices and projection : 0.000 s (12.686 %) +Hessian update/contruction : 0.000 s (37.652 %) +Making the step : 0.000 s ( 5.803 %) +Converting the step to Cartesian: 0.000 s ( 4.049 %) +Storing new data : 0.000 s ( 3.104 %) +Checking convergence : 0.000 s ( 1.350 %) +Final printing : 0.000 s (24.022 %) +Total time : 0.001 s + +Time for energy+gradient : 8.206 s +Time for complete geometry iter : 9.139 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.000789 -0.670062 -0.259757 + O -0.137599 0.589043 -0.399401 + O 0.694729 1.375267 0.229423 + H -0.575048 -1.156404 0.426027 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.001492 -1.266234 -0.490870 + 1 O 8.0000 0 15.999 -0.260025 1.113130 -0.754758 + 2 O 8.0000 0 15.999 1.312847 2.598879 0.433546 + 3 H 1.0000 0 1.008 -1.086683 -2.185288 0.805075 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.274191049760 0.00000000 0.00000000 + O 2 1 0 1.306268397314 118.26746511 0.00000000 + H 1 2 3 1.018136581151 119.03098579 96.92307672 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.407872126339 0.00000000 0.00000000 + O 2 1 0 2.468489528319 118.26746511 0.00000000 + H 1 2 3 1.923999305302 119.03098579 96.92307672 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1669 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.830100080524 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.839e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22306 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.5 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.4963530537349357 0.00e+00 5.73e-05 5.90e-04 1.03e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.4963570688340724 -4.02e-06 6.41e-05 7.16e-04 3.36e-04 0.0 + 3 -205.4963501180843650 6.95e-06 4.82e-05 5.86e-04 1.44e-03 0.1 + 4 -205.4963578595545641 -7.74e-06 1.10e-05 1.70e-04 6.84e-05 0.1 + 5 -205.4963576819166633 1.78e-07 7.49e-06 1.16e-04 1.65e-04 0.0 + 6 -205.4963579076907649 -2.26e-07 1.68e-06 1.50e-05 4.71e-06 0.0 + 7 -205.4963579085621745 -8.71e-10 7.38e-07 7.26e-06 3.13e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49635790856217 Eh -5591.84018 eV + +Components: +Nuclear Repulsion : 69.83010008052351 Eh 1900.17363 eV +Electronic Energy : -275.32645798908567 Eh -7492.01381 eV +One Electron Energy: -419.32145023362739 Eh -11410.31675 eV +Two Electron Energy: 143.99499224454172 Eh 3918.30294 eV + +Virial components: +Potential Energy : -410.29316282399242 Eh -11164.64456 eV +Kinetic Energy : 204.79680491543024 Eh 5572.80438 eV +Virial Ratio : 2.00341583938978 + +DFT components: +N(Alpha) : 11.999998734866 electrons +N(Beta) : 11.999998734866 electrons +N(Total) : 23.999997469732 electrons +E(X) : -23.330540171106 Eh +E(C) : -0.806154562541 Eh +E(XC) : -24.136694733647 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 8.7141e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.2586e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 7.3752e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.3380e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.1297e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.2300e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 3.6 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 40.0 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361025 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006721443 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.489997490456 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003265 -0.000005965 0.000001521 + 2 O : -0.000000185 0.000000869 -0.000000653 + 3 O : 0.000003557 0.000007984 0.000000870 + 4 H : -0.000000106 -0.000002888 -0.000001738 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000117597 +RMS gradient ... 0.0000033947 +MAX gradient ... 0.0000079840 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.021052641 -0.002418310 -0.011530011 + 2 O : 0.016221279 -0.001178820 -0.011626045 + 3 O : -0.007364483 0.001052456 0.011189125 + 4 H : 0.012195845 0.002544674 0.011966931 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000046356 -0.0000089141 0.0000034594 + +Norm of the Cartesian gradient ... 0.0382184341 +RMS gradient ... 0.0110327116 +MAX gradient ... 0.0210526406 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.149 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.6%) +RI-J Coulomb gradient .... 0.064 sec ( 43.0%) +XC gradient .... 0.019 sec ( 13.0%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.489997490 Eh +Current gradient norm .... 0.038218434 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999972345 +Lowest eigenvalues of augmented Hessian: + -0.000012578 0.224068628 0.385167789 0.412402842 0.552902432 +Length of the computed step .... 0.007437213 +The final length of the internal step .... 0.007437213 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0030362293 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0013883095 RMS(Int)= 0.0030363575 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000006289 +Previously predicted energy change .... -0.000005282 +Actually observed energy change .... -0.000008301 +Ratio of predicted to observed change .... 1.571587519 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000083009 0.0000050000 NO + RMS gradient 0.0006949620 0.0001000000 NO + MAX gradient 0.0013271993 0.0003000000 NO + RMS step 0.0030362293 0.0020000000 NO + MAX step 0.0059361990 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0031 Max(Angles) 0.11 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2742 -0.001028 0.0021 1.2763 + 2. B(O 2,O 1) 1.3063 0.001327 -0.0031 1.3031 + 3. B(H 3,N 0) 1.0181 -0.000034 0.0001 1.0183 + 4. A(O 1,N 0,H 3) 119.03 0.000271 -0.11 118.93 + 5. A(N 0,O 1,O 2) 118.27 -0.000070 0.03 118.30 + 6. D(O 2,O 1,N 0,H 3) 96.92 -0.029063 -0.00 96.92 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 7.971 %) +Internal coordinates : 0.000 s ( 3.019 %) +B/P matrices and projection : 0.000 s (11.232 %) +Hessian update/contruction : 0.000 s (34.783 %) +Making the step : 0.000 s ( 5.072 %) +Converting the step to Cartesian: 0.000 s ( 3.986 %) +Storing new data : 0.000 s ( 3.019 %) +Checking convergence : 0.000 s ( 1.208 %) +Final printing : 0.000 s (29.348 %) +Total time : 0.001 s + +Time for energy+gradient : 8.286 s +Time for complete geometry iter : 9.096 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 4 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N -0.000336 -0.670917 -0.260047 + O -0.136925 0.590500 -0.398566 + O 0.693808 1.374417 0.228726 + H -0.575255 -1.156156 0.426180 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 -0.000635 -1.267849 -0.491418 + 1 O 8.0000 0 15.999 -0.258751 1.115883 -0.753181 + 2 O 8.0000 0 15.999 1.311108 2.597272 0.432229 + 3 H 1.0000 0 1.008 -1.087075 -2.184818 0.805363 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.276329337509 0.00000000 0.00000000 + O 2 1 0 1.303127096081 118.29891828 0.00000000 + H 1 2 3 1.018281332708 118.92581096 96.92307672 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.411912904582 0.00000000 0.00000000 + O 2 1 0 2.462553329286 118.29891828 0.00000000 + H 1 2 3 1.924272846103 118.92581096 96.92307672 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.855834413962 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.810e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22306 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.5 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.4963485766328972 0.00e+00 1.06e-04 1.44e-03 1.90e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.4963631380179550 -1.46e-05 1.04e-04 1.11e-03 5.45e-04 0.0 + 3 -205.4963471795326200 1.60e-05 7.41e-05 8.81e-04 2.25e-03 0.0 + 4 -205.4963654608782804 -1.83e-05 1.61e-05 1.80e-04 5.97e-05 0.0 + 5 -205.4963654183417248 4.25e-08 1.06e-05 1.06e-04 1.33e-04 0.0 + 6 -205.4963655920221868 -1.74e-07 1.17e-05 7.74e-05 2.57e-05 0.0 + 7 -205.4963656288989569 -3.69e-08 1.83e-05 1.46e-04 1.43e-05 0.0 + 8 -205.4963656532003711 -2.43e-08 2.96e-06 2.44e-05 1.40e-05 0.0 + 9 -205.4963656558861658 -2.69e-09 9.97e-07 1.23e-05 3.36e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49636565588617 Eh -5591.84039 eV + +Components: +Nuclear Repulsion : 69.85583441396216 Eh 1900.87389 eV +Electronic Energy : -275.35220006984832 Eh -7492.71429 eV +One Electron Energy: -419.36742464791371 Eh -11411.56778 eV +Two Electron Energy: 144.01522457806536 Eh 3918.85349 eV + +Virial components: +Potential Energy : -410.29397695865237 Eh -11164.66671 eV +Kinetic Energy : 204.79761130276617 Eh 5572.82632 eV +Virial Ratio : 2.00341192628505 + +DFT components: +N(Alpha) : 11.999998673895 electrons +N(Beta) : 11.999998673895 electrons +N(Total) : 23.999997347790 electrons +E(X) : -23.330999985871 Eh +E(C) : -0.806172175546 Eh +E(XC) : -24.137172161417 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.6858e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.2346e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 9.9679e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.3923e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.3627e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.3587e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 3.5 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 40.2 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361040 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006722029 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.490004667480 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003264 -0.000005961 0.000001524 + 2 O : -0.000000179 0.000000878 -0.000000649 + 3 O : 0.000003544 0.000007970 0.000000864 + 4 H : -0.000000101 -0.000002888 -0.000001739 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000117447 +RMS gradient ... 0.0000033904 +MAX gradient ... 0.0000079703 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.021497928 -0.003222609 -0.011617593 + 2 O : 0.017481862 0.000368909 -0.011280845 + 3 O : -0.008391054 0.000442356 0.010734252 + 4 H : 0.012407119 0.002411344 0.012164187 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000054886 -0.0000138490 0.0000025633 + +Norm of the Cartesian gradient ... 0.0391672300 +RMS gradient ... 0.0113066054 +MAX gradient ... 0.0214979276 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.123 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.9%) +RI-J Coulomb gradient .... 0.057 sec ( 46.6%) +XC gradient .... 0.019 sec ( 15.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.490004667 Eh +Current gradient norm .... 0.039167230 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999996693 +Lowest eigenvalues of augmented Hessian: + -0.000001456 0.165702969 0.412178066 0.426338978 0.579786251 +Length of the computed step .... 0.002571589 +The final length of the internal step .... 0.002571589 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0010498468 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0007492144 RMS(Int)= 0.0010498251 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000728 +Previously predicted energy change .... -0.000006289 +Actually observed energy change .... -0.000007177 +Ratio of predicted to observed change .... 1.141165311 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000071770 0.0000050000 NO + RMS gradient 0.0002714378 0.0001000000 NO + MAX gradient 0.0005382055 0.0003000000 NO + RMS step 0.0010498468 0.0020000000 YES + MAX step 0.0019296541 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0007 Max(Angles) 0.11 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2763 -0.000112 0.0005 1.2769 + 2. B(O 2,O 1) 1.3031 0.000084 -0.0007 1.3025 + 3. B(H 3,N 0) 1.0183 0.000044 0.0000 1.0183 + 4. A(O 1,N 0,H 3) 118.93 0.000538 -0.11 118.82 + 5. A(N 0,O 1,O 2) 118.30 0.000362 -0.03 118.27 + 6. D(O 2,O 1,N 0,H 3) 96.92 -0.029546 0.00 96.92 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 2.046 %) +Internal coordinates : 0.000 s ( 0.525 %) +B/P matrices and projection : 0.000 s ( 2.011 %) +Hessian update/contruction : 0.000 s ( 5.142 %) +Making the step : 0.000 s ( 0.927 %) +Converting the step to Cartesian: 0.000 s ( 0.857 %) +Storing new data : 0.000 s ( 0.595 %) +Checking convergence : 0.000 s ( 0.245 %) +Final printing : 0.005 s (87.618 %) +Total time : 0.006 s + +Time for energy+gradient : 7.909 s +Time for complete geometry iter : 8.783 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 5 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.000111 -0.671257 -0.260418 + O -0.137122 0.590689 -0.398425 + O 0.693468 1.373728 0.228784 + H -0.575165 -1.155315 0.426351 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.000211 -1.268493 -0.492118 + 1 O 8.0000 0 15.999 -0.259123 1.116240 -0.752915 + 2 O 8.0000 0 15.999 1.310465 2.595969 0.432339 + 3 H 1.0000 0 1.008 -1.086905 -2.183229 0.805687 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.276866298866 0.00000000 0.00000000 + O 2 1 0 1.302467283764 118.26726954 0.00000000 + H 1 2 3 1.018286038154 118.81524992 96.92307672 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.412927614490 0.00000000 0.00000000 + O 2 1 0 2.461306464706 118.26726954 0.00000000 + H 1 2 3 1.924281738107 118.81524992 96.92307672 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.863578148509 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.805e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22306 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.4963685981276171 0.00e+00 3.02e-05 3.86e-04 5.46e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.4963698773824490 -1.28e-06 2.26e-05 2.40e-04 1.04e-04 0.0 + 3 -205.4963695933883514 2.84e-07 1.70e-05 1.64e-04 3.67e-04 0.0 + 4 -205.4963701102317941 -5.17e-07 8.54e-06 7.91e-05 2.80e-05 0.0 + 5 -205.4963701461383039 -3.59e-08 1.85e-05 1.50e-04 1.79e-05 0.0 + 6 -205.4963701740971374 -2.80e-08 1.27e-05 9.41e-05 2.14e-05 0.0 + 7 -205.4963701726974818 1.40e-09 6.45e-06 4.98e-05 3.37e-05 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49637017269748 Eh -5591.84052 eV + +Components: +Nuclear Repulsion : 69.86357814850892 Eh 1901.08461 eV +Electronic Energy : -275.35994832120639 Eh -7492.92513 eV +One Electron Energy: -419.38158119538184 Eh -11411.95300 eV +Two Electron Energy: 144.02163287417542 Eh 3919.02787 eV + +Virial components: +Potential Energy : -410.29453621211587 Eh -11164.68193 eV +Kinetic Energy : 204.79816603941842 Eh 5572.84142 eV +Virial Ratio : 2.00340923039879 + +DFT components: +N(Alpha) : 11.999998650345 electrons +N(Beta) : 11.999998650345 electrons +N(Total) : 23.999997300690 electrons +E(X) : -23.331127387380 Eh +E(C) : -0.806171042312 Eh +E(XC) : -24.137298429691 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.3997e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.9789e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 6.4547e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.9498e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.3681e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.1274e-04 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 3.6 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 40.4 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361058 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006725389 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.490005840904 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003264 -0.000005955 0.000001526 + 2 O : -0.000000179 0.000000879 -0.000000647 + 3 O : 0.000003538 0.000007959 0.000000864 + 4 H : -0.000000095 -0.000002882 -0.000001742 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000117314 +RMS gradient ... 0.0000033866 +MAX gradient ... 0.0000079589 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.021706384 -0.003388855 -0.011665929 + 2 O : 0.017752857 0.000653624 -0.011410944 + 3 O : -0.008638281 0.000247160 0.010796407 + 4 H : 0.012591809 0.002488070 0.012280466 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000101972 -0.0000288865 0.0000141881 + +Norm of the Cartesian gradient ... 0.0396401760 +RMS gradient ... 0.0114431331 +MAX gradient ... 0.0217063842 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.136 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.8%) +RI-J Coulomb gradient .... 0.063 sec ( 46.3%) +XC gradient .... 0.019 sec ( 14.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.490005841 Eh +Current gradient norm .... 0.039640176 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999977710 +Lowest eigenvalues of augmented Hessian: + -0.000003138 0.063400540 0.408307934 0.430186647 0.539095547 +Length of the computed step .... 0.006676936 +The final length of the internal step .... 0.006676936 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0027258479 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0021144457 RMS(Int)= 0.0027259873 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000001569 +Previously predicted energy change .... -0.000000728 +Actually observed energy change .... -0.000001173 +Ratio of predicted to observed change .... 1.611748638 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000011734 0.0000050000 YES + RMS gradient 0.0002354003 0.0001000000 NO + MAX gradient 0.0005100654 0.0003000000 NO + RMS step 0.0027258479 0.0020000000 NO + MAX step 0.0060018365 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0010 Max(Angles) 0.34 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2769 -0.000024 0.0010 1.2779 + 2. B(O 2,O 1) 1.3025 -0.000160 -0.0009 1.3016 + 3. B(H 3,N 0) 1.0183 -0.000015 0.0002 1.0184 + 4. A(O 1,N 0,H 3) 118.82 0.000510 -0.34 118.47 + 5. A(N 0,O 1,O 2) 118.27 0.000215 -0.08 118.19 + 6. D(O 2,O 1,N 0,H 3) 96.92 -0.029957 -0.00 96.92 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.271 %) +Internal coordinates : 0.000 s ( 2.709 %) +B/P matrices and projection : 0.000 s (10.497 %) +Hessian update/contruction : 0.000 s (29.571 %) +Making the step : 0.000 s ( 6.095 %) +Converting the step to Cartesian: 0.000 s ( 3.386 %) +Storing new data : 0.000 s ( 2.709 %) +Checking convergence : 0.000 s ( 1.242 %) +Final printing : 0.000 s (33.409 %) +Total time : 0.001 s + +Time for energy+gradient : 8.104 s +Time for complete geometry iter : 8.894 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 6 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.001392 -0.672269 -0.261714 + O -0.137909 0.590693 -0.398060 + O 0.692758 1.372176 0.229174 + H -0.574949 -1.152755 0.426892 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.002630 -1.270405 -0.494568 + 1 O 8.0000 0 15.999 -0.260610 1.116248 -0.752224 + 2 O 8.0000 0 15.999 1.309123 2.593036 0.433077 + 3 H 1.0000 0 1.008 -1.086496 -2.178392 0.806708 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.277915568517 0.00000000 0.00000000 + O 2 1 0 1.301593235082 118.19000610 0.00000000 + H 1 2 3 1.018436832898 118.47137002 96.92307672 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.414910446771 0.00000000 0.00000000 + O 2 1 0 2.459654752069 118.19000610 0.00000000 + H 1 2 3 1.924566698875 118.47137002 96.92307672 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.870709753692 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.799e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22307 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.4963731628892560 0.00e+00 6.81e-05 6.78e-04 1.32e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.4963798646421083 -6.70e-06 4.85e-05 4.73e-04 1.75e-04 0.0 + 3 -205.4963801587261401 -2.94e-07 7.63e-05 6.45e-04 5.08e-04 0.0 + 4 -205.4963811514639360 -9.93e-07 2.51e-05 2.12e-04 2.08e-04 0.0 + 5 -205.4963817715146206 -6.20e-07 2.40e-05 1.66e-04 4.19e-05 0.0 + 6 -205.4963819200160628 -1.49e-07 3.63e-05 2.57e-04 3.10e-05 0.1 + 7 -205.4963819642842964 -4.43e-08 9.67e-06 8.56e-05 7.16e-05 0.0 + 8 -205.4963819889059096 -2.46e-08 1.02e-05 7.78e-05 2.97e-05 0.0 + 9 -205.4963820036724087 -1.48e-08 1.46e-06 1.80e-05 4.30e-06 0.0 + 10 -205.4963820044789031 -8.06e-10 9.44e-07 7.03e-06 2.29e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 10 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49638200447890 Eh -5591.84084 eV + +Components: +Nuclear Repulsion : 69.87070975369221 Eh 1901.27867 eV +Electronic Energy : -275.36709175817111 Eh -7493.11951 eV +One Electron Energy: -419.39315449272652 Eh -11412.26792 eV +Two Electron Energy: 144.02606273455541 Eh 3919.14841 eV + +Virial components: +Potential Energy : -410.29535496912092 Eh -11164.70421 eV +Kinetic Energy : 204.79897296464199 Eh 5572.86337 eV +Virial Ratio : 2.00340533465447 + +DFT components: +N(Alpha) : 11.999998600244 electrons +N(Beta) : 11.999998600244 electrons +N(Total) : 23.999997200488 electrons +E(X) : -23.331111403075 Eh +E(C) : -0.806146732995 Eh +E(XC) : -24.137258136070 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 8.0649e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.0347e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 9.4405e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.2830e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.2870e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.7584e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 3.5 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 40.6 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361101 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006735232 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.490007874056 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003263 -0.000005941 0.000001530 + 2 O : -0.000000180 0.000000876 -0.000000644 + 3 O : 0.000003524 0.000007933 0.000000866 + 4 H : -0.000000081 -0.000002868 -0.000001753 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000117008 +RMS gradient ... 0.0000033777 +MAX gradient ... 0.0000079329 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.022237350 -0.003605357 -0.011991121 + 2 O : 0.018257314 0.000934171 -0.011870675 + 3 O : -0.009057777 -0.000042058 0.011160774 + 4 H : 0.013037812 0.002713245 0.012701022 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000044808 -0.0000139851 0.0000025535 + +Norm of the Cartesian gradient ... 0.0408860686 +RMS gradient ... 0.0118027914 +MAX gradient ... 0.0222373500 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.132 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.7%) +RI-J Coulomb gradient .... 0.058 sec ( 44.2%) +XC gradient .... 0.019 sec ( 14.7%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.490007874 Eh +Current gradient norm .... 0.040886069 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999992172 +Lowest eigenvalues of augmented Hessian: + -0.000001140 0.044889929 0.381754066 0.414827803 0.561044057 +Length of the computed step .... 0.003956741 +The final length of the internal step .... 0.003956741 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0016153327 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0012261599 RMS(Int)= 0.0016154624 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000570 +Previously predicted energy change .... -0.000001569 +Actually observed energy change .... -0.000002033 +Ratio of predicted to observed change .... 1.295694575 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000020332 0.0000050000 YES + RMS gradient 0.0002181627 0.0001000000 NO + MAX gradient 0.0004275973 0.0003000000 NO + RMS step 0.0016153327 0.0020000000 YES + MAX step 0.0038094418 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0005 Max(Angles) 0.22 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2779 -0.000045 0.0005 1.2784 + 2. B(O 2,O 1) 1.3016 -0.000428 0.0001 1.3017 + 3. B(H 3,N 0) 1.0184 -0.000071 0.0001 1.0186 + 4. A(O 1,N 0,H 3) 118.47 0.000284 -0.22 118.25 + 5. A(N 0,O 1,O 2) 118.19 -0.000123 -0.02 118.17 + 6. D(O 2,O 1,N 0,H 3) 96.92 -0.031138 -0.00 96.92 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (12.794 %) +Internal coordinates : 0.000 s ( 3.133 %) +B/P matrices and projection : 0.000 s (15.535 %) +Hessian update/contruction : 0.000 s (28.068 %) +Making the step : 0.000 s ( 5.614 %) +Converting the step to Cartesian: 0.000 s ( 3.916 %) +Storing new data : 0.000 s ( 3.264 %) +Checking convergence : 0.000 s ( 1.436 %) +Final printing : 0.000 s (25.979 %) +Total time : 0.001 s + +Time for energy+gradient : 7.938 s +Time for complete geometry iter : 8.728 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 7 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.002102 -0.673008 -0.262616 + O -0.138439 0.590439 -0.397802 + O 0.692521 1.371666 0.229492 + H -0.574891 -1.151253 0.427218 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.003971 -1.271801 -0.496273 + 1 O 8.0000 0 15.999 -0.261613 1.115768 -0.751737 + 2 O 8.0000 0 15.999 1.308675 2.592073 0.433678 + 3 H 1.0000 0 1.008 -1.086386 -2.175553 0.807325 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.278407854175 0.00000000 0.00000000 + O 2 1 0 1.301656240275 118.16510913 0.00000000 + H 1 2 3 1.018582261090 118.25310508 96.92307672 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.415840731844 0.00000000 0.00000000 + O 2 1 0 2.459773814630 118.16510913 0.00000000 + H 1 2 3 1.924841518331 118.25310508 96.92307672 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.861671496625 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.800e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22306 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.4963853312521564 0.00e+00 3.55e-05 3.27e-04 8.30e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.4963872995543852 -1.97e-06 2.67e-05 2.06e-04 7.46e-05 0.0 + 3 -205.4963876746305118 -3.75e-07 6.04e-05 4.79e-04 8.51e-05 0.0 + 4 -205.4963872941152658 3.81e-07 2.24e-05 1.69e-04 3.14e-04 0.0 + 5 -205.4963879227168491 -6.29e-07 1.44e-05 1.82e-04 7.61e-05 0.0 + 6 -205.4963878001867101 1.23e-07 1.25e-05 1.41e-04 1.67e-04 0.0 + 7 -205.4963880193464547 -2.19e-07 7.25e-06 5.36e-05 1.24e-05 0.0 + 8 -205.4963880324358456 -1.31e-08 1.11e-05 7.02e-05 7.96e-06 0.0 + 9 -205.4963880400570702 -7.62e-09 1.07e-06 1.13e-05 5.09e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49638804005707 Eh -5591.84100 eV + +Components: +Nuclear Repulsion : 69.86167149662533 Eh 1901.03273 eV +Electronic Energy : -275.35805953668239 Eh -7492.87373 eV +One Electron Energy: -419.37532335135126 Eh -11411.78271 eV +Two Electron Energy: 144.01726381466887 Eh 3918.90898 eV + +Virial components: +Potential Energy : -410.29474247358905 Eh -11164.68754 eV +Kinetic Energy : 204.79835443353198 Eh 5572.84654 eV +Virial Ratio : 2.00340839460579 + +DFT components: +N(Alpha) : 11.999998580393 electrons +N(Beta) : 11.999998580393 electrons +N(Total) : 23.999997160786 electrons +E(X) : -23.330854090710 Eh +E(C) : -0.806112801746 Eh +E(XC) : -24.136966892456 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 7.6212e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.1303e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.0722e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 4.5415e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 5.0886e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.3835e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 3.5 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 40.7 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361118 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006740535 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.490008623694 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003263 -0.000005936 0.000001532 + 2 O : -0.000000182 0.000000873 -0.000000643 + 3 O : 0.000003519 0.000007924 0.000000869 + 4 H : -0.000000073 -0.000002862 -0.000001759 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000116902 +RMS gradient ... 0.0000033747 +MAX gradient ... 0.0000079243 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.022536082 -0.003801723 -0.012238727 + 2 O : 0.018398782 0.000896600 -0.012213207 + 3 O : -0.009116135 0.000053073 0.011495393 + 4 H : 0.013253435 0.002852050 0.012956542 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000091442 -0.0000150808 -0.0000055948 + +Norm of the Cartesian gradient ... 0.0415632833 +RMS gradient ... 0.0119982864 +MAX gradient ... 0.0225360815 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.135 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.0%) +RI-J Coulomb gradient .... 0.065 sec ( 48.3%) +XC gradient .... 0.021 sec ( 15.6%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.490008624 Eh +Current gradient norm .... 0.041563283 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999998827 +Lowest eigenvalues of augmented Hessian: + -0.000000292 0.042889046 0.304921172 0.413751852 0.537151427 +Length of the computed step .... 0.001531961 +The final length of the internal step .... 0.001531961 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0006254204 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0004414534 RMS(Int)= 0.0006254474 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000146 +Previously predicted energy change .... -0.000000570 +Actually observed energy change .... -0.000000750 +Ratio of predicted to observed change .... 1.314910291 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000007496 0.0000050000 YES + RMS gradient 0.0001232123 0.0001000000 NO + MAX gradient 0.0002486700 0.0003000000 YES + RMS step 0.0006254204 0.0020000000 YES + MAX step 0.0014010321 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0003 Max(Angles) 0.08 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2784 -0.000005 0.0001 1.2785 + 2. B(O 2,O 1) 1.3017 -0.000249 0.0003 1.3019 + 3. B(H 3,N 0) 1.0186 -0.000072 0.0001 1.0187 + 4. A(O 1,N 0,H 3) 118.25 0.000096 -0.08 118.17 + 5. A(N 0,O 1,O 2) 118.17 -0.000122 0.00 118.17 + 6. D(O 2,O 1,N 0,H 3) 96.92 -0.031802 -0.00 96.92 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (11.656 %) +Internal coordinates : 0.000 s ( 4.294 %) +B/P matrices and projection : 0.000 s (11.411 %) +Hessian update/contruction : 0.000 s (30.798 %) +Making the step : 0.000 s ( 4.663 %) +Converting the step to Cartesian: 0.000 s ( 3.926 %) +Storing new data : 0.000 s ( 3.190 %) +Checking convergence : 0.000 s ( 1.350 %) +Final printing : 0.000 s (27.853 %) +Total time : 0.001 s + +Time for energy+gradient : 8.142 s +Time for complete geometry iter : 8.972 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 8 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.002329 -0.673301 -0.262999 + O -0.138646 0.590231 -0.397700 + O 0.692525 1.371682 0.229641 + H -0.574916 -1.150768 0.427349 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.004401 -1.272354 -0.496996 + 1 O 8.0000 0 15.999 -0.262002 1.115374 -0.751544 + 2 O 8.0000 0 15.999 1.308683 2.592103 0.433959 + 3 H 1.0000 0 1.008 -1.086435 -2.174637 0.807573 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.278487161658 0.00000000 0.00000000 + O 2 1 0 1.301947811327 118.16637374 0.00000000 + H 1 2 3 1.018709126997 118.17283185 96.92307672 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.415990601268 0.00000000 0.00000000 + O 2 1 0 2.460324804066 118.16637374 0.00000000 + H 1 2 3 1.925081260151 118.17283185 96.92307672 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.852844946229 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.803e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.001 sec +Total time needed ... 0.004 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22305 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.4963893754811295 0.00e+00 1.42e-05 1.23e-04 3.47e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.4963896996106030 -3.24e-07 1.11e-05 8.33e-05 3.55e-05 0.1 + 3 -205.4963897473318468 -4.77e-08 1.89e-05 1.75e-04 6.33e-05 0.0 + 4 -205.4963897112777715 3.61e-08 7.87e-06 7.89e-05 1.24e-04 0.0 + 5 -205.4963897806150328 -6.93e-08 6.56e-06 7.77e-05 4.07e-05 0.0 + 6 -205.4963897648165982 1.58e-08 5.47e-06 5.61e-05 6.31e-05 0.0 + 7 -205.4963897972686198 -3.25e-08 2.50e-06 1.85e-05 5.12e-06 0.0 + 8 -205.4963897992957129 -2.03e-09 5.01e-06 3.43e-05 3.60e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49638979929571 Eh -5591.84105 eV + +Components: +Nuclear Repulsion : 69.85284494622894 Eh 1900.79255 eV +Electronic Energy : -275.34923474552465 Eh -7492.63360 eV +One Electron Energy: -419.35803812692347 Eh -11411.31236 eV +Two Electron Energy: 144.00880338139882 Eh 3918.67876 eV + +Virial components: +Potential Energy : -410.29424040459651 Eh -11164.67388 eV +Kinetic Energy : 204.79785060530077 Eh 5572.83283 eV +Virial Ratio : 2.00341087170559 + +DFT components: +N(Alpha) : 11.999998578596 electrons +N(Beta) : 11.999998578596 electrons +N(Total) : 23.999997157192 electrons +E(X) : -23.330578717539 Eh +E(C) : -0.806092165128 Eh +E(XC) : -24.136670882667 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.0271e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.4328e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 5.0064e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.7105e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.6039e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.7029e-04 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 3.5 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 40.9 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361121 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006742137 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.490008782603 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003264 -0.000005935 0.000001532 + 2 O : -0.000000183 0.000000872 -0.000000642 + 3 O : 0.000003519 0.000007924 0.000000871 + 4 H : -0.000000072 -0.000002861 -0.000001761 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000116902 +RMS gradient ... 0.0000033747 +MAX gradient ... 0.0000079244 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.022598452 -0.003853333 -0.012382889 + 2 O : 0.018374849 0.000768749 -0.012345787 + 3 O : -0.009052322 0.000203162 0.011652805 + 4 H : 0.013275925 0.002881422 0.013075871 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000027810 -0.0000090969 0.0000038368 + +Norm of the Cartesian gradient ... 0.0417471375 +RMS gradient ... 0.0120513605 +MAX gradient ... 0.0225984516 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.112 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.1%) +RI-J Coulomb gradient .... 0.054 sec ( 47.8%) +XC gradient .... 0.016 sec ( 13.8%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.490008783 Eh +Current gradient norm .... 0.041747138 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999972 +Lowest eigenvalues of augmented Hessian: + -0.000000009 0.047589662 0.263778277 0.413095867 0.520868828 +Length of the computed step .... 0.000238011 +The final length of the internal step .... 0.000238011 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0000971674 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0000672870 RMS(Int)= 0.0000971681 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000005 +Previously predicted energy change .... -0.000000146 +Actually observed energy change .... -0.000000159 +Ratio of predicted to observed change .... 1.087207487 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000001589 0.0000050000 YES + RMS gradient 0.0000212186 0.0001000000 YES + MAX gradient 0.0000421774 0.0003000000 YES + RMS step 0.0000971674 0.0020000000 YES + MAX step 0.0001602346 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2785 0.000005 -0.0001 1.2784 + 2. B(O 2,O 1) 1.3019 -0.000042 0.0001 1.3020 + 3. B(H 3,N 0) 1.0187 -0.000012 0.0000 1.0187 + 4. A(O 1,N 0,H 3) 118.17 0.000000 0.01 118.18 + 5. A(N 0,O 1,O 2) 118.17 -0.000027 0.00 118.17 + 6. D(O 2,O 1,N 0,H 3) 96.92 -0.032002 -0.00 96.92 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (13.903 %) +Internal coordinates : 0.000 s ( 2.781 %) +B/P matrices and projection : 0.000 s (14.499 %) +Hessian update/contruction : 0.000 s (33.366 %) +Making the step : 0.000 s ( 5.263 %) +Converting the step to Cartesian: 0.000 s ( 3.078 %) +Storing new data : 0.000 s ( 2.781 %) +Checking convergence : 0.000 s ( 0.993 %) +Final printing : 0.000 s (23.039 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 8 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.002293 -0.673281 -0.262980 + O -0.138634 0.590201 -0.397709 + O 0.692562 1.371759 0.229642 + H -0.574929 -1.150836 0.427339 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.004333 -1.272316 -0.496961 + 1 O 8.0000 0 15.999 -0.261981 1.115319 -0.751561 + 2 O 8.0000 0 15.999 1.308753 2.592249 0.433960 + 3 H 1.0000 0 1.008 -1.086459 -2.174764 0.807554 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.278436398342 0.00000000 0.00000000 + O 2 1 0 1.302032603847 118.17001975 0.00000000 + H 1 2 3 1.018717412589 118.18040640 96.92307672 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.415894672502 0.00000000 0.00000000 + O 2 1 0 2.460485038707 118.17001975 0.00000000 + H 1 2 3 1.925096917650 118.18040640 96.92307672 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.851486708610 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.804e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22305 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.8514867086 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.4963895046378184 0.00e+00 3.05e-06 4.06e-05 7.25e-06 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.4963895180945883 -1.35e-08 2.35e-06 2.72e-05 1.08e-05 0.0 + 3 -205.4963895140539307 4.04e-09 1.59e-06 1.70e-05 3.97e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 3 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.49638951405393 Eh -5591.84104 eV + +Components: +Nuclear Repulsion : 69.85148670861015 Eh 1900.75559 eV +Electronic Energy : -275.34787622266401 Eh -7492.59663 eV +One Electron Energy: -419.35571226446996 Eh -11411.24907 eV +Two Electron Energy: 144.00783604180592 Eh 3918.65244 eV + +Virial components: +Potential Energy : -410.29412629181274 Eh -11164.67078 eV +Kinetic Energy : 204.79773677775879 Eh 5572.82973 eV +Virial Ratio : 2.00341142801326 + +DFT components: +N(Alpha) : 11.999998581185 electrons +N(Beta) : 11.999998581185 electrons +N(Total) : 23.999997162369 electrons +E(X) : -23.330576463106 Eh +E(C) : -0.806091008312 Eh +E(XC) : -24.136667471418 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -4.0407e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.7005e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.5941e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.5707e-05 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.9672e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.9569e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.204468 -522.5801 + 1 2.0000 -19.049190 -518.3548 + 2 2.0000 -14.219546 -386.9335 + 3 2.0000 -1.255306 -34.1586 + 4 2.0000 -0.967122 -26.3167 + 5 2.0000 -0.708066 -19.2675 + 6 2.0000 -0.574266 -15.6266 + 7 2.0000 -0.521410 -14.1883 + 8 2.0000 -0.512741 -13.9524 + 9 2.0000 -0.325368 -8.8537 + 10 2.0000 -0.279493 -7.6054 + 11 2.0000 -0.226839 -6.1726 + 12 0.0000 -0.222457 -6.0534 + 13 0.0000 0.042433 1.1547 + 14 0.0000 0.115153 3.1335 + 15 0.0000 0.138117 3.7584 + 16 0.0000 0.243737 6.6324 + 17 0.0000 0.261969 7.1285 + 18 0.0000 0.319995 8.7075 + 19 0.0000 0.328931 8.9507 + 20 0.0000 0.349543 9.5115 + 21 0.0000 0.381628 10.3846 + 22 0.0000 0.390426 10.6240 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.432150 + 1 O : 0.193325 + 2 O : -0.071748 + 3 H : 0.310573 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.736829 s : 3.736829 + pz : 1.260388 p : 3.650469 + px : 1.606388 + py : 0.783694 + dz2 : 0.004918 d : 0.044852 + dxz : 0.004259 + dyz : 0.013778 + dx2y2 : 0.011453 + dxy : 0.010443 + + 1 O s : 3.771052 s : 3.771052 + pz : 1.407094 p : 3.911724 + px : 1.369560 + py : 1.135070 + dz2 : 0.016785 d : 0.123898 + dxz : 0.015046 + dyz : 0.037055 + dx2y2 : 0.039517 + dxy : 0.015494 + + 2 O s : 3.924780 s : 3.924780 + pz : 1.320694 p : 4.129471 + px : 1.306547 + py : 1.502230 + dz2 : 0.005130 d : 0.017498 + dxz : 0.000514 + dyz : 0.004900 + dx2y2 : 0.002348 + dxy : 0.004605 + + 3 H s : 0.654054 s : 0.654054 + pz : 0.014616 p : 0.035372 + px : 0.013716 + py : 0.007040 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.171432 + 1 O : -0.156946 + 2 O : 0.033460 + 3 H : 0.294918 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.237218 s : 3.237218 + pz : 1.193990 p : 3.634158 + px : 1.490895 + py : 0.949272 + dz2 : 0.029705 d : 0.300056 + dxz : 0.014994 + dyz : 0.079749 + dx2y2 : 0.079095 + dxy : 0.096513 + + 1 O s : 3.369209 s : 3.369209 + pz : 1.343761 p : 3.999894 + px : 1.344803 + py : 1.311330 + dz2 : 0.066028 d : 0.787843 + dxz : 0.068934 + dyz : 0.203611 + dx2y2 : 0.201403 + dxy : 0.247868 + + 2 O s : 3.611523 s : 3.611523 + pz : 1.289681 p : 4.104720 + px : 1.302190 + py : 1.512848 + dz2 : 0.037989 d : 0.250297 + dxz : 0.055711 + dyz : 0.040837 + dx2y2 : 0.059903 + dxy : 0.055857 + + 3 H s : 0.618769 s : 0.618769 + pz : 0.036195 p : 0.086313 + px : 0.034228 + py : 0.015890 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.4322 7.0000 -0.4322 2.5892 2.5892 -0.0000 + 1 O 7.8067 8.0000 0.1933 2.6853 2.6853 -0.0000 + 2 O 8.0717 8.0000 -0.0717 1.6723 1.6723 -0.0000 + 3 H 0.6894 1.0000 0.3106 0.8949 0.8949 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.4279 B( 0-N , 2-O ) : 0.3725 B( 0-N , 3-H ) : 0.7888 +B( 1-O , 2-O ) : 1.2256 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 3 sec + +Total time .... 3.302 sec +Sum of individual times .... 3.285 sec ( 99.5%) + +SCF preparation .... 1.095 sec ( 33.2%) +Fock matrix formation .... 0.087 sec ( 2.6%) + Startup .... 0.006 sec ( 6.7% of F) + Split-RI-J .... 0.012 sec ( 14.3% of F) + XC integration .... 0.057 sec ( 66.0% of F) + Basis function eval. .... 0.003 sec ( 5.9% of XC) + Density eval. .... 0.005 sec ( 9.3% of XC) + XC-Functional eval. .... 0.003 sec ( 5.1% of XC) + XC-Potential eval. .... 0.005 sec ( 8.4% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.005 sec ( 0.2%) +Total Energy calculation .... 0.006 sec ( 0.2%) +Population analysis .... 2.058 sec ( 62.3%) +Orbital Transformation .... 0.006 sec ( 0.2%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.010 sec ( 0.3%) +SOSCF solution .... 0.018 sec ( 0.5%) +Finished LeanSCF after 5.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 41.2 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000361119 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006741852 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.490008780847 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.031.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.031.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.334224 0.836022 -0.238832 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.4963895140539307 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.123159559 1.108180167 -0.284386154 +Nuclear contribution : -0.703314770 -1.484952838 0.519990727 + ----------------------------------------- +Total Dipole Moment : -0.580155211 -0.376772671 0.235604573 + ----------------------------------------- +Magnitude (a.u.) : 0.730785351 +Magnitude (Debye) : 1.857508744 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.085417 0.421221 0.382439 +Rotational constants in MHz : 92498.465886 12627.884683 11465.242081 + +Dipole components along the rotational axes: +x,y,z [a.u.] : 0.495807 -0.099552 -0.527553 +x,y,z [Debye]: 1.260240 -0.253040 -1.340934 + + + +Dipole moment calculation done in 0.7 sec + +Maximum memory used throughout the entire PROP-calculation: 21.6 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 32 * + * * + * Dihedral ( 2, 1, 0, 3) : 106.15384615 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2789 0.755101 + 2. B(O 2,O 1) 1.3039 0.692403 + 3. B(H 3,N 0) 1.0218 0.419070 + 4. A(O 1,N 0,H 3) 118.0022 0.366587 + 5. A(N 0,O 1,O 2) 118.0714 0.446799 + 6. D(O 2,O 1,N 0,H 3) 106.1538 0.045333 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.023491 -0.669111 -0.234341 + O -0.150754 0.590914 -0.366638 + O 0.708119 1.391915 0.199822 + H -0.599564 -1.175875 0.397449 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.044391 -1.264436 -0.442839 + 1 O 8.0000 0 15.999 -0.284883 1.116667 -0.692845 + 2 O 8.0000 0 15.999 1.338151 2.630339 0.377608 + 3 H 1.0000 0 1.008 -1.133012 -2.222082 0.751069 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.278436398342 0.00000000 0.00000000 + O 2 1 0 1.302032603847 118.17001975 0.00000000 + H 1 2 3 1.018717412589 118.18040640 96.92307672 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.415894672502 0.00000000 0.00000000 + O 2 1 0 2.460485038707 118.17001975 0.00000000 + H 1 2 3 1.925096917650 118.18040640 96.92307672 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1668 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.758717987808 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.851e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.003 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.7587179878 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.5 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.4978528037719343 0.00e+00 4.88e-04 4.13e-03 2.15e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.012) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.4990264721529911 -1.17e-03 7.85e-04 5.71e-03 1.70e-02 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.5003568144386463 -1.33e-03 7.16e-04 5.62e-03 1.22e-02 0.700 0.0 + 4 -205.5013939705697794 -1.04e-03 2.14e-03 1.67e-02 8.78e-03 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5040083870720764 -2.61e-03 4.25e-04 3.06e-03 2.71e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -205.5042190937559781 -2.11e-04 9.20e-04 6.22e-03 3.08e-03 0.1 + 7 -205.5045584152429683 -3.39e-04 3.42e-03 2.32e-02 2.42e-03 0.0 + 8 -205.5033501430223737 1.21e-03 2.00e-03 1.60e-02 1.57e-02 0.0 + 9 -205.5047552149538888 -1.41e-03 5.27e-04 6.87e-03 3.03e-03 0.0 + 10 -205.5045721486596335 1.83e-04 4.96e-04 4.85e-03 6.44e-03 0.0 + 11 -205.5048339487892122 -2.62e-04 4.83e-05 2.96e-04 1.09e-04 0.0 + 12 -205.5048342684333988 -3.20e-07 1.12e-05 1.63e-04 6.32e-05 0.0 + 13 -205.5048343983187920 -1.30e-07 3.61e-06 4.37e-05 1.37e-05 0.0 + 14 -205.5048344044225246 -6.10e-09 1.49e-06 1.76e-05 7.62e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 14 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50483440442252 Eh -5592.07084 eV + +Components: +Nuclear Repulsion : 69.75871798780842 Eh 1898.23122 eV +Electronic Energy : -275.26355239223096 Eh -7490.30206 eV +One Electron Energy: -419.20078080944171 Eh -11407.03317 eV +Two Electron Energy: 143.93722841721072 Eh 3916.73111 eV + +Virial components: +Potential Energy : -410.31635539434097 Eh -11165.27566 eV +Kinetic Energy : 204.81152098991845 Eh 5573.20482 eV +Virial Ratio : 2.00338512897689 + +DFT components: +N(Alpha) : 11.999998517197 electrons +N(Beta) : 11.999998517197 electrons +N(Total) : 23.999997034395 electrons +E(X) : -23.334358302337 Eh +E(C) : -0.805403866205 Eh +E(XC) : -24.139762168543 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 6.1037e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.7639e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.4902e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.7148e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 7.6240e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.5037e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.194919 -522.3203 + 1 2.0000 -19.044070 -518.2155 + 2 2.0000 -14.232288 -387.2803 + 3 2.0000 -1.251745 -34.0617 + 4 2.0000 -0.967570 -26.3289 + 5 2.0000 -0.709051 -19.2943 + 6 2.0000 -0.572350 -15.5744 + 7 2.0000 -0.516989 -14.0680 + 8 2.0000 -0.512114 -13.9353 + 9 2.0000 -0.322996 -8.7892 + 10 2.0000 -0.276133 -7.5140 + 11 2.0000 -0.235309 -6.4031 + 12 0.0000 -0.216334 -5.8867 + 13 0.0000 0.040296 1.0965 + 14 0.0000 0.109809 2.9880 + 15 0.0000 0.138713 3.7746 + 16 0.0000 0.241603 6.5743 + 17 0.0000 0.262361 7.1392 + 18 0.0000 0.318627 8.6703 + 19 0.0000 0.330715 8.9992 + 20 0.0000 0.343271 9.3409 + 21 0.0000 0.384652 10.4669 + 22 0.0000 0.391657 10.6575 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.404350 + 1 O : 0.201781 + 2 O : -0.094902 + 3 H : 0.297471 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.786934 s : 3.786934 + pz : 1.132016 p : 3.573218 + px : 1.639972 + py : 0.801231 + dz2 : 0.004379 d : 0.044198 + dxz : 0.005027 + dyz : 0.012909 + dx2y2 : 0.011699 + dxy : 0.010184 + + 1 O s : 3.761327 s : 3.761327 + pz : 1.393703 p : 3.918720 + px : 1.410703 + py : 1.114314 + dz2 : 0.014265 d : 0.118171 + dxz : 0.014952 + dyz : 0.036683 + dx2y2 : 0.042587 + dxy : 0.009684 + + 2 O s : 3.931254 s : 3.931254 + pz : 1.298494 p : 4.143390 + px : 1.380752 + py : 1.464144 + dz2 : 0.004889 d : 0.020259 + dxz : 0.001610 + dyz : 0.005574 + dx2y2 : 0.003411 + dxy : 0.004774 + + 3 H s : 0.668743 s : 0.668743 + pz : 0.012890 p : 0.033785 + px : 0.013239 + py : 0.007657 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.145854 + 1 O : -0.169314 + 2 O : 0.024918 + 3 H : 0.290250 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.266673 s : 3.266673 + pz : 1.073639 p : 3.569279 + px : 1.532390 + py : 0.963250 + dz2 : 0.029225 d : 0.309902 + dxz : 0.016590 + dyz : 0.075223 + dx2y2 : 0.077815 + dxy : 0.111048 + + 1 O s : 3.365243 s : 3.365243 + pz : 1.316588 p : 4.022228 + px : 1.403309 + py : 1.302331 + dz2 : 0.061988 d : 0.781843 + dxz : 0.064826 + dyz : 0.196225 + dx2y2 : 0.209757 + dxy : 0.249046 + + 2 O s : 3.610668 s : 3.610668 + pz : 1.267927 p : 4.113895 + px : 1.367675 + py : 1.478294 + dz2 : 0.037710 d : 0.250519 + dxz : 0.051600 + dyz : 0.039451 + dx2y2 : 0.062462 + dxy : 0.059295 + + 3 H s : 0.625358 s : 0.625358 + pz : 0.031898 p : 0.084393 + px : 0.034931 + py : 0.017564 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.4044 7.0000 -0.4044 2.5965 2.5965 -0.0000 + 1 O 7.7982 8.0000 0.2018 2.6371 2.6371 -0.0000 + 2 O 8.0949 8.0000 -0.0949 1.6679 1.6679 0.0000 + 3 H 0.7025 1.0000 0.2975 0.8968 0.8968 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3972 B( 0-N , 2-O ) : 0.3873 B( 0-N , 3-H ) : 0.8119 +B( 1-O , 2-O ) : 1.2178 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 3 sec + +Total time .... 3.929 sec +Sum of individual times .... 3.909 sec ( 99.5%) + +SCF preparation .... 1.118 sec ( 28.5%) +Fock matrix formation .... 0.418 sec ( 10.6%) + Startup .... 0.021 sec ( 5.1% of F) + Split-RI-J .... 0.068 sec ( 16.3% of F) + XC integration .... 0.264 sec ( 63.2% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.018 sec ( 6.7% of XC) + Density eval. .... 0.024 sec ( 9.0% of XC) + XC-Functional eval. .... 0.014 sec ( 5.2% of XC) + XC-Potential eval. .... 0.021 sec ( 7.9% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.028 sec ( 0.7%) +Total Energy calculation .... 0.031 sec ( 0.8%) +Population analysis .... 2.169 sec ( 55.2%) +Orbital Transformation .... 0.014 sec ( 0.4%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.071 sec ( 1.8%) +SOSCF solution .... 0.059 sec ( 1.5%) +Finished LeanSCF after 6.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 41.6 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360643 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006743923 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.498451124695 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003369 -0.000006044 0.000001408 + 2 O : -0.000000204 0.000000876 -0.000000592 + 3 O : 0.000003689 0.000008241 0.000000722 + 4 H : -0.000000115 -0.000003073 -0.000001538 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000120372 +RMS gradient ... 0.0000034749 +MAX gradient ... 0.0000082414 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.058800609 0.004272612 -0.021615531 + 2 O : 0.046647944 -0.006798824 -0.027087170 + 3 O : -0.017607201 0.005962952 0.023412627 + 4 H : 0.029759866 -0.003436740 0.025290074 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000182160 -0.0000102675 0.0000016676 + +Norm of the Cartesian gradient ... 0.0965905668 +RMS gradient ... 0.0278832949 +MAX gradient ... 0.0588006094 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.128 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.8%) +RI-J Coulomb gradient .... 0.061 sec ( 47.6%) +XC gradient .... 0.019 sec ( 14.8%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.498451125 Eh +Current gradient norm .... 0.096590567 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.997609312 +Lowest eigenvalues of augmented Hessian: + -0.001852606 0.367175451 0.414286296 0.446521951 0.687690338 +Length of the computed step .... 0.069271762 +The final length of the internal step .... 0.069271762 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0282800785 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0254050669 RMS(Int)= 0.0282700999 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000003 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0109968701 0.0001000000 NO + MAX gradient 0.0228289192 0.0003000000 NO + RMS step 0.0282800785 0.0020000000 NO + MAX step 0.0620996165 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0031 Max(Angles) 3.56 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2789 -0.004400 0.0031 1.2820 + 2. B(O 2,O 1) 1.3039 0.002238 -0.0017 1.3022 + 3. B(H 3,N 0) 1.0218 -0.000807 0.0010 1.0229 + 4. A(O 1,N 0,H 3) 118.00 0.022829 -3.56 114.44 + 5. A(N 0,O 1,O 2) 118.07 0.013394 -1.71 116.36 + 6. D(O 2,O 1,N 0,H 3) 106.15 -0.063722 0.00 106.15 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.673 %) +Internal coordinates : 0.000 s ( 3.268 %) +B/P matrices and projection : 0.000 s (17.647 %) +Hessian update/contruction : 0.000 s (26.928 %) +Making the step : 0.000 s ( 7.451 %) +Converting the step to Cartesian: 0.000 s ( 4.444 %) +Storing new data : 0.000 s ( 3.660 %) +Checking convergence : 0.000 s ( 0.000 %) +Final printing : 0.000 s (26.667 %) +Total time : 0.001 s + +Time for energy+gradient : 11.110 s +Time for complete geometry iter : 11.999 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.039727 -0.673680 -0.245978 + O -0.164695 0.586025 -0.367514 + O 0.701579 1.370383 0.206958 + H -0.595318 -1.144884 0.402827 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.075073 -1.273071 -0.464831 + 1 O 8.0000 0 15.999 -0.311229 1.107427 -0.694501 + 2 O 8.0000 0 15.999 1.325791 2.589648 0.391093 + 3 H 1.0000 0 1.008 -1.124987 -2.163517 0.761232 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.281958470383 0.00000000 0.00000000 + O 2 1 0 1.302177038591 116.35819588 0.00000000 + H 1 2 3 1.022869405574 114.44414020 106.15384621 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.422550424084 0.00000000 0.00000000 + O 2 1 0 2.460757980817 116.35819588 0.00000000 + H 1 2 3 1.932943047301 114.44414020 106.15384621 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1675 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.913012010556 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.868e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22309 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5056715625467518 0.00e+00 2.20e-04 1.87e-03 7.94e-03 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.019) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5058702311434331 -1.99e-04 2.60e-04 2.11e-03 6.02e-03 0.700 0.1 + ***Turning on AO-DIIS*** + 3 -205.5060490769203625 -1.79e-04 2.07e-04 1.49e-03 4.10e-03 0.700 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 4 -205.5061782634323890 -1.29e-04 5.70e-04 3.83e-03 2.88e-03 0.0 + *** Restarting incremental Fock matrix formation *** + 5 -205.5064926889799040 -3.14e-04 2.62e-04 2.06e-03 9.06e-04 0.1 + 6 -205.5064885326179933 4.16e-06 3.18e-04 2.29e-03 2.80e-03 0.0 + 7 -205.5065276940940748 -3.92e-05 6.94e-05 8.20e-04 3.35e-04 0.0 + 8 -205.5065245950405597 3.10e-06 3.89e-05 5.58e-04 9.08e-04 0.0 + 9 -205.5065291349802692 -4.54e-06 9.24e-06 9.36e-05 4.68e-05 0.0 + 10 -205.5065291806675418 -4.57e-08 3.24e-06 2.82e-05 2.99e-05 0.0 + 11 -205.5065291989507159 -1.83e-08 9.82e-07 8.36e-06 3.69e-06 0.0 + 12 -205.5065291992951870 -3.44e-10 6.64e-07 6.06e-06 1.66e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50652919929519 Eh -5592.11696 eV + +Components: +Nuclear Repulsion : 69.91301201055563 Eh 1902.42977 eV +Electronic Energy : -275.41954120985082 Eh -7494.54673 eV +One Electron Energy: -419.50185266905748 Eh -11415.22575 eV +Two Electron Energy: 144.08231145920666 Eh 3920.67902 eV + +Virial components: +Potential Energy : -410.34621276357808 Eh -11166.08812 eV +Kinetic Energy : 204.83968356428289 Eh 5573.97117 eV +Virial Ratio : 2.00325545140184 + +DFT components: +N(Alpha) : 11.999998629616 electrons +N(Beta) : 11.999998629616 electrons +N(Total) : 23.999997259231 electrons +E(X) : -23.337794250439 Eh +E(C) : -0.805285605180 Eh +E(XC) : -24.143079855619 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.4447e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.0625e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 6.6394e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.8802e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.6616e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.2306e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 3.7 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 41.8 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361280 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.006889218 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.500001260914 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003352 -0.000005855 0.000001460 + 2 O : -0.000000242 0.000000820 -0.000000568 + 3 O : 0.000003520 0.000007881 0.000000763 + 4 H : 0.000000074 -0.000002846 -0.000001655 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000116029 +RMS gradient ... 0.0000033495 +MAX gradient ... 0.0000078810 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.055975524 0.008485311 -0.021661202 + 2 O : 0.042441302 -0.008737312 -0.032553604 + 3 O : -0.018030721 0.000086642 0.026936789 + 4 H : 0.031564943 0.000165359 0.027278017 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000177463 -0.0000104136 0.0000081896 + +Norm of the Cartesian gradient ... 0.0969689516 +RMS gradient ... 0.0279925252 +MAX gradient ... 0.0559755240 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.123 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.9%) +RI-J Coulomb gradient .... 0.057 sec ( 46.2%) +XC gradient .... 0.019 sec ( 15.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.500001261 Eh +Current gradient norm .... 0.096968952 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.976271951 +Lowest eigenvalues of augmented Hessian: + -0.004477307 0.089424284 0.414437120 0.527219832 0.687904325 +Length of the computed step .... 0.221811245 +The final length of the internal step .... 0.221811245 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0905540614 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0704848198 RMS(Int)= 0.0908505977 + Iter 5: RMS(Cart)= 0.0000013896 RMS(Int)= 0.0000013827 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000008 RMS(Int)= 0.0000000002 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.002348796 +Previously predicted energy change .... -0.000930748 +Actually observed energy change .... -0.001550136 +Ratio of predicted to observed change .... 1.665473804 +New trust radius .... 0.200000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0015501362 0.0000050000 NO + RMS gradient 0.0088401881 0.0001000000 NO + MAX gradient 0.0179217949 0.0003000000 NO + RMS step 0.0905540614 0.0020000000 NO + MAX step 0.2106585158 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0271 Max(Angles) 12.07 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2820 -0.011861 0.0271 1.3091 + 2. B(O 2,O 1) 1.3022 -0.000058 -0.0019 1.3002 + 3. B(H 3,N 0) 1.0229 -0.002372 0.0097 1.0326 + 4. A(O 1,N 0,H 3) 114.44 0.017922 -12.07 102.37 + 5. A(N 0,O 1,O 2) 116.36 0.001178 -2.46 113.90 + 6. D(O 2,O 1,N 0,H 3) 106.15 -0.071458 0.00 106.15 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 8.333 %) +Internal coordinates : 0.000 s ( 3.056 %) +B/P matrices and projection : 0.000 s (12.222 %) +Hessian update/contruction : 0.000 s (38.056 %) +Making the step : 0.000 s ( 5.833 %) +Converting the step to Cartesian: 0.000 s ( 4.861 %) +Storing new data : 0.000 s ( 3.333 %) +Checking convergence : 0.000 s ( 1.389 %) +Final printing : 0.000 s (22.639 %) +Total time : 0.001 s + +Time for energy+gradient : 8.481 s +Time for complete geometry iter : 9.262 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.085024 -0.709505 -0.288833 + O -0.197798 0.567082 -0.352384 + O 0.683295 1.331032 0.222681 + H -0.589229 -1.050764 0.414828 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.160672 -1.340771 -0.545816 + 1 O 8.0000 0 15.999 -0.373784 1.071629 -0.665910 + 2 O 8.0000 0 15.999 1.291240 2.515286 0.420807 + 3 H 1.0000 0 1.008 -1.113481 -1.985657 0.783911 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.309084079508 0.00000000 0.00000000 + O 2 1 0 1.300247895020 113.89655086 0.00000000 + H 1 2 3 1.032575925716 102.37429633 106.15384622 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.473810396546 0.00000000 0.00000000 + O 2 1 0 2.457112427795 113.89655086 0.00000000 + H 1 2 3 1.951285712083 102.37429633 106.15384622 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1674 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.694332012337 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.932e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22303 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.5 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5010091112811779 0.00e+00 6.31e-04 7.29e-03 2.00e-02 0.700 0.1 +Warning: op=0 Small HOMO/LUMO gap ( 0.018) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5027561382833596 -1.75e-03 7.27e-04 7.47e-03 1.56e-02 0.700 0.1 + ***Turning on AO-DIIS*** + 3 -205.5043571067434982 -1.60e-03 5.92e-04 5.35e-03 1.12e-02 0.700 0.0 + 4 -205.5055354475278477 -1.18e-03 1.62e-03 1.38e-02 7.99e-03 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5083770216537573 -2.84e-03 2.59e-04 2.05e-03 1.72e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -205.5084586638214432 -8.16e-05 4.82e-04 3.58e-03 1.52e-03 0.0 + 7 -205.5085457530782946 -8.71e-05 1.25e-03 9.49e-03 2.50e-03 0.0 + 8 -205.5084018786924958 1.44e-04 6.38e-04 4.82e-03 5.58e-03 0.0 + 9 -205.5085942779385846 -1.92e-04 4.31e-04 3.75e-03 1.35e-03 0.0 + 10 -205.5085344706785691 5.98e-05 3.17e-04 2.72e-03 3.00e-03 0.0 + 11 -205.5086091088448939 -7.46e-05 8.61e-06 7.16e-05 4.38e-05 0.0 + 12 -205.5086091411627081 -3.23e-08 2.74e-06 2.44e-05 2.68e-05 0.0 + 13 -205.5086091523551204 -1.12e-08 4.51e-07 3.11e-06 1.97e-06 0.0 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 13 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50860915235512 Eh -5592.17356 eV + +Components: +Nuclear Repulsion : 69.69433201233686 Eh 1896.47919 eV +Electronic Energy : -275.20294116469199 Eh -7488.65274 eV +One Electron Energy: -419.07778007733793 Eh -11403.68615 eV +Two Electron Energy: 143.87483891264594 Eh 3915.03340 eV + +Virial components: +Potential Energy : -410.36650773704014 Eh -11166.64038 eV +Kinetic Energy : 204.85789858468505 Eh 5574.46682 eV +Virial Ratio : 2.00317639970031 + +DFT components: +N(Alpha) : 11.999998211742 electrons +N(Beta) : 11.999998211742 electrons +N(Total) : 23.999996423483 electrons +E(X) : -23.330438176035 Eh +E(C) : -0.804120786427 Eh +E(XC) : -24.134558962462 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.1192e-08 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.1092e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.5057e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.7218e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.9670e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 6.9636e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 3.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 41.9 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000362481 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007292244 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.501679389692 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003326 -0.000005439 0.000001542 + 2 O : -0.000000366 0.000000647 -0.000000462 + 3 O : 0.000003136 0.000007195 0.000000911 + 4 H : 0.000000556 -0.000002403 -0.000001991 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000107827 +RMS gradient ... 0.0000031127 +MAX gradient ... 0.0000071949 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.036916064 0.003804766 -0.025246575 + 2 O : 0.024556631 -0.009784674 -0.040753474 + 3 O : -0.016127096 -0.007864089 0.033960157 + 4 H : 0.028486530 0.013843996 0.032039891 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000056385 -0.0000100744 0.0000163690 + +Norm of the Cartesian gradient ... 0.0887647888 +RMS gradient ... 0.0256241874 +MAX gradient ... 0.0407534736 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.123 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 3.8%) +RI-J Coulomb gradient .... 0.058 sec ( 47.2%) +XC gradient .... 0.018 sec ( 14.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.501679390 Eh +Current gradient norm .... 0.088764789 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.200 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.998267444 +Lowest eigenvalues of augmented Hessian: + -0.001027928 0.124084122 0.414399312 0.529208736 0.688768319 +Length of the computed step .... 0.058941819 +The final length of the internal step .... 0.058941819 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0240628970 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0243561571 RMS(Int)= 0.0240712286 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000515750 +Previously predicted energy change .... -0.002348796 +Actually observed energy change .... -0.001678129 +Ratio of predicted to observed change .... 0.714463431 +New trust radius .... 0.200000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0016781288 0.0000050000 NO + RMS gradient 0.0108094406 0.0001000000 NO + MAX gradient 0.0187033941 0.0003000000 NO + RMS step 0.0240628970 0.0020000000 NO + MAX step 0.0541440101 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0026 Max(Angles) 3.10 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3091 -0.018703 0.0026 1.3117 + 2. B(O 2,O 1) 1.3002 -0.000528 0.0001 1.3003 + 3. B(H 3,N 0) 1.0326 -0.001342 -0.0012 1.0314 + 4. A(O 1,N 0,H 3) 102.37 -0.010992 3.10 105.48 + 5. A(N 0,O 1,O 2) 113.90 -0.015111 1.30 115.19 + 6. D(O 2,O 1,N 0,H 3) 106.15 -0.085157 -0.00 106.15 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 8.883 %) +Internal coordinates : 0.000 s ( 2.961 %) +B/P matrices and projection : 0.000 s (11.978 %) +Hessian update/contruction : 0.000 s (34.455 %) +Making the step : 0.000 s ( 6.191 %) +Converting the step to Cartesian: 0.000 s ( 4.307 %) +Storing new data : 0.000 s ( 3.230 %) +Checking convergence : 0.000 s ( 1.346 %) +Final printing : 0.000 s (26.514 %) +Total time : 0.001 s + +Time for energy+gradient : 8.439 s +Time for complete geometry iter : 9.240 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 4 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.071923 -0.707405 -0.279562 + O -0.185502 0.576659 -0.354007 + O 0.689463 1.350638 0.217168 + H -0.594592 -1.082048 0.412693 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.135916 -1.336801 -0.528296 + 1 O 8.0000 0 15.999 -0.350549 1.089728 -0.668976 + 2 O 8.0000 0 15.999 1.302897 2.552336 0.410388 + 3 H 1.0000 0 1.008 -1.123617 -2.044775 0.779877 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.311728047856 0.00000000 0.00000000 + O 2 1 0 1.300326160123 115.19398570 0.00000000 + H 1 2 3 1.031415980936 105.47651960 106.15384621 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.478806772632 0.00000000 0.00000000 + O 2 1 0 2.457260327405 115.19398570 0.00000000 + H 1 2 3 1.949093734118 105.47651960 106.15384621 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1673 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.461267412489 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.913e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22298 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.5 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5085961095045661 0.00e+00 1.73e-04 2.02e-03 6.37e-03 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.021) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5087030944784772 -1.07e-04 1.79e-04 1.65e-03 4.78e-03 0.700 0.0 + ***Turning on AO-DIIS*** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 3 -205.5087916612985453 -8.86e-05 4.49e-04 3.91e-03 3.25e-03 0.0 + *** Restarting incremental Fock matrix formation *** + 4 -205.5089954142438557 -2.04e-04 1.95e-04 2.65e-03 9.21e-04 0.0 + 5 -205.5089480259151458 4.74e-05 1.45e-04 1.76e-03 2.90e-03 0.0 + 6 -205.5090046930082792 -5.67e-05 1.47e-04 2.29e-03 6.48e-04 0.0 + 7 -205.5089669642609636 3.77e-05 1.20e-04 1.67e-03 2.33e-03 0.0 + 8 -205.5090108978991168 -4.39e-05 2.52e-05 2.08e-04 5.59e-05 0.0 + 9 -205.5090110978458995 -2.00e-07 2.26e-05 1.66e-04 2.22e-05 0.0 + 10 -205.5090111412032172 -4.34e-08 4.32e-06 3.95e-05 1.77e-05 0.0 + 11 -205.5090111503915011 -9.19e-09 4.60e-07 3.29e-06 2.41e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50901115039150 Eh -5592.18449 eV + +Components: +Nuclear Repulsion : 69.46126741248864 Eh 1890.13718 eV +Electronic Energy : -274.97027856288014 Eh -7482.32167 eV +One Electron Energy: -418.62295704420393 Eh -11391.30978 eV +Two Electron Energy: 143.65267848132382 Eh 3908.98811 eV + +Virial components: +Potential Energy : -410.33509230595507 Eh -11165.78552 eV +Kinetic Energy : 204.82608115556354 Eh 5573.60102 eV +Virial Ratio : 2.00333419450773 + +DFT components: +N(Alpha) : 11.999998259020 electrons +N(Beta) : 11.999998259020 electrons +N(Total) : 23.999996518041 electrons +E(X) : -23.325514761420 Eh +E(C) : -0.803831365594 Eh +E(XC) : -24.129346127014 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 9.1883e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.2921e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.5969e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.2459e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.4088e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.0009e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 3.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 42.1 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361935 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007145443 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502227642393 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.0 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003356 -0.000005624 0.000001511 + 2 O : -0.000000324 0.000000715 -0.000000496 + 3 O : 0.000003294 0.000007534 0.000000875 + 4 H : 0.000000386 -0.000002624 -0.000001890 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000111809 +RMS gradient ... 0.0000032277 +MAX gradient ... 0.0000075336 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.044308746 -0.000716416 -0.024281639 + 2 O : 0.031316492 -0.004919401 -0.040398986 + 3 O : -0.016527357 -0.001836833 0.033185043 + 4 H : 0.029519611 0.007472651 0.031495583 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000095673 -0.0000120518 0.0000233903 + +Norm of the Cartesian gradient ... 0.0921269330 +RMS gradient ... 0.0265947548 +MAX gradient ... 0.0443087461 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.097 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.7%) +RI-J Coulomb gradient .... 0.048 sec ( 48.9%) +XC gradient .... 0.013 sec ( 13.8%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.502227642 Eh +Current gradient norm .... 0.092126933 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.200 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999711483 +Lowest eigenvalues of augmented Hessian: + -0.000218851 0.181186373 0.414443533 0.524119065 0.571313640 +Length of the computed step .... 0.024026711 +The final length of the internal step .... 0.024026711 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0098088638 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0057525688 RMS(Int)= 0.0098171753 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000109488 +Previously predicted energy change .... -0.000515750 +Actually observed energy change .... -0.000548253 +Ratio of predicted to observed change .... 1.063020636 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0005482527 0.0000050000 NO + RMS gradient 0.0041882562 0.0001000000 NO + MAX gradient 0.0091086219 0.0003000000 NO + RMS step 0.0098088638 0.0020000000 NO + MAX step 0.0187549001 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0099 Max(Angles) 0.72 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3117 -0.009109 0.0099 1.3217 + 2. B(O 2,O 1) 1.3003 0.002364 -0.0026 1.2978 + 3. B(H 3,N 0) 1.0314 -0.000651 0.0012 1.0327 + 4. A(O 1,N 0,H 3) 105.48 0.000890 -0.72 104.75 + 5. A(N 0,O 1,O 2) 115.19 -0.003934 0.35 115.54 + 6. D(O 2,O 1,N 0,H 3) 106.15 -0.082280 -0.00 106.15 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.791 %) +Internal coordinates : 0.000 s ( 3.597 %) +B/P matrices and projection : 0.000 s (12.662 %) +Hessian update/contruction : 0.000 s (28.921 %) +Making the step : 0.000 s ( 6.043 %) +Converting the step to Cartesian: 0.000 s ( 4.604 %) +Storing new data : 0.000 s ( 3.597 %) +Checking convergence : 0.000 s ( 1.295 %) +Final printing : 0.000 s (28.058 %) +Total time : 0.001 s + +Time for energy+gradient : 7.437 s +Time for complete geometry iter : 8.213 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 5 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.073290 -0.715185 -0.282863 + O -0.184360 0.579331 -0.350761 + O 0.688611 1.354085 0.216558 + H -0.596249 -1.080387 0.413358 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.138498 -1.351503 -0.534533 + 1 O 8.0000 0 15.999 -0.348391 1.094777 -0.662843 + 2 O 8.0000 0 15.999 1.301287 2.558849 0.409235 + 3 H 1.0000 0 1.008 -1.126748 -2.041636 0.781133 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.321652713541 0.00000000 0.00000000 + O 2 1 0 1.297757275924 115.54008759 0.00000000 + H 1 2 3 1.032656317184 104.75180699 106.15384621 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.497561672746 0.00000000 0.00000000 + O 2 1 0 2.452405839800 115.54008759 0.00000000 + H 1 2 3 1.951437629941 104.75180699 106.15384621 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1672 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.273699849897 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.893e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22300 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5575 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5090198916774966 0.00e+00 7.87e-05 7.24e-04 5.11e-03 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.020) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5090589236233996 -3.90e-05 8.93e-05 7.96e-04 3.73e-03 0.700 0.0 + ***Turning on AO-DIIS*** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 3 -205.5090907292143356 -3.18e-05 2.39e-04 2.10e-03 2.70e-03 0.0 + *** Restarting incremental Fock matrix formation *** + 4 -205.5091622823776447 -7.16e-05 1.19e-04 1.54e-03 6.89e-04 0.0 + 5 -205.5091398620575092 2.24e-05 8.79e-05 1.35e-03 1.89e-03 0.0 + 6 -205.5091657737618789 -2.59e-05 1.20e-04 1.44e-03 4.68e-04 0.0 + 7 -205.5091440780507810 2.17e-05 8.45e-05 1.19e-03 1.50e-03 0.0 + 8 -205.5091683303956529 -2.43e-05 1.45e-05 1.05e-04 3.32e-05 0.0 + 9 -205.5091684154018026 -8.50e-08 1.71e-05 1.42e-04 1.77e-05 0.0 + 10 -205.5091684407928483 -2.54e-08 3.18e-06 2.64e-05 1.02e-05 0.0 + 11 -205.5091684449236595 -4.13e-09 1.73e-07 1.47e-06 9.99e-07 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50916844492366 Eh -5592.18877 eV + +Components: +Nuclear Repulsion : 69.27369984989667 Eh 1885.03321 eV +Electronic Energy : -274.78286829482033 Eh -7477.22198 eV +One Electron Energy: -418.25544972976269 Eh -11381.30940 eV +Two Electron Energy: 143.47258143494236 Eh 3904.08742 eV + +Virial components: +Potential Energy : -410.31996691531674 Eh -11165.37394 eV +Kinetic Energy : 204.81079847039311 Eh 5573.18516 eV +Virial Ratio : 2.00340982985148 + +DFT components: +N(Alpha) : 11.999998221088 electrons +N(Beta) : 11.999998221088 electrons +N(Total) : 23.999996442176 electrons +E(X) : -23.320856269993 Eh +E(C) : -0.803464170345 Eh +E(XC) : -24.124320440338 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 4.1308e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.4744e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.7317e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.6963e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 9.9877e-07 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 4.9837e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 3.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 42.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361840 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007143181 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502387103926 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003366 -0.000005655 0.000001505 + 2 O : -0.000000322 0.000000727 -0.000000489 + 3 O : 0.000003301 0.000007595 0.000000882 + 4 H : 0.000000387 -0.000002668 -0.000001899 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000112554 +RMS gradient ... 0.0000032492 +MAX gradient ... 0.0000075954 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.043563970 -0.005497398 -0.024414327 + 2 O : 0.031312653 -0.001125346 -0.040576255 + 3 O : -0.016781978 -0.000499887 0.033289712 + 4 H : 0.029033294 0.007122631 0.031700870 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000078228 -0.0000135199 0.0000155078 + +Norm of the Cartesian gradient ... 0.0918748073 +RMS gradient ... 0.0265219724 +MAX gradient ... 0.0435639699 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.110 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.2%) +RI-J Coulomb gradient .... 0.054 sec ( 49.0%) +XC gradient .... 0.019 sec ( 17.6%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.502387104 Eh +Current gradient norm .... 0.091874807 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999673772 +Lowest eigenvalues of augmented Hessian: + -0.000114387 0.131704317 0.373353948 0.415249881 0.535577214 +Length of the computed step .... 0.025549467 +The final length of the internal step .... 0.025549467 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0104305261 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0054161485 RMS(Int)= 0.0104354396 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000057231 +Previously predicted energy change .... -0.000109488 +Actually observed energy change .... -0.000159462 +Ratio of predicted to observed change .... 1.456423181 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0001594615 0.0000050000 NO + RMS gradient 0.0020786705 0.0001000000 NO + MAX gradient 0.0040513565 0.0003000000 NO + RMS step 0.0104305261 0.0020000000 NO + MAX step 0.0189063842 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0100 Max(Angles) 0.81 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3217 -0.004051 0.0100 1.3317 + 2. B(O 2,O 1) 1.2978 0.002967 -0.0050 1.2928 + 3. B(H 3,N 0) 1.0327 0.000029 0.0006 1.0333 + 4. A(O 1,N 0,H 3) 104.75 0.000617 -0.81 103.94 + 5. A(N 0,O 1,O 2) 115.54 -0.000573 0.12 115.66 + 6. D(O 2,O 1,N 0,H 3) 106.15 -0.082229 0.00 106.15 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.791 %) +Internal coordinates : 0.000 s ( 3.022 %) +B/P matrices and projection : 0.000 s (13.525 %) +Hessian update/contruction : 0.000 s (31.655 %) +Making the step : 0.000 s ( 5.612 %) +Converting the step to Cartesian: 0.000 s ( 3.885 %) +Storing new data : 0.000 s ( 3.165 %) +Checking convergence : 0.000 s ( 1.295 %) +Final printing : 0.000 s (26.763 %) +Total time : 0.001 s + +Time for energy+gradient : 7.656 s +Time for complete geometry iter : 8.361 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 6 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.075596 -0.722075 -0.285795 + O -0.184024 0.582551 -0.347919 + O 0.686653 1.354023 0.216025 + H -0.596934 -1.076655 0.413981 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.142856 -1.364524 -0.540074 + 1 O 8.0000 0 15.999 -0.347755 1.100862 -0.657472 + 2 O 8.0000 0 15.999 1.297587 2.558733 0.408228 + 3 H 1.0000 0 1.008 -1.128041 -2.034584 0.782310 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.331657541162 0.00000000 0.00000000 + O 2 1 0 1.292780313658 115.65720549 0.00000000 + H 1 2 3 1.033300276419 103.93907716 106.15384621 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.516468056967 0.00000000 0.00000000 + O 2 1 0 2.443000744139 115.65720549 0.00000000 + H 1 2 3 1.952654536537 103.93907716 106.15384621 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1670 + la=0 lb=0: 144 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.172422121057 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.852e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22302 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5090851097905897 0.00e+00 8.24e-05 7.53e-04 5.22e-03 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.020) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5091270799210292 -4.20e-05 8.94e-05 7.62e-04 3.77e-03 0.700 0.0 + ***Turning on AO-DIIS*** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 3 -205.5091610617919855 -3.40e-05 2.35e-04 1.94e-03 2.72e-03 0.0 + *** Restarting incremental Fock matrix formation *** + 4 -205.5092382761253020 -7.72e-05 1.12e-04 1.31e-03 5.94e-04 0.0 + 5 -205.5092192679226173 1.90e-05 8.19e-05 1.26e-03 1.80e-03 0.0 + 6 -205.5092408887549595 -2.16e-05 1.07e-04 1.39e-03 4.32e-04 0.0 + 7 -205.5092235643532490 1.73e-05 7.40e-05 1.12e-03 1.46e-03 0.0 + 8 -205.5092430949265463 -1.95e-05 1.29e-05 9.62e-05 2.93e-05 0.0 + 9 -205.5092431615414057 -6.66e-08 1.48e-05 1.26e-04 1.55e-05 0.0 + 10 -205.5092431798742609 -1.83e-08 2.86e-06 2.51e-05 1.00e-05 0.0 + 11 -205.5092431834344779 -3.56e-09 2.01e-07 1.46e-06 1.01e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 11 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50924318343448 Eh -5592.19081 eV + +Components: +Nuclear Repulsion : 69.17242212105684 Eh 1882.27730 eV +Electronic Energy : -274.68166530449133 Eh -7474.46811 eV +One Electron Energy: -418.05395990522277 Eh -11375.82658 eV +Two Electron Energy: 143.37229460073144 Eh 3901.35848 eV + +Virial components: +Potential Energy : -410.31392232448377 Eh -11165.20945 eV +Kinetic Energy : 204.80467914104932 Eh 5573.01865 eV +Virial Ratio : 2.00344017551425 + +DFT components: +N(Alpha) : 11.999998254597 electrons +N(Beta) : 11.999998254597 electrons +N(Total) : 23.999996509195 electrons +E(X) : -23.318301451268 Eh +E(C) : -0.803249286598 Eh +E(XC) : -24.121550737866 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.5602e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.4648e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.0126e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.7233e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.0098e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 4.2705e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 3.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 42.5 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361823 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007152626 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502452380376 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.0 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003371 -0.000005663 0.000001506 + 2 O : -0.000000318 0.000000743 -0.000000478 + 3 O : 0.000003282 0.000007601 0.000000885 + 4 H : 0.000000407 -0.000002681 -0.000001913 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000112663 +RMS gradient ... 0.0000032523 +MAX gradient ... 0.0000076011 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.042309637 -0.009240874 -0.024251854 + 2 O : 0.031544933 0.002994911 -0.040120016 + 3 O : -0.017961069 -0.001041484 0.032730816 + 4 H : 0.028725772 0.007287447 0.031641054 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000011331 -0.0000153711 0.0000098571 + +Norm of the Cartesian gradient ... 0.0913878745 +RMS gradient ... 0.0263814070 +MAX gradient ... 0.0423096366 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.095 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.004 sec ( 4.6%) +RI-J Coulomb gradient .... 0.046 sec ( 48.0%) +XC gradient .... 0.013 sec ( 14.0%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.502452380 Eh +Current gradient norm .... 0.091387875 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999987096 +Lowest eigenvalues of augmented Hessian: + -0.000007465 0.127172903 0.325778844 0.415066904 0.536994396 +Length of the computed step .... 0.005080257 +The final length of the internal step .... 0.005080257 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0020740064 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0009860470 RMS(Int)= 0.0020737702 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000003733 +Previously predicted energy change .... -0.000057231 +Actually observed energy change .... -0.000065276 +Ratio of predicted to observed change .... 1.140584492 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000652765 0.0000050000 NO + RMS gradient 0.0007368985 0.0001000000 NO + MAX gradient 0.0015604335 0.0003000000 NO + RMS step 0.0020740064 0.0020000000 NO + MAX step 0.0035780622 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0019 Max(Angles) 0.05 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3317 -0.000390 0.0018 1.3335 + 2. B(O 2,O 1) 1.2928 0.001560 -0.0019 1.2909 + 3. B(H 3,N 0) 1.0333 0.000231 -0.0002 1.0331 + 4. A(O 1,N 0,H 3) 103.94 -0.000237 -0.04 103.90 + 5. A(N 0,O 1,O 2) 115.66 0.000749 -0.05 115.61 + 6. D(O 2,O 1,N 0,H 3) 106.15 -0.082164 0.00 106.15 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (11.940 %) +Internal coordinates : 0.000 s ( 3.134 %) +B/P matrices and projection : 0.000 s (13.433 %) +Hessian update/contruction : 0.000 s (30.299 %) +Making the step : 0.000 s ( 5.522 %) +Converting the step to Cartesian: 0.000 s ( 3.881 %) +Storing new data : 0.000 s ( 3.284 %) +Checking convergence : 0.000 s ( 1.343 %) +Final printing : 0.000 s (26.716 %) +Total time : 0.001 s + +Time for energy+gradient : 7.353 s +Time for complete geometry iter : 8.324 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 7 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.075940 -0.722624 -0.285679 + O -0.183927 0.583789 -0.347782 + O 0.686110 1.353104 0.215759 + H -0.596831 -1.076425 0.413993 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.143505 -1.365561 -0.539855 + 1 O 8.0000 0 15.999 -0.347572 1.103201 -0.657212 + 2 O 8.0000 0 15.999 1.296560 2.556996 0.407726 + 3 H 1.0000 0 1.008 -1.127847 -2.034148 0.782334 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.333454590188 0.00000000 0.00000000 + O 2 1 0 1.290886884677 115.60685726 0.00000000 + H 1 2 3 1.033119830335 103.89522895 106.15384621 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.519863987476 0.00000000 0.00000000 + O 2 1 0 2.439422681910 115.60685726 0.00000000 + H 1 2 3 1.952313542856 103.89522895 106.15384621 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 146 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.185252665403 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.836e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22302 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.5 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5092419932551593 0.00e+00 5.97e-05 6.26e-04 1.29e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5092486665004685 -6.67e-06 6.03e-05 6.58e-04 2.86e-04 0.0 + 3 -205.5092433141537072 5.35e-06 4.52e-05 5.86e-04 1.10e-03 0.0 + 4 -205.5092494966716004 -6.18e-06 1.23e-05 1.96e-04 8.30e-05 0.0 + 5 -205.5092492655720662 2.31e-07 8.67e-06 1.46e-04 2.14e-04 0.0 + 6 -205.5092495500422274 -2.84e-07 1.78e-06 1.38e-05 5.82e-06 0.0 + 7 -205.5092495513905533 -1.35e-09 1.16e-06 1.12e-05 2.49e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50924955139055 Eh -5592.19098 eV + +Components: +Nuclear Repulsion : 69.18525266540348 Eh 1882.62644 eV +Electronic Energy : -274.69450221679404 Eh -7474.81742 eV +One Electron Energy: -418.07752825428372 Eh -11376.46791 eV +Two Electron Energy: 143.38302603748971 Eh 3901.65049 eV + +Virial components: +Potential Energy : -410.31550011984820 Eh -11165.25239 eV +Kinetic Energy : 204.80625056845764 Eh 5573.06141 eV +Virial Ratio : 2.00343250746001 + +DFT components: +N(Alpha) : 11.999998285445 electrons +N(Beta) : 11.999998285445 electrons +N(Total) : 23.999996570891 electrons +E(X) : -23.318589526474 Eh +E(C) : -0.803268029405 Eh +E(XC) : -24.121857555879 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.3483e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.1228e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.1578e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.3870e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.4940e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.1401e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 3.6 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 42.6 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361835 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007154318 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502457068793 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003370 -0.000005660 0.000001508 + 2 O : -0.000000315 0.000000750 -0.000000477 + 3 O : 0.000003274 0.000007588 0.000000882 + 4 H : 0.000000412 -0.000002679 -0.000001913 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000112531 +RMS gradient ... 0.0000032485 +MAX gradient ... 0.0000075884 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.042143341 -0.009671731 -0.024035624 + 2 O : 0.031931866 0.004150407 -0.039767328 + 3 O : -0.018584684 -0.001756028 0.032303081 + 4 H : 0.028796158 0.007277352 0.031499871 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000032233 -0.0000125903 0.0000050126 + +Norm of the Cartesian gradient ... 0.0912798374 +RMS gradient ... 0.0263502193 +MAX gradient ... 0.0421433411 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.124 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.8%) +RI-J Coulomb gradient .... 0.054 sec ( 43.3%) +XC gradient .... 0.018 sec ( 14.1%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.502457069 Eh +Current gradient norm .... 0.091279837 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999998395 +Lowest eigenvalues of augmented Hessian: + -0.000001177 0.138371656 0.270807273 0.414990479 0.515512660 +Length of the computed step .... 0.001791790 +The final length of the internal step .... 0.001791790 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0007314951 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0005263063 RMS(Int)= 0.0007313985 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000589 +Previously predicted energy change .... -0.000003733 +Actually observed energy change .... -0.000004688 +Ratio of predicted to observed change .... 1.256024536 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000046884 0.0000050000 YES + RMS gradient 0.0002945657 0.0001000000 NO + MAX gradient 0.0005298763 0.0003000000 NO + RMS step 0.0007314951 0.0020000000 YES + MAX step 0.0013090218 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0007 Max(Angles) 0.05 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3335 0.000092 0.0002 1.3337 + 2. B(O 2,O 1) 1.2909 0.000530 -0.0007 1.2902 + 3. B(H 3,N 0) 1.0331 0.000089 -0.0001 1.0330 + 4. A(O 1,N 0,H 3) 103.90 -0.000143 0.04 103.94 + 5. A(N 0,O 1,O 2) 115.61 0.000450 -0.05 115.56 + 6. D(O 2,O 1,N 0,H 3) 106.15 -0.082056 0.00 106.15 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (11.353 %) +Internal coordinates : 0.000 s ( 2.778 %) +B/P matrices and projection : 0.000 s (11.836 %) +Hessian update/contruction : 0.000 s (34.058 %) +Making the step : 0.000 s ( 4.831 %) +Converting the step to Cartesian: 0.000 s ( 3.623 %) +Storing new data : 0.000 s ( 3.019 %) +Checking convergence : 0.000 s ( 1.329 %) +Final printing : 0.000 s (27.053 %) +Total time : 0.001 s + +Time for energy+gradient : 7.873 s +Time for complete geometry iter : 8.643 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 8 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.075990 -0.722319 -0.285357 + O -0.183952 0.584262 -0.347987 + O 0.685954 1.352479 0.215668 + H -0.596701 -1.076578 0.413968 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.143601 -1.364986 -0.539246 + 1 O 8.0000 0 15.999 -0.347619 1.104096 -0.657601 + 2 O 8.0000 0 15.999 1.296266 2.555814 0.407553 + 3 H 1.0000 0 1.008 -1.127601 -2.034437 0.782287 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.333659740729 0.00000000 0.00000000 + O 2 1 0 1.290194180156 115.55674208 0.00000000 + H 1 2 3 1.032989840827 103.93659634 106.15384621 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.520251665813 0.00000000 0.00000000 + O 2 1 0 2.438113660073 115.55674208 0.00000000 + H 1 2 3 1.952067898286 103.93659634 106.15384621 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 146 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.202082918451 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.830e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22302 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5092498626787574 0.00e+00 2.24e-05 1.91e-04 6.44e-05 0.6 + *** Restarting incremental Fock matrix formation *** + 2 -205.5092507833938384 -9.21e-07 1.92e-05 1.74e-04 6.97e-05 0.3 + 3 -205.5092506045949676 1.79e-07 1.41e-05 1.80e-04 2.19e-04 0.2 + 4 -205.5092509014309030 -2.97e-07 8.50e-06 1.23e-04 7.23e-05 0.1 + 5 -205.5092508243633347 7.71e-08 5.62e-06 9.48e-05 1.40e-04 0.2 + 6 -205.5092509421660907 -1.18e-07 2.71e-06 2.41e-05 9.34e-06 0.2 + 7 -205.5092509440590334 -1.89e-09 8.90e-07 1.09e-05 6.80e-06 0.2 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50925094405903 Eh -5592.19102 eV + +Components: +Nuclear Repulsion : 69.20208291845107 Eh 1883.08441 eV +Electronic Energy : -274.71133386251017 Eh -7475.27543 eV +One Electron Energy: -418.10957472278591 Eh -11377.33994 eV +Two Electron Energy: 143.39824086027576 Eh 3902.06451 eV + +Virial components: +Potential Energy : -410.31702689725387 Eh -11165.29393 eV +Kinetic Energy : 204.80777595319481 Eh 5573.10291 eV +Virial Ratio : 2.00342504081009 + +DFT components: +N(Alpha) : 11.999998301138 electrons +N(Beta) : 11.999998301138 electrons +N(Total) : 23.999996602277 electrons +E(X) : -23.318933375636 Eh +E(C) : -0.803296291296 Eh +E(XC) : -24.122229666932 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.8929e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.0872e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 8.8978e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.0150e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 6.7994e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 9.4149e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 3 sec +Finished LeanSCF after 5.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 42.8 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361846 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007155070 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502457719959 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.0 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003369 -0.000005656 0.000001509 + 2 O : -0.000000314 0.000000752 -0.000000477 + 3 O : 0.000003270 0.000007579 0.000000880 + 4 H : 0.000000413 -0.000002675 -0.000001912 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000112428 +RMS gradient ... 0.0000032455 +MAX gradient ... 0.0000075791 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.042111549 -0.009593862 -0.023929372 + 2 O : 0.032112011 0.004493671 -0.039607351 + 3 O : -0.018849015 -0.002156497 0.032100331 + 4 H : 0.028848554 0.007256689 0.031436392 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000037251 -0.0000173864 0.0000109424 + +Norm of the Cartesian gradient ... 0.0912231800 +RMS gradient ... 0.0263338638 +MAX gradient ... 0.0421115495 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.217 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.004 sec ( 1.9%) +RI-J Coulomb gradient .... 0.044 sec ( 20.2%) +XC gradient .... 0.015 sec ( 6.9%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.502457720 Eh +Current gradient norm .... 0.091223180 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999932 +Lowest eigenvalues of augmented Hessian: + -0.000000038 0.138030347 0.275857415 0.414269296 0.475785371 +Length of the computed step .... 0.000368260 +The final length of the internal step .... 0.000368260 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0001503414 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001191050 RMS(Int)= 0.0001503383 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000019 +Previously predicted energy change .... -0.000000589 +Actually observed energy change .... -0.000000651 +Ratio of predicted to observed change .... 1.106217562 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000006512 0.0000050000 YES + RMS gradient 0.0000500942 0.0001000000 YES + MAX gradient 0.0001016546 0.0003000000 YES + RMS step 0.0001503414 0.0020000000 YES + MAX step 0.0002369612 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3337 0.000056 -0.0001 1.3336 + 2. B(O 2,O 1) 1.2902 0.000031 -0.0000 1.2902 + 3. B(H 3,N 0) 1.0330 0.000007 -0.0000 1.0330 + 4. A(O 1,N 0,H 3) 103.94 -0.000022 0.01 103.95 + 5. A(N 0,O 1,O 2) 115.56 0.000102 -0.01 115.54 + 6. D(O 2,O 1,N 0,H 3) 106.15 -0.082005 0.00 106.15 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.186 %) +Internal coordinates : 0.000 s ( 0.039 %) +B/P matrices and projection : 0.000 s ( 0.165 %) +Hessian update/contruction : 0.012 s (16.967 %) +Making the step : 0.000 s ( 0.076 %) +Converting the step to Cartesian: 0.000 s ( 0.056 %) +Storing new data : 0.000 s ( 0.045 %) +Checking convergence : 0.000 s ( 0.020 %) +Final printing : 0.056 s (82.443 %) +Total time : 0.068 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 8 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.075987 -0.722185 -0.285280 + O -0.183987 0.584286 -0.348068 + O 0.685961 1.352367 0.215674 + H -0.596669 -1.076624 0.413965 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.143595 -1.364732 -0.539101 + 1 O 8.0000 0 15.999 -0.347684 1.104140 -0.657752 + 2 O 8.0000 0 15.999 1.296278 2.555603 0.407566 + 3 H 1.0000 0 1.008 -1.127541 -2.034524 0.782280 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.333564887416 0.00000000 0.00000000 + O 2 1 0 1.290179302709 115.54449363 0.00000000 + H 1 2 3 1.032974460745 103.95017322 106.15384621 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.520072419029 0.00000000 0.00000000 + O 2 1 0 2.438085545773 115.54449363 0.00000000 + H 1 2 3 1.952038834143 103.95017322 106.15384621 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 146 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.205424977377 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.830e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22302 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.2054249774 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.2 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.9 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5092511468978955 0.00e+00 4.36e-06 3.22e-05 1.26e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5092511791140168 -3.22e-08 3.95e-06 4.69e-05 1.75e-05 0.0 + 3 -205.5092511726182352 6.50e-09 3.25e-06 3.88e-05 4.20e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 3 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.50925117261824 Eh -5592.19103 eV + +Components: +Nuclear Repulsion : 69.20542497737733 Eh 1883.17535 eV +Electronic Energy : -274.71467614999557 Eh -7475.36638 eV +One Electron Energy: -418.11630650265886 Eh -11377.52312 eV +Two Electron Energy: 143.40163035266329 Eh 3902.15674 eV + +Virial components: +Potential Energy : -410.31705151691676 Eh -11165.29460 eV +Kinetic Energy : 204.80780034429850 Eh 5573.10358 eV +Virial Ratio : 2.00342492242552 + +DFT components: +N(Alpha) : 11.999998303450 electrons +N(Beta) : 11.999998303450 electrons +N(Total) : 23.999996606900 electrons +E(X) : -23.319039469623 Eh +E(C) : -0.803302527989 Eh +E(XC) : -24.122341997612 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -6.4958e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.8810e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.2476e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 4.5579e-05 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.1978e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 8.7462e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.187058 -522.1064 + 1 2.0000 -19.053285 -518.4662 + 2 2.0000 -14.240215 -387.4959 + 3 2.0000 -1.247978 -33.9592 + 4 2.0000 -0.956640 -26.0315 + 5 2.0000 -0.709897 -19.3173 + 6 2.0000 -0.559090 -15.2136 + 7 2.0000 -0.515396 -14.0246 + 8 2.0000 -0.504160 -13.7189 + 9 2.0000 -0.337170 -9.1749 + 10 2.0000 -0.278832 -7.5874 + 11 2.0000 -0.243278 -6.6199 + 12 0.0000 -0.223039 -6.0692 + 13 0.0000 0.046136 1.2554 + 14 0.0000 0.093708 2.5499 + 15 0.0000 0.123329 3.3560 + 16 0.0000 0.226181 6.1547 + 17 0.0000 0.265304 7.2193 + 18 0.0000 0.318337 8.6624 + 19 0.0000 0.329413 8.9638 + 20 0.0000 0.350232 9.5303 + 21 0.0000 0.381069 10.3694 + 22 0.0000 0.390797 10.6341 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.394417 + 1 O : 0.191162 + 2 O : -0.081633 + 3 H : 0.284888 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.880218 s : 3.880218 + pz : 1.083239 p : 3.468251 + px : 1.585393 + py : 0.799619 + dz2 : 0.003773 d : 0.045948 + dxz : 0.009593 + dyz : 0.011391 + dx2y2 : 0.011301 + dxy : 0.009890 + + 1 O s : 3.775580 s : 3.775580 + pz : 1.382395 p : 3.915456 + px : 1.426824 + py : 1.106238 + dz2 : 0.012783 d : 0.117802 + dxz : 0.013057 + dyz : 0.036332 + dx2y2 : 0.042671 + dxy : 0.012959 + + 2 O s : 3.938070 s : 3.938070 + pz : 1.220427 p : 4.123230 + px : 1.392619 + py : 1.510184 + dz2 : 0.004472 d : 0.020334 + dxz : 0.002790 + dyz : 0.005667 + dx2y2 : 0.002811 + dxy : 0.004593 + + 3 H s : 0.683685 s : 0.683685 + pz : 0.013193 p : 0.031427 + px : 0.012141 + py : 0.006093 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.134635 + 1 O : -0.176008 + 2 O : 0.026919 + 3 H : 0.283724 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.355367 s : 3.355367 + pz : 1.038148 p : 3.484037 + px : 1.505873 + py : 0.940017 + dz2 : 0.030194 d : 0.295231 + dxz : 0.022347 + dyz : 0.065514 + dx2y2 : 0.074840 + dxy : 0.102336 + + 1 O s : 3.385037 s : 3.385037 + pz : 1.302453 p : 4.036371 + px : 1.437029 + py : 1.296889 + dz2 : 0.065138 d : 0.754600 + dxz : 0.064454 + dyz : 0.185836 + dx2y2 : 0.210439 + dxy : 0.228733 + + 2 O s : 3.600949 s : 3.600949 + pz : 1.205263 p : 4.109119 + px : 1.385530 + py : 1.518326 + dz2 : 0.042482 d : 0.263013 + dxz : 0.053496 + dyz : 0.039301 + dx2y2 : 0.067582 + dxy : 0.060152 + + 3 H s : 0.636948 s : 0.636948 + pz : 0.033285 p : 0.079328 + px : 0.033625 + py : 0.012418 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3944 7.0000 -0.3944 2.5725 2.5725 -0.0000 + 1 O 7.8088 8.0000 0.1912 2.5690 2.5690 -0.0000 + 2 O 8.0816 8.0000 -0.0816 1.6834 1.6834 0.0000 + 3 H 0.7151 1.0000 0.2849 0.9036 0.9036 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3252 B( 0-N , 2-O ) : 0.4064 B( 0-N , 3-H ) : 0.8409 +B( 1-O , 2-O ) : 1.2290 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 3 sec + +Total time .... 3.231 sec +Sum of individual times .... 3.220 sec ( 99.7%) + +SCF preparation .... 1.098 sec ( 34.0%) +Fock matrix formation .... 0.083 sec ( 2.6%) + Startup .... 0.005 sec ( 6.2% of F) + Split-RI-J .... 0.010 sec ( 12.7% of F) + XC integration .... 0.057 sec ( 69.3% of F) + Basis function eval. .... 0.003 sec ( 5.1% of XC) + Density eval. .... 0.004 sec ( 7.6% of XC) + XC-Functional eval. .... 0.003 sec ( 4.4% of XC) + XC-Potential eval. .... 0.004 sec ( 7.8% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.004 sec ( 0.1%) +Total Energy calculation .... 0.006 sec ( 0.2%) +Population analysis .... 1.997 sec ( 61.8%) +Orbital Transformation .... 0.006 sec ( 0.2%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.009 sec ( 0.3%) +SOSCF solution .... 0.016 sec ( 0.5%) +Finished LeanSCF after 5.3 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 43.1 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000361849 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007155296 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.502457725264 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.032.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.032.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.341423 0.795219 -0.228987 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5092511726182352 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.049430789 1.076956124 -0.262913242 +Nuclear contribution : -0.727781053 -1.394957858 0.502778028 + ----------------------------------------- +Total Dipole Moment : -0.678350263 -0.318001735 0.239864786 + ----------------------------------------- +Magnitude (a.u.) : 0.786650684 +Magnitude (Debye) : 1.999507136 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.818271 0.421181 0.380574 +Rotational constants in MHz : 84489.638178 12626.690067 11409.329999 + +Dipole components along the rotational axes: +x,y,z [a.u.] : -0.452056 -0.314422 0.561786 +x,y,z [Debye]: -1.149034 -0.799197 1.427947 + + + +Dipole moment calculation done in 0.8 sec + +Maximum memory used throughout the entire PROP-calculation: 22.6 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 33 * + * * + * Dihedral ( 2, 1, 0, 3) : 115.38461538 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.3340 0.616667 + 2. B(O 2,O 1) 1.2928 0.723219 + 3. B(H 3,N 0) 1.0365 0.397686 + 4. A(O 1,N 0,H 3) 103.8566 0.351026 + 5. A(N 0,O 1,O 2) 115.4164 0.434153 + 6. D(O 2,O 1,N 0,H 3) 115.3846 0.029012 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.095567 -0.716025 -0.256391 + O -0.194907 0.584867 -0.308965 + O 0.703979 1.374342 0.180972 + H -0.623347 -1.105340 0.380677 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.180595 -1.353092 -0.484509 + 1 O 8.0000 0 15.999 -0.368321 1.105239 -0.583859 + 2 O 8.0000 0 15.999 1.330328 2.597130 0.341987 + 3 H 1.0000 0 1.008 -1.177955 -2.088790 0.719375 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.333564887416 0.00000000 0.00000000 + O 2 1 0 1.290179302709 115.54449363 0.00000000 + H 1 2 3 1.032974460745 103.95017322 106.15384621 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.520072419029 0.00000000 0.00000000 + O 2 1 0 2.438085545773 115.54449363 0.00000000 + H 1 2 3 1.952038834143 103.95017322 106.15384621 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1670 + la=0 lb=0: 144 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.090031462248 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.871e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22300 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5575 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.0900314622 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.2 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 1.1 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5172760159678660 0.00e+00 4.05e-04 3.22e-03 2.57e-02 0.700 0.6 +Warning: op=0 Small HOMO/LUMO gap ( 0.036) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5185041486625437 -1.23e-03 5.01e-04 3.93e-03 2.02e-02 0.700 0.5 + ***Turning on AO-DIIS*** + 3 -205.5195469167791202 -1.04e-03 3.95e-04 2.96e-03 1.44e-02 0.700 0.2 + 4 -205.5202789207554019 -7.32e-04 1.03e-03 7.40e-03 1.02e-02 0.000 0.1 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5219947221354460 -1.72e-03 1.10e-04 8.99e-04 1.03e-03 0.3 + *** Restarting incremental Fock matrix formation *** + 6 -205.5220067393265708 -1.20e-05 2.12e-04 2.72e-03 7.41e-04 0.3 + 7 -205.5219919515454876 1.48e-05 2.04e-04 1.65e-03 2.04e-03 0.1 + 8 -205.5220201980881143 -2.82e-05 1.85e-04 2.85e-03 1.02e-03 0.1 + 9 -205.5219690958143701 5.11e-05 1.28e-04 2.22e-03 3.02e-03 0.1 + 10 -205.5220304946338956 -6.14e-05 1.04e-05 9.41e-05 3.80e-05 0.1 + 11 -205.5220305294322429 -3.48e-08 3.11e-06 4.11e-05 2.22e-05 0.1 + 12 -205.5220305415312509 -1.21e-08 9.92e-07 9.40e-06 3.87e-06 0.1 + 13 -205.5220305417931286 -2.62e-10 3.43e-07 3.07e-06 2.31e-06 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 13 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.52203054179313 Eh -5592.53877 eV + +Components: +Nuclear Repulsion : 69.09003146224831 Eh 1880.03534 eV +Electronic Energy : -274.61206200404138 Eh -7472.57411 eV +One Electron Energy: -417.92257158404283 Eh -11372.25133 eV +Two Electron Energy: 143.31050958000142 Eh 3899.67722 eV + +Virial components: +Potential Energy : -410.31229233323199 Eh -11165.16510 eV +Kinetic Energy : 204.79026179143887 Eh 5572.62633 eV +Virial Ratio : 2.00357325950928 + +DFT components: +N(Alpha) : 11.999997300662 electrons +N(Beta) : 11.999997300662 electrons +N(Total) : 23.999994601324 electrons +E(X) : -23.317797663345 Eh +E(C) : -0.803011397380 Eh +E(XC) : -24.120809060725 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.6188e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.0683e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.4270e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.0346e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.3104e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 7.7945e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.185752 -522.0709 + 1 2.0000 -19.045876 -518.2646 + 2 2.0000 -14.248522 -387.7220 + 3 2.0000 -1.244451 -33.8632 + 4 2.0000 -0.955843 -26.0098 + 5 2.0000 -0.709093 -19.2954 + 6 2.0000 -0.557973 -15.1832 + 7 2.0000 -0.512956 -13.9582 + 8 2.0000 -0.503818 -13.7096 + 9 2.0000 -0.335637 -9.1331 + 10 2.0000 -0.274872 -7.4796 + 11 2.0000 -0.252742 -6.8775 + 12 0.0000 -0.215028 -5.8512 + 13 0.0000 0.044511 1.2112 + 14 0.0000 0.089814 2.4440 + 15 0.0000 0.122554 3.3349 + 16 0.0000 0.224455 6.1077 + 17 0.0000 0.267276 7.2729 + 18 0.0000 0.316398 8.6096 + 19 0.0000 0.332492 9.0476 + 20 0.0000 0.342694 9.3252 + 21 0.0000 0.380416 10.3516 + 22 0.0000 0.395185 10.7535 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.366990 + 1 O : 0.193114 + 2 O : -0.105735 + 3 H : 0.279611 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.889199 s : 3.889199 + pz : 1.081642 p : 3.430169 + px : 1.538620 + py : 0.809908 + dz2 : 0.004004 d : 0.047621 + dxz : 0.010147 + dyz : 0.011540 + dx2y2 : 0.011389 + dxy : 0.010542 + + 1 O s : 3.773302 s : 3.773302 + pz : 1.386787 p : 3.915374 + px : 1.436020 + py : 1.092567 + dz2 : 0.011008 d : 0.118209 + dxz : 0.012930 + dyz : 0.036350 + dx2y2 : 0.044975 + dxy : 0.012947 + + 2 O s : 3.941008 s : 3.941008 + pz : 1.248992 p : 4.143476 + px : 1.405822 + py : 1.488662 + dz2 : 0.003960 d : 0.021251 + dxz : 0.003930 + dyz : 0.005053 + dx2y2 : 0.002946 + dxy : 0.005361 + + 3 H s : 0.689810 s : 0.689810 + pz : 0.011981 p : 0.030579 + px : 0.012233 + py : 0.006366 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.116402 + 1 O : -0.178727 + 2 O : 0.013341 + 3 H : 0.281788 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.365470 s : 3.365470 + pz : 1.031287 p : 3.452923 + px : 1.473856 + py : 0.947780 + dz2 : 0.030267 d : 0.298009 + dxz : 0.021755 + dyz : 0.065153 + dx2y2 : 0.073583 + dxy : 0.107251 + + 1 O s : 3.385166 s : 3.385166 + pz : 1.299349 p : 4.039541 + px : 1.452469 + py : 1.287723 + dz2 : 0.063292 d : 0.754020 + dxz : 0.057944 + dyz : 0.183788 + dx2y2 : 0.217121 + dxy : 0.231875 + + 2 O s : 3.601436 s : 3.601436 + pz : 1.221026 p : 4.122838 + px : 1.401664 + py : 1.500148 + dz2 : 0.039627 d : 0.262385 + dxz : 0.049007 + dyz : 0.037603 + dx2y2 : 0.071974 + dxy : 0.064174 + + 3 H s : 0.640579 s : 0.640579 + pz : 0.030006 p : 0.077633 + px : 0.034485 + py : 0.013142 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3670 7.0000 -0.3670 2.6118 2.6118 0.0000 + 1 O 7.8069 8.0000 0.1931 2.5747 2.5747 0.0000 + 2 O 8.1057 8.0000 -0.1057 1.6961 1.6961 -0.0000 + 3 H 0.7204 1.0000 0.2796 0.9058 0.9058 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3335 B( 0-N , 2-O ) : 0.4266 B( 0-N , 3-H ) : 0.8517 +B( 1-O , 2-O ) : 1.2283 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 6 sec + +Total time .... 6.399 sec +Sum of individual times .... 6.294 sec ( 98.4%) + +SCF preparation .... 1.035 sec ( 16.2%) +Fock matrix formation .... 1.758 sec ( 27.5%) + Startup .... 0.144 sec ( 8.2% of F) + Split-RI-J .... 0.048 sec ( 2.7% of F) + XC integration .... 0.338 sec ( 19.3% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.013 sec ( 3.9% of XC) + Density eval. .... 0.018 sec ( 5.3% of XC) + XC-Functional eval. .... 0.013 sec ( 3.8% of XC) + XC-Potential eval. .... 0.019 sec ( 5.7% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.362 sec ( 5.7%) +Total Energy calculation .... 0.027 sec ( 0.4%) +Population analysis .... 2.164 sec ( 33.8%) +Orbital Transformation .... 0.269 sec ( 4.2%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.498 sec ( 7.8%) +SOSCF solution .... 0.181 sec ( 2.8%) +Finished LeanSCF after 8.7 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 43.5 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000361360 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007154595 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.515237306287 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.0 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003479 -0.000005790 0.000001383 + 2 O : -0.000000338 0.000000752 -0.000000422 + 3 O : 0.000003471 0.000007927 0.000000710 + 4 H : 0.000000346 -0.000002890 -0.000001671 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000116215 +RMS gradient ... 0.0000033548 +MAX gradient ... 0.0000079275 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.034175594 -0.013134114 -0.023174229 + 2 O : 0.023443449 0.011179503 -0.041115273 + 3 O : -0.013084498 -0.001116172 0.032012006 + 4 H : 0.023816643 0.003070783 0.032277496 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000306003 0.0000055559 -0.0000149615 + +Norm of the Cartesian gradient ... 0.0840135749 +RMS gradient ... 0.0242526301 +MAX gradient ... 0.0411152730 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.210 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.004 sec ( 2.1%) +RI-J Coulomb gradient .... 0.050 sec ( 23.7%) +XC gradient .... 0.016 sec ( 7.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.515237306 Eh +Current gradient norm .... 0.084013575 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999747752 +Lowest eigenvalues of augmented Hessian: + -0.000226814 0.350280650 0.392632301 0.433294889 0.615864866 +Length of the computed step .... 0.022465243 +The final length of the internal step .... 0.022465243 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0091713969 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0090520258 RMS(Int)= 0.0091665008 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0042858855 0.0001000000 NO + MAX gradient 0.0079186289 0.0003000000 NO + RMS step 0.0091713969 0.0020000000 NO + MAX step 0.0169756993 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0068 Max(Angles) 0.97 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3340 0.007919 -0.0068 1.3272 + 2. B(O 2,O 1) 1.2928 0.002353 -0.0017 1.2911 + 3. B(H 3,N 0) 1.0365 0.002163 -0.0029 1.0336 + 4. A(O 1,N 0,H 3) 103.86 0.005948 -0.97 102.88 + 5. A(N 0,O 1,O 2) 115.42 -0.001381 0.18 115.60 + 6. D(O 2,O 1,N 0,H 3) 115.38 -0.076172 0.00 115.38 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.271 %) +Internal coordinates : 0.000 s ( 0.095 %) +B/P matrices and projection : 0.000 s ( 0.379 %) +Hessian update/contruction : 0.013 s (56.162 %) +Making the step : 0.000 s ( 0.215 %) +Converting the step to Cartesian: 0.000 s ( 0.155 %) +Storing new data : 0.000 s ( 0.129 %) +Checking convergence : 0.000 s ( 0.000 %) +Final printing : 0.010 s (42.582 %) +Total time : 0.023 s + +Time for energy+gradient : 14.433 s +Time for complete geometry iter : 15.390 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.097746 -0.716175 -0.259811 + O -0.195449 0.577401 -0.305153 + O 0.700227 1.369772 0.181393 + H -0.621233 -1.093155 0.379863 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.184714 -1.353374 -0.490971 + 1 O 8.0000 0 15.999 -0.369345 1.091130 -0.576656 + 2 O 8.0000 0 15.999 1.323238 2.588495 0.342783 + 3 H 1.0000 0 1.008 -1.173959 -2.065763 0.717836 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.327161753448 0.00000000 0.00000000 + O 2 1 0 1.291051776860 115.59897983 0.00000000 + H 1 2 3 1.033550351676 102.88395380 115.38461512 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.507972249431 0.00000000 0.00000000 + O 2 1 0 2.439734282978 115.59897983 0.00000000 + H 1 2 3 1.953127110285 102.88395380 115.38461512 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1679 + la=0 lb=0: 146 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.313256203778 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.847e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22299 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5575 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.9 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5221104174298432 0.00e+00 1.99e-04 1.50e-03 5.97e-04 0.9 + *** Restarting incremental Fock matrix formation *** + 2 -205.5221791067965285 -6.87e-05 2.35e-04 2.25e-03 6.65e-04 0.6 + 3 -205.5221247905375606 5.43e-05 1.61e-04 2.63e-03 3.48e-03 0.2 + 4 -205.5221912569840299 -6.65e-05 1.11e-04 1.79e-03 6.35e-04 0.4 + 5 -205.5221771910277369 1.41e-05 7.01e-05 1.29e-03 1.72e-03 0.4 + 6 -205.5221949592475710 -1.78e-05 3.28e-05 5.08e-04 1.14e-04 0.3 + 7 -205.5221949359884377 2.33e-08 1.69e-05 2.89e-04 1.20e-04 0.2 + 8 -205.5221952949495687 -3.59e-07 1.58e-06 1.15e-05 4.68e-06 0.4 + 9 -205.5221952964864442 -1.54e-09 8.85e-07 5.39e-06 2.80e-06 0.4 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.52219529648644 Eh -5592.54325 eV + +Components: +Nuclear Repulsion : 69.31325620377780 Eh 1886.10959 eV +Electronic Energy : -274.83545150026430 Eh -7478.65284 eV +One Electron Energy: -418.34798798458297 Eh -11383.82750 eV +Two Electron Energy: 143.51253648431870 Eh 3905.17465 eV + +Virial components: +Potential Energy : -410.33776799952489 Eh -11165.85833 eV +Kinetic Energy : 204.81557270303847 Eh 5573.31508 eV +Virial Ratio : 2.00345004329565 + +DFT components: +N(Alpha) : 11.999996915110 electrons +N(Beta) : 11.999996915110 electrons +N(Total) : 23.999993830219 electrons +E(X) : -23.324544330721 Eh +E(C) : -0.803463266287 Eh +E(XC) : -24.128007597009 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.5369e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.3906e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 8.8455e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.8489e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.7958e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.7622e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 5 sec +Finished LeanSCF after 7.7 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 43.7 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361547 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007177186 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.515379658360 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.0 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003471 -0.000005724 0.000001395 + 2 O : -0.000000347 0.000000712 -0.000000402 + 3 O : 0.000003410 0.000007812 0.000000719 + 4 H : 0.000000408 -0.000002799 -0.000001712 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000114744 +RMS gradient ... 0.0000033124 +MAX gradient ... 0.0000078120 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.034738690 -0.010521669 -0.022861645 + 2 O : 0.024493828 0.007481891 -0.040369488 + 3 O : -0.014762981 -0.003147951 0.031779852 + 4 H : 0.025007843 0.006187729 0.031451280 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000309897 0.0000050486 -0.0000027587 + +Norm of the Cartesian gradient ... 0.0837641699 +RMS gradient ... 0.0241806330 +MAX gradient ... 0.0403694881 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.304 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.004 sec ( 1.4%) +RI-J Coulomb gradient .... 0.048 sec ( 15.8%) +XC gradient .... 0.014 sec ( 4.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.515379658 Eh +Current gradient norm .... 0.083764170 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999938087 +Lowest eigenvalues of augmented Hessian: + -0.000037434 0.271927046 0.392512457 0.447212453 0.563432040 +Length of the computed step .... 0.011128235 +The final length of the internal step .... 0.011128235 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0045430829 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0036631908 RMS(Int)= 0.0045418240 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000008 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000018719 +Previously predicted energy change .... -0.000113464 +Actually observed energy change .... -0.000142352 +Ratio of predicted to observed change .... 1.254599587 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0001423521 0.0000050000 NO + RMS gradient 0.0014131946 0.0001000000 NO + MAX gradient 0.0023685407 0.0003000000 NO + RMS step 0.0045430829 0.0020000000 NO + MAX step 0.0069906030 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0033 Max(Angles) 0.40 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3272 0.002369 -0.0033 1.3239 + 2. B(O 2,O 1) 1.2911 -0.000196 0.0001 1.2911 + 3. B(H 3,N 0) 1.0336 -0.000190 0.0001 1.0337 + 4. A(O 1,N 0,H 3) 102.88 0.001228 -0.35 102.54 + 5. A(N 0,O 1,O 2) 115.60 -0.002189 0.40 116.00 + 6. D(O 2,O 1,N 0,H 3) 115.38 -0.077392 0.00 115.38 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.098 %) +Internal coordinates : 0.000 s ( 0.036 %) +B/P matrices and projection : 0.000 s ( 0.149 %) +Hessian update/contruction : 0.053 s (93.599 %) +Making the step : 0.000 s ( 0.092 %) +Converting the step to Cartesian: 0.000 s ( 0.057 %) +Storing new data : 0.000 s ( 0.046 %) +Checking convergence : 0.000 s ( 0.018 %) +Final printing : 0.003 s ( 5.903 %) +Total time : 0.056 s + +Time for energy+gradient : 13.634 s +Time for complete geometry iter : 14.426 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.097826 -0.717101 -0.262128 + O -0.193884 0.573621 -0.302526 + O 0.698918 1.371055 0.181155 + H -0.621567 -1.089731 0.379791 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.184864 -1.355124 -0.495349 + 1 O 8.0000 0 15.999 -0.366389 1.083987 -0.571692 + 2 O 8.0000 0 15.999 1.320764 2.590918 0.342332 + 3 H 1.0000 0 1.008 -1.174592 -2.059293 0.717702 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.323891972741 0.00000000 0.00000000 + O 2 1 0 1.291101988787 115.99951185 0.00000000 + H 1 2 3 1.033653336901 102.53665303 115.38461512 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.501793259378 0.00000000 0.00000000 + O 2 1 0 2.439829169769 115.99951185 0.00000000 + H 1 2 3 1.953321724156 102.53665303 115.38461512 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 555 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1681 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.364213189658 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.840e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22300 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5575 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.6 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5221673609259483 0.00e+00 1.41e-04 9.96e-04 4.07e-04 0.5 + *** Restarting incremental Fock matrix formation *** + 2 -205.5222037868298344 -3.64e-05 1.08e-04 9.13e-04 3.44e-04 0.3 + 3 -205.5222071380917441 -3.35e-06 1.71e-04 2.03e-03 7.18e-04 0.1 + 4 -205.5221971070488394 1.00e-05 1.28e-04 1.28e-03 1.11e-03 0.2 + 5 -205.5222108769004308 -1.38e-05 1.65e-05 2.20e-04 7.78e-05 0.2 + 6 -205.5222107629862194 1.14e-07 9.77e-06 1.49e-04 1.81e-04 0.1 + 7 -205.5222109829903729 -2.20e-07 9.59e-06 1.46e-04 5.15e-05 0.1 + 8 -205.5222109816756983 1.31e-09 5.17e-06 7.71e-05 3.89e-05 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.52221098167570 Eh -5592.54368 eV + +Components: +Nuclear Repulsion : 69.36421318965755 Eh 1887.49620 eV +Electronic Energy : -274.88642417133326 Eh -7480.03988 eV +One Electron Energy: -418.44494086717208 Eh -11386.46572 eV +Two Electron Energy: 143.55851669583882 Eh 3906.42584 eV + +Virial components: +Potential Energy : -410.34345946628810 Eh -11166.01320 eV +Kinetic Energy : 204.82124848461237 Eh 5573.46952 eV +Virial Ratio : 2.00342231336958 + +DFT components: +N(Alpha) : 11.999996651090 electrons +N(Beta) : 11.999996651090 electrons +N(Total) : 23.999993302181 electrons +E(X) : -23.326554781176 Eh +E(C) : -0.803600914095 Eh +E(XC) : -24.130155695272 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.3147e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.7133e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 5.1724e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.4883e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.8850e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 4.5056e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 2 sec +Finished LeanSCF after 5.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 43.9 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361560 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007173190 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.515399351923 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003473 -0.000005719 0.000001396 + 2 O : -0.000000349 0.000000695 -0.000000394 + 3 O : 0.000003404 0.000007814 0.000000724 + 4 H : 0.000000418 -0.000002790 -0.000001725 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000114709 +RMS gradient ... 0.0000033114 +MAX gradient ... 0.0000078142 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.035398779 -0.009307603 -0.023371632 + 2 O : 0.025885036 0.005257602 -0.040202428 + 3 O : -0.015422337 -0.002768012 0.031899624 + 4 H : 0.024936080 0.006818012 0.031674436 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000355671 0.0000171167 -0.0000312994 + +Norm of the Cartesian gradient ... 0.0844660323 +RMS gradient ... 0.0243832432 +MAX gradient ... 0.0402024283 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.105 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.004 sec ( 4.2%) +RI-J Coulomb gradient .... 0.052 sec ( 49.3%) +XC gradient .... 0.015 sec ( 14.6%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.515399352 Eh +Current gradient norm .... 0.084466032 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999998923 +Lowest eigenvalues of augmented Hessian: + -0.000000988 0.278988878 0.389529627 0.418966890 0.554597949 +Length of the computed step .... 0.001467636 +The final length of the internal step .... 0.001467636 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0005991598 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0003862937 RMS(Int)= 0.0005991952 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000494 +Previously predicted energy change .... -0.000018719 +Actually observed energy change .... -0.000019694 +Ratio of predicted to observed change .... 1.052055351 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000196936 0.0000050000 NO + RMS gradient 0.0002854351 0.0001000000 NO + MAX gradient 0.0004238093 0.0003000000 NO + RMS step 0.0005991598 0.0020000000 YES + MAX step 0.0009185896 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0005 Max(Angles) 0.04 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3239 0.000378 -0.0005 1.3234 + 2. B(O 2,O 1) 1.2911 -0.000424 0.0003 1.2914 + 3. B(H 3,N 0) 1.0337 -0.000146 0.0002 1.0338 + 4. A(O 1,N 0,H 3) 102.54 -0.000302 0.03 102.57 + 5. A(N 0,O 1,O 2) 116.00 -0.000231 0.04 116.04 + 6. D(O 2,O 1,N 0,H 3) 115.38 -0.077949 0.00 115.38 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.480 %) +Internal coordinates : 0.000 s ( 3.211 %) +B/P matrices and projection : 0.000 s (12.844 %) +Hessian update/contruction : 0.000 s (30.734 %) +Making the step : 0.000 s ( 6.116 %) +Converting the step to Cartesian: 0.000 s ( 4.128 %) +Storing new data : 0.000 s ( 3.364 %) +Checking convergence : 0.000 s ( 1.529 %) +Final printing : 0.000 s (28.287 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.097633 -0.716948 -0.262163 + O -0.193663 0.573372 -0.302475 + O 0.699029 1.371482 0.181120 + H -0.621706 -1.090062 0.379810 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.184499 -1.354835 -0.495416 + 1 O 8.0000 0 15.999 -0.365971 1.083516 -0.571595 + 2 O 8.0000 0 15.999 1.320973 2.591726 0.342267 + 3 H 1.0000 0 1.008 -1.174855 -2.059920 0.717737 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.323405876081 0.00000000 0.00000000 + O 2 1 0 1.291411629614 116.04036380 0.00000000 + H 1 2 3 1.033824651687 102.57077106 115.38461512 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.500874669814 0.00000000 0.00000000 + O 2 1 0 2.440414306132 116.04036380 0.00000000 + H 1 2 3 1.953645462185 102.57077106 115.38461512 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 553 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1673 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 170 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.362891908332 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.842e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22300 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5575 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.3628919083 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5222091405869946 0.00e+00 1.75e-05 1.60e-04 3.80e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5222096217564172 -4.81e-07 1.07e-05 1.06e-04 4.32e-05 0.0 + 3 -205.5222095852957978 3.65e-08 9.84e-06 1.17e-04 1.20e-04 0.0 + 4 -205.5222096389409785 -5.36e-08 8.27e-06 9.23e-05 4.08e-05 0.0 + 5 -205.5222096345352725 4.41e-09 4.01e-06 6.38e-05 7.91e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.52220963453527 Eh -5592.54364 eV + +Components: +Nuclear Repulsion : 69.36289190833172 Eh 1887.46025 eV +Electronic Energy : -274.88510154286701 Eh -7480.00389 eV +One Electron Energy: -418.44116623878074 Eh -11386.36300 eV +Two Electron Energy: 143.55606469591376 Eh 3906.35912 eV + +Virial components: +Potential Energy : -410.34325763365189 Eh -11166.00771 eV +Kinetic Energy : 204.82104799911659 Eh 5573.46407 eV +Virial Ratio : 2.00342328897478 + +DFT components: +N(Alpha) : 11.999996633127 electrons +N(Beta) : 11.999996633127 electrons +N(Total) : 23.999993266255 electrons +E(X) : -23.326357801675 Eh +E(C) : -0.803596783867 Eh +E(XC) : -24.129954585542 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -4.4057e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.3841e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.0082e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.4791e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 7.9058e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 8.3135e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.185966 -522.0767 + 1 2.0000 -19.045071 -518.2427 + 2 2.0000 -14.248214 -387.7136 + 3 2.0000 -1.248002 -33.9599 + 4 2.0000 -0.960849 -26.1460 + 5 2.0000 -0.707396 -19.2492 + 6 2.0000 -0.559699 -15.2302 + 7 2.0000 -0.514448 -13.9988 + 8 2.0000 -0.505009 -13.7420 + 9 2.0000 -0.336696 -9.1620 + 10 2.0000 -0.274767 -7.4768 + 11 2.0000 -0.252450 -6.8695 + 12 0.0000 -0.213834 -5.8187 + 13 0.0000 0.048303 1.3144 + 14 0.0000 0.088906 2.4193 + 15 0.0000 0.129545 3.5251 + 16 0.0000 0.225794 6.1442 + 17 0.0000 0.266401 7.2491 + 18 0.0000 0.316969 8.6252 + 19 0.0000 0.331007 9.0071 + 20 0.0000 0.342791 9.3278 + 21 0.0000 0.381790 10.3890 + 22 0.0000 0.394840 10.7441 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.368091 + 1 O : 0.196092 + 2 O : -0.108785 + 3 H : 0.280784 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.890357 s : 3.890357 + pz : 1.079127 p : 3.429016 + px : 1.538191 + py : 0.811698 + dz2 : 0.004127 d : 0.048718 + dxz : 0.010423 + dyz : 0.011956 + dx2y2 : 0.011743 + dxy : 0.010469 + + 1 O s : 3.767484 s : 3.767484 + pz : 1.382108 p : 3.916532 + px : 1.443786 + py : 1.090638 + dz2 : 0.010898 d : 0.119893 + dxz : 0.012809 + dyz : 0.037355 + dx2y2 : 0.045522 + dxy : 0.013309 + + 2 O s : 3.940208 s : 3.940208 + pz : 1.242252 p : 4.147527 + px : 1.420579 + py : 1.484695 + dz2 : 0.003820 d : 0.021050 + dxz : 0.004002 + dyz : 0.005121 + dx2y2 : 0.002694 + dxy : 0.005413 + + 3 H s : 0.688356 s : 0.688356 + pz : 0.012170 p : 0.030860 + px : 0.012297 + py : 0.006393 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.114064 + 1 O : -0.182807 + 2 O : 0.014075 + 3 H : 0.282797 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.360290 s : 3.360290 + pz : 1.028063 p : 3.452497 + px : 1.470931 + py : 0.953503 + dz2 : 0.030720 d : 0.301278 + dxz : 0.022014 + dyz : 0.065754 + dx2y2 : 0.074481 + dxy : 0.108309 + + 1 O s : 3.379202 s : 3.379202 + pz : 1.293864 p : 4.041601 + px : 1.458107 + py : 1.289630 + dz2 : 0.063617 d : 0.762004 + dxz : 0.056772 + dyz : 0.187365 + dx2y2 : 0.219124 + dxy : 0.235127 + + 2 O s : 3.600200 s : 3.600200 + pz : 1.213595 p : 4.124477 + px : 1.413033 + py : 1.497849 + dz2 : 0.039187 d : 0.261248 + dxz : 0.047805 + dyz : 0.037723 + dx2y2 : 0.072056 + dxy : 0.064477 + + 3 H s : 0.639294 s : 0.639294 + pz : 0.030444 p : 0.077910 + px : 0.034595 + py : 0.012871 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3681 7.0000 -0.3681 2.6083 2.6083 0.0000 + 1 O 7.8039 8.0000 0.1961 2.5752 2.5752 -0.0000 + 2 O 8.1088 8.0000 -0.1088 1.6929 1.6929 -0.0000 + 3 H 0.7192 1.0000 0.2808 0.9056 0.9056 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3343 B( 0-N , 2-O ) : 0.4226 B( 0-N , 3-H ) : 0.8514 +B( 1-O , 2-O ) : 1.2285 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 3 sec + +Total time .... 3.373 sec +Sum of individual times .... 3.360 sec ( 99.6%) + +SCF preparation .... 1.102 sec ( 32.7%) +Fock matrix formation .... 0.120 sec ( 3.6%) + Startup .... 0.007 sec ( 5.7% of F) + Split-RI-J .... 0.015 sec ( 12.4% of F) + XC integration .... 0.082 sec ( 68.2% of F) + Basis function eval. .... 0.004 sec ( 4.3% of XC) + Density eval. .... 0.006 sec ( 7.1% of XC) + XC-Functional eval. .... 0.004 sec ( 4.8% of XC) + XC-Potential eval. .... 0.006 sec ( 7.2% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.007 sec ( 0.2%) +Total Energy calculation .... 0.009 sec ( 0.3%) +Population analysis .... 2.081 sec ( 61.7%) +Orbital Transformation .... 0.006 sec ( 0.2%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.009 sec ( 0.3%) +SOSCF solution .... 0.025 sec ( 0.7%) +Finished LeanSCF after 5.5 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 44.2 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000361552 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007171123 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.515400064220 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.033.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.033.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.354777 0.802898 -0.210258 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5222096345352725 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.039596351 1.002333171 -0.245545494 +Nuclear contribution : -0.757978445 -1.411370530 0.461379164 + ----------------------------------------- +Total Dipole Moment : -0.718382094 -0.409037359 0.215833671 + ----------------------------------------- +Magnitude (a.u.) : 0.854381979 +Magnitude (Debye) : 2.171666407 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 2.924775 0.420745 0.380572 +Rotational constants in MHz : 87682.551616 12613.627738 11409.252837 + +Dipole components along the rotational axes: +x,y,z [a.u.] : -0.560755 -0.394411 0.509865 +x,y,z [Debye]: -1.425326 -1.002514 1.295974 + + + +Dipole moment calculation done in 0.7 sec + +Maximum memory used throughout the entire PROP-calculation: 23.1 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 34 * + * * + * Dihedral ( 2, 1, 0, 3) : 124.61538462 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.3237 0.640117 + 2. B(O 2,O 1) 1.2942 0.719952 + 3. B(H 3,N 0) 1.0373 0.396446 + 4. A(O 1,N 0,H 3) 102.5050 0.353062 + 5. A(N 0,O 1,O 2) 115.9129 0.436725 + 6. D(O 2,O 1,N 0,H 3) 124.6154 0.031462 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.114689 -0.710905 -0.232041 + O -0.202233 0.573996 -0.260621 + O 0.715067 1.391906 0.144873 + H -0.646232 -1.117154 0.344081 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.216732 -1.343415 -0.438494 + 1 O 8.0000 0 15.999 -0.382165 1.084696 -0.492503 + 2 O 8.0000 0 15.999 1.351281 2.630321 0.273770 + 3 H 1.0000 0 1.008 -1.221201 -2.111115 0.650220 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.323405876081 0.00000000 0.00000000 + O 2 1 0 1.291411629614 116.04036380 0.00000000 + H 1 2 3 1.033824651687 102.57077106 115.38461512 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.500874669814 0.00000000 0.00000000 + O 2 1 0 2.440414306132 116.04036380 0.00000000 + H 1 2 3 1.953645462185 102.57077106 115.38461512 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1666 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.249234193354 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.880e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22306 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.2492341934 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5294203963793507 0.00e+00 4.07e-04 3.28e-03 2.58e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.053) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5306497678365645 -1.23e-03 4.88e-04 4.29e-03 2.03e-02 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.5316752848031001 -1.03e-03 3.78e-04 3.22e-03 1.44e-02 0.700 0.0 + 4 -205.5323931736691065 -7.18e-04 9.57e-04 8.10e-03 1.02e-02 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5340674489632420 -1.67e-03 8.61e-05 7.39e-04 8.47e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 6 -205.5340736578887118 -6.21e-06 2.01e-04 3.39e-03 7.40e-04 0.1 + 7 -205.5340265536028710 4.71e-05 1.71e-04 1.94e-03 3.05e-03 0.0 + 8 -205.5340831384700664 -5.66e-05 1.34e-04 2.24e-03 7.01e-04 0.0 + 9 -205.5340528335037789 3.03e-05 9.40e-05 1.65e-03 2.35e-03 0.0 + 10 -205.5340880578930864 -3.52e-05 5.79e-06 6.72e-05 2.55e-05 0.0 + 11 -205.5340880692312453 -1.13e-08 1.64e-06 1.61e-05 1.46e-05 0.0 + 12 -205.5340880728193156 -3.59e-09 4.47e-07 4.59e-06 1.98e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.53408807281932 Eh -5592.86687 eV + +Components: +Nuclear Repulsion : 69.24923419335448 Eh 1884.36746 eV +Electronic Energy : -274.78332226617374 Eh -7477.23433 eV +One Electron Energy: -418.24334108192630 Eh -11380.97991 eV +Two Electron Energy: 143.46001881575253 Eh 3903.74557 eV + +Virial components: +Potential Energy : -410.33231906139542 Eh -11165.71006 eV +Kinetic Energy : 204.79823098857608 Eh 5572.84318 eV +Virial Ratio : 2.00359308320532 + +DFT components: +N(Alpha) : 11.999997930191 electrons +N(Beta) : 11.999997930191 electrons +N(Total) : 23.999995860382 electrons +E(X) : -23.324163623574 Eh +E(C) : -0.803316255130 Eh +E(XC) : -24.127479878704 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.5881e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.5924e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.4657e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.4695e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.9792e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 8.0138e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.186492 -522.0910 + 1 2.0000 -19.038588 -518.0663 + 2 2.0000 -14.254881 -387.8950 + 3 2.0000 -1.245351 -33.8877 + 4 2.0000 -0.960052 -26.1243 + 5 2.0000 -0.706502 -19.2249 + 6 2.0000 -0.559135 -15.2148 + 7 2.0000 -0.512822 -13.9546 + 8 2.0000 -0.505089 -13.7442 + 9 2.0000 -0.335046 -9.1171 + 10 2.0000 -0.271826 -7.3968 + 11 2.0000 -0.260510 -7.0888 + 12 0.0000 -0.206492 -5.6189 + 13 0.0000 0.046278 1.2593 + 14 0.0000 0.085760 2.3337 + 15 0.0000 0.128249 3.4898 + 16 0.0000 0.223696 6.0871 + 17 0.0000 0.268417 7.3040 + 18 0.0000 0.314668 8.5626 + 19 0.0000 0.332371 9.0443 + 20 0.0000 0.339260 9.2317 + 21 0.0000 0.380649 10.3580 + 22 0.0000 0.398238 10.8366 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.347192 + 1 O : 0.199925 + 2 O : -0.130065 + 3 H : 0.277331 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.894972 s : 3.894972 + pz : 1.081206 p : 3.401560 + px : 1.501800 + py : 0.818555 + dz2 : 0.004635 d : 0.050659 + dxz : 0.010768 + dyz : 0.012086 + dx2y2 : 0.011936 + dxy : 0.011233 + + 1 O s : 3.766322 s : 3.766322 + pz : 1.385913 p : 3.912400 + px : 1.446660 + py : 1.079826 + dz2 : 0.009202 d : 0.121353 + dxz : 0.012637 + dyz : 0.037764 + dx2y2 : 0.047505 + dxy : 0.014246 + + 2 O s : 3.942740 s : 3.942740 + pz : 1.278598 p : 4.165215 + px : 1.423156 + py : 1.463461 + dz2 : 0.003346 d : 0.022109 + dxz : 0.005162 + dyz : 0.004596 + dx2y2 : 0.002893 + dxy : 0.006112 + + 3 H s : 0.692513 s : 0.692513 + pz : 0.010970 p : 0.030155 + px : 0.012575 + py : 0.006610 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.100110 + 1 O : -0.183997 + 2 O : 0.002309 + 3 H : 0.281798 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.367457 s : 3.367457 + pz : 1.024826 p : 3.429524 + px : 1.446596 + py : 0.958102 + dz2 : 0.031413 d : 0.303129 + dxz : 0.020539 + dyz : 0.065006 + dx2y2 : 0.073408 + dxy : 0.112763 + + 1 O s : 3.379928 s : 3.379928 + pz : 1.291666 p : 4.041683 + px : 1.467138 + py : 1.282878 + dz2 : 0.062567 d : 0.762387 + dxz : 0.049785 + dyz : 0.185947 + dx2y2 : 0.224505 + dxy : 0.239583 + + 2 O s : 3.601132 s : 3.601132 + pz : 1.236719 p : 4.136211 + px : 1.420000 + py : 1.479491 + dz2 : 0.036649 d : 0.260348 + dxz : 0.043450 + dyz : 0.036239 + dx2y2 : 0.075723 + dxy : 0.068287 + + 3 H s : 0.641850 s : 0.641850 + pz : 0.027152 p : 0.076352 + px : 0.035701 + py : 0.013498 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3472 7.0000 -0.3472 2.6393 2.6393 -0.0000 + 1 O 7.8001 8.0000 0.1999 2.5873 2.5873 -0.0000 + 2 O 8.1301 8.0000 -0.1301 1.7055 1.7055 -0.0000 + 3 H 0.7227 1.0000 0.2773 0.9074 0.9074 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3435 B( 0-N , 2-O ) : 0.4368 B( 0-N , 3-H ) : 0.8590 +B( 1-O , 2-O ) : 1.2320 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 3 sec + +Total time .... 3.623 sec +Sum of individual times .... 3.611 sec ( 99.7%) + +SCF preparation .... 1.105 sec ( 30.5%) +Fock matrix formation .... 0.275 sec ( 7.6%) + Startup .... 0.012 sec ( 4.5% of F) + Split-RI-J .... 0.047 sec ( 17.3% of F) + XC integration .... 0.173 sec ( 63.0% of F) + Basis function eval. .... 0.012 sec ( 6.8% of XC) + Density eval. .... 0.016 sec ( 9.0% of XC) + XC-Functional eval. .... 0.009 sec ( 5.4% of XC) + XC-Potential eval. .... 0.016 sec ( 9.3% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.019 sec ( 0.5%) +Total Energy calculation .... 0.023 sec ( 0.6%) +Population analysis .... 2.075 sec ( 57.3%) +Orbital Transformation .... 0.013 sec ( 0.3%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.063 sec ( 1.7%) +SOSCF solution .... 0.038 sec ( 1.1%) +Finished LeanSCF after 5.7 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 44.5 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000361070 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007172329 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.527276812929 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003568 -0.000005846 0.000001264 + 2 O : -0.000000370 0.000000692 -0.000000338 + 3 O : 0.000003596 0.000008146 0.000000552 + 4 H : 0.000000342 -0.000002992 -0.000001478 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000118353 +RMS gradient ... 0.0000034166 +MAX gradient ... 0.0000081455 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.025451228 -0.012934057 -0.022286625 + 2 O : 0.015231801 0.010913353 -0.039384603 + 3 O : -0.008473095 -0.000636537 0.030541670 + 4 H : 0.018692522 0.002657240 0.031129558 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000139794 0.0000169466 -0.0000434802 + +Norm of the Cartesian gradient ... 0.0744615156 +RMS gradient ... 0.0214951880 +MAX gradient ... 0.0393846028 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.326 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.005 sec ( 1.5%) +RI-J Coulomb gradient .... 0.053 sec ( 16.1%) +XC gradient .... 0.015 sec ( 4.6%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.527276813 Eh +Current gradient norm .... 0.074461516 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999805970 +Lowest eigenvalues of augmented Hessian: + -0.000198137 0.352282036 0.391457208 0.435848674 0.639499617 +Length of the computed step .... 0.019702116 +The final length of the internal step .... 0.019702116 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0080433551 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0075668744 RMS(Int)= 0.0080382041 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0042605039 0.0001000000 NO + MAX gradient 0.0085524813 0.0003000000 NO + RMS step 0.0080433551 0.0020000000 NO + MAX step 0.0133719567 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0071 Max(Angles) 0.66 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3237 0.008552 -0.0071 1.3166 + 2. B(O 2,O 1) 1.2942 0.003160 -0.0023 1.2918 + 3. B(H 3,N 0) 1.0373 0.002534 -0.0034 1.0339 + 4. A(O 1,N 0,H 3) 102.50 0.004060 -0.66 101.84 + 5. A(N 0,O 1,O 2) 115.91 -0.001696 0.22 116.14 + 6. D(O 2,O 1,N 0,H 3) 124.62 -0.069385 0.00 124.62 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.608 %) +Internal coordinates : 0.000 s ( 0.212 %) +B/P matrices and projection : 0.000 s ( 0.859 %) +Hessian update/contruction : 0.006 s (56.568 %) +Making the step : 0.000 s ( 0.425 %) +Converting the step to Cartesian: 0.000 s ( 0.299 %) +Storing new data : 0.000 s ( 0.328 %) +Checking convergence : 0.000 s ( 0.000 %) +Final printing : 0.004 s (40.672 %) +Total time : 0.010 s + +Time for energy+gradient : 10.743 s +Time for complete geometry iter : 11.931 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.115821 -0.710220 -0.234278 + O -0.201603 0.567373 -0.257517 + O 0.711351 1.387955 0.144896 + H -0.644278 -1.107265 0.343192 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.218871 -1.342121 -0.442721 + 1 O 8.0000 0 15.999 -0.380974 1.072180 -0.486637 + 2 O 8.0000 0 15.999 1.344259 2.622855 0.273813 + 3 H 1.0000 0 1.008 -1.217509 -2.092427 0.648538 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.316640906812 0.00000000 0.00000000 + O 2 1 0 1.291811421457 116.13575806 0.00000000 + H 1 2 3 1.033859669772 101.84486610 124.61538461 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.488090730592 0.00000000 0.00000000 + O 2 1 0 2.441169803226 116.13575806 0.00000000 + H 1 2 3 1.953711636775 101.84486610 124.61538461 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1668 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.489550485304 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.849e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22306 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.8 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5341513242876204 0.00e+00 1.86e-04 1.23e-03 4.59e-04 0.6 + *** Restarting incremental Fock matrix formation *** + 2 -205.5342117299589972 -6.04e-05 2.25e-04 2.33e-03 6.29e-04 0.3 + 3 -205.5341522701320969 5.95e-05 1.60e-04 2.71e-03 3.28e-03 0.2 + 4 -205.5342189403447151 -6.67e-05 1.27e-04 2.13e-03 5.97e-04 0.2 + 5 -205.5341987738653415 2.02e-05 8.23e-05 1.52e-03 1.85e-03 0.2 + 6 -205.5342230649280282 -2.43e-05 3.19e-05 5.37e-04 1.08e-04 0.2 + 7 -205.5342230013009157 6.36e-08 1.69e-05 2.97e-04 1.17e-04 0.1 + 8 -205.5342233603259388 -3.59e-07 6.97e-07 7.88e-06 2.98e-06 0.2 + 9 -205.5342233609483742 -6.22e-10 2.49e-07 1.92e-06 2.33e-06 0.2 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.53422336094837 Eh -5592.87055 eV + +Components: +Nuclear Repulsion : 69.48955048530428 Eh 1890.90680 eV +Electronic Energy : -275.02377384625265 Eh -7483.77735 eV +One Electron Energy: -418.70109800790675 Eh -11393.43611 eV +Two Electron Energy: 143.67732416165413 Eh 3909.65875 eV + +Virial components: +Potential Energy : -410.35962352107435 Eh -11166.45305 eV +Kinetic Energy : 204.82540016012598 Eh 5573.58249 eV +Virial Ratio : 2.00346062158438 + +DFT components: +N(Alpha) : 11.999997809243 electrons +N(Beta) : 11.999997809243 electrons +N(Total) : 23.999995618487 electrons +E(X) : -23.331574515067 Eh +E(C) : -0.803805997490 Eh +E(XC) : -24.135380512557 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 6.2244e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.9158e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.4878e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.1664e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.3282e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 5.4644e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 3 sec +Finished LeanSCF after 6.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 44.7 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361238 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007183850 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.527400748261 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003562 -0.000005790 0.000001275 + 2 O : -0.000000374 0.000000660 -0.000000323 + 3 O : 0.000003540 0.000008041 0.000000556 + 4 H : 0.000000396 -0.000002911 -0.000001508 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000117013 +RMS gradient ... 0.0000033779 +MAX gradient ... 0.0000080412 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.027026150 -0.009902399 -0.021779659 + 2 O : 0.017325370 0.007151329 -0.038690112 + 3 O : -0.010546251 -0.002721933 0.030215930 + 4 H : 0.020247031 0.005473003 0.030253841 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000118034 0.0000203854 -0.0000358009 + +Norm of the Cartesian gradient ... 0.0744169619 +RMS gradient ... 0.0214823265 +MAX gradient ... 0.0386901116 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.202 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 2.4%) +RI-J Coulomb gradient .... 0.063 sec ( 31.4%) +XC gradient .... 0.019 sec ( 9.6%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.527400748 Eh +Current gradient norm .... 0.074416962 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999953220 +Lowest eigenvalues of augmented Hessian: + -0.000032883 0.312872713 0.380757785 0.436857710 0.547281767 +Length of the computed step .... 0.009672997 +The final length of the internal step .... 0.009672997 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0039489844 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0027471516 RMS(Int)= 0.0039471456 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000016443 +Previously predicted energy change .... -0.000099107 +Actually observed energy change .... -0.000123935 +Ratio of predicted to observed change .... 1.250523976 +New trust radius .... 0.300000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0001239353 0.0000050000 NO + RMS gradient 0.0014123695 0.0001000000 NO + MAX gradient 0.0028166654 0.0003000000 NO + RMS step 0.0039489844 0.0020000000 NO + MAX step 0.0069880739 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0037 Max(Angles) 0.36 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3166 0.002817 -0.0037 1.3129 + 2. B(O 2,O 1) 1.2918 0.000229 -0.0004 1.2914 + 3. B(H 3,N 0) 1.0339 -0.000091 -0.0001 1.0337 + 4. A(O 1,N 0,H 3) 101.84 0.000249 -0.11 101.73 + 5. A(N 0,O 1,O 2) 116.14 -0.001978 0.36 116.50 + 6. D(O 2,O 1,N 0,H 3) 124.62 -0.070382 0.00 124.62 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.099 %) +Internal coordinates : 0.000 s ( 0.039 %) +B/P matrices and projection : 0.000 s ( 0.153 %) +Hessian update/contruction : 0.057 s (95.287 %) +Making the step : 0.000 s ( 0.187 %) +Converting the step to Cartesian: 0.000 s ( 0.084 %) +Storing new data : 0.000 s ( 0.077 %) +Checking convergence : 0.000 s ( 0.022 %) +Final printing : 0.002 s ( 4.048 %) +Total time : 0.059 s + +Time for energy+gradient : 12.463 s +Time for complete geometry iter : 13.424 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.115347 -0.710131 -0.235597 + O -0.199541 0.564334 -0.255699 + O 0.710096 1.388994 0.144514 + H -0.644610 -1.105353 0.343075 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.217975 -1.341953 -0.445215 + 1 O 8.0000 0 15.999 -0.377078 1.066436 -0.483201 + 2 O 8.0000 0 15.999 1.341886 2.624819 0.273092 + 3 H 1.0000 0 1.008 -1.218136 -2.088815 0.648317 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.312942977243 0.00000000 0.00000000 + O 2 1 0 1.291384841966 116.49952153 0.00000000 + H 1 2 3 1.033729252378 101.73443282 124.61538461 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.481102656444 0.00000000 0.00000000 + O 2 1 0 2.440363684813 116.49952153 0.00000000 + H 1 2 3 1.953465183617 101.73443282 124.61538461 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1676 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.563306062266 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.838e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22307 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.7 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5342004258349391 0.00e+00 1.28e-04 8.80e-04 3.16e-04 1.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5342280576603855 -2.76e-05 9.36e-05 8.44e-04 2.72e-04 0.5 + 3 -205.5342287041144402 -6.46e-07 1.13e-04 1.44e-03 6.84e-04 0.3 + 4 -205.5342250330794229 3.67e-06 9.45e-05 7.76e-04 6.92e-04 0.4 + 5 -205.5342308768171904 -5.84e-06 5.21e-05 6.40e-04 4.06e-04 0.2 + 6 -205.5342289366979287 1.94e-06 4.53e-05 4.38e-04 6.85e-04 0.3 + 7 -205.5342321071080676 -3.17e-06 1.02e-05 1.66e-04 4.32e-05 0.2 + 8 -205.5342321210794978 -1.40e-08 4.63e-06 6.30e-05 3.51e-05 0.3 + 9 -205.5342321529079470 -3.18e-08 2.74e-07 2.28e-06 1.07e-06 0.2 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.53423215290795 Eh -5592.87079 eV + +Components: +Nuclear Repulsion : 69.56330606226643 Eh 1892.91379 eV +Electronic Energy : -275.09753821517438 Eh -7485.78458 eV +One Electron Energy: -418.84028475260959 Eh -11397.22357 eV +Two Electron Energy: 143.74274653743518 Eh 3911.43899 eV + +Virial components: +Potential Energy : -410.36729533186679 Eh -11166.66181 eV +Kinetic Energy : 204.83306317895887 Eh 5573.79102 eV +Virial Ratio : 2.00342312399701 + +DFT components: +N(Alpha) : 11.999997803217 electrons +N(Beta) : 11.999997803217 electrons +N(Total) : 23.999995606434 electrons +E(X) : -23.333994295600 Eh +E(C) : -0.803977823845 Eh +E(XC) : -24.137972119445 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.1828e-08 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.2820e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.7356e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.7233e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.0731e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 6.3811e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 5 sec +Finished LeanSCF after 7.6 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 44.9 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361248 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007174938 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.527418463621 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003562 -0.000005786 0.000001276 + 2 O : -0.000000373 0.000000649 -0.000000318 + 3 O : 0.000003534 0.000008041 0.000000557 + 4 H : 0.000000401 -0.000002904 -0.000001515 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000116967 +RMS gradient ... 0.0000033765 +MAX gradient ... 0.0000080415 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.028220134 -0.008148560 -0.022075094 + 2 O : 0.019438094 0.004944857 -0.038506820 + 3 O : -0.011546318 -0.002600795 0.030181620 + 4 H : 0.020328359 0.005804498 0.030400295 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000120007 0.0000206433 -0.0000318320 + +Norm of the Cartesian gradient ... 0.0752148602 +RMS gradient ... 0.0217126599 +MAX gradient ... 0.0385068204 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.130 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.006 sec ( 4.3%) +RI-J Coulomb gradient .... 0.062 sec ( 47.9%) +XC gradient .... 0.021 sec ( 16.1%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.527418464 Eh +Current gradient norm .... 0.075214860 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999997922 +Lowest eigenvalues of augmented Hessian: + -0.000001698 0.316686866 0.373971696 0.411091578 0.533933456 +Length of the computed step .... 0.002038483 +The final length of the internal step .... 0.002038483 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0008322073 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0005017478 RMS(Int)= 0.0008322431 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000849 +Previously predicted energy change .... -0.000016443 +Actually observed energy change .... -0.000017715 +Ratio of predicted to observed change .... 1.077370105 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000177154 0.0000050000 NO + RMS gradient 0.0003549454 0.0001000000 NO + MAX gradient 0.0005232179 0.0003000000 NO + RMS step 0.0008322073 0.0020000000 YES + MAX step 0.0013495019 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0007 Max(Angles) 0.08 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3129 0.000513 -0.0007 1.3122 + 2. B(O 2,O 1) 1.2914 -0.000442 0.0003 1.2917 + 3. B(H 3,N 0) 1.0337 -0.000148 0.0002 1.0339 + 4. A(O 1,N 0,H 3) 101.73 -0.000523 0.08 101.81 + 5. A(N 0,O 1,O 2) 116.50 -0.000042 0.02 116.52 + 6. D(O 2,O 1,N 0,H 3) 124.62 -0.070812 -0.00 124.62 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.343 %) +Internal coordinates : 0.000 s ( 3.358 %) +B/P matrices and projection : 0.000 s (12.847 %) +Hessian update/contruction : 0.000 s (32.701 %) +Making the step : 0.000 s ( 5.839 %) +Converting the step to Cartesian: 0.000 s ( 4.234 %) +Storing new data : 0.000 s ( 3.504 %) +Checking convergence : 0.000 s ( 1.460 %) +Final printing : 0.000 s (26.277 %) +Total time : 0.001 s + +Time for energy+gradient : 13.262 s +Time for complete geometry iter : 14.241 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 4 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.115058 -0.709669 -0.235437 + O -0.199353 0.564173 -0.255816 + O 0.710277 1.389269 0.144476 + H -0.644690 -1.105929 0.343069 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.217429 -1.341081 -0.444912 + 1 O 8.0000 0 15.999 -0.376723 1.066133 -0.483422 + 2 O 8.0000 0 15.999 1.342229 2.625339 0.273020 + 3 H 1.0000 0 1.008 -1.218287 -2.089904 0.648306 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.312228851608 0.00000000 0.00000000 + O 2 1 0 1.291682796971 116.52225892 0.00000000 + H 1 2 3 1.033880328186 101.81083714 124.61538461 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.479753154570 0.00000000 0.00000000 + O 2 1 0 2.440926738172 116.52225892 0.00000000 + H 1 2 3 1.953750675520 101.81083714 124.61538461 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1668 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.568462737674 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.840e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22306 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.6 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5342303439641114 0.00e+00 2.21e-05 2.85e-04 3.44e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5342310183010568 -6.74e-07 1.56e-05 1.95e-04 6.75e-05 0.0 + 3 -205.5342307904832637 2.28e-07 1.19e-05 1.74e-04 2.08e-04 0.0 + 4 -205.5342310460595172 -2.56e-07 1.36e-05 2.19e-04 5.84e-05 0.0 + 5 -205.5342307926789545 2.53e-07 8.98e-06 1.61e-04 1.94e-04 0.0 + 6 -205.5342310976446925 -3.05e-07 1.50e-06 2.17e-05 5.07e-06 0.0 + 7 -205.5342310983579068 -7.13e-10 6.30e-07 1.00e-05 4.38e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.53423109835791 Eh -5592.87076 eV + +Components: +Nuclear Repulsion : 69.56846273767383 Eh 1893.05411 eV +Electronic Energy : -275.10269383603179 Eh -7485.92488 eV +One Electron Energy: -418.85023395109221 Eh -11397.49430 eV +Two Electron Energy: 143.74754011506045 Eh 3911.56943 eV + +Virial components: +Potential Energy : -410.36750307152340 Eh -11166.66746 eV +Kinetic Energy : 204.83327197316549 Eh 5573.79670 eV +Virial Ratio : 2.00342209602200 + +DFT components: +N(Alpha) : 11.999997805435 electrons +N(Beta) : 11.999997805435 electrons +N(Total) : 23.999995610869 electrons +E(X) : -23.334107401592 Eh +E(C) : -0.803987560160 Eh +E(XC) : -24.138094961751 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 7.1321e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.0015e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 6.2981e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.7146e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.3778e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 5.1496e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 4.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 45.1 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361243 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007172609 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.527419732277 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.0 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003562 -0.000005788 0.000001275 + 2 O : -0.000000373 0.000000648 -0.000000318 + 3 O : 0.000003538 0.000008046 0.000000557 + 4 H : 0.000000397 -0.000002906 -0.000001513 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000117017 +RMS gradient ... 0.0000033780 +MAX gradient ... 0.0000080459 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.028413550 -0.007754788 -0.022148407 + 2 O : 0.019657888 0.004575354 -0.038546791 + 3 O : -0.011525078 -0.002469598 0.030212060 + 4 H : 0.020280740 0.005649032 0.030483138 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000095523 0.0000199806 -0.0000274201 + +Norm of the Cartesian gradient ... 0.0753350960 +RMS gradient ... 0.0217473690 +MAX gradient ... 0.0385467911 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.100 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 5.0%) +RI-J Coulomb gradient .... 0.044 sec ( 44.2%) +XC gradient .... 0.014 sec ( 13.8%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.527419732 Eh +Current gradient norm .... 0.075335096 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999997055 +Lowest eigenvalues of augmented Hessian: + -0.000001184 0.188565733 0.355699704 0.406570579 0.523303589 +Length of the computed step .... 0.002426880 +The final length of the internal step .... 0.002426880 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0009907697 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0006665229 RMS(Int)= 0.0009907148 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000592 +Previously predicted energy change .... -0.000000849 +Actually observed energy change .... -0.000001269 +Ratio of predicted to observed change .... 1.494331736 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000012687 0.0000050000 YES + RMS gradient 0.0002106584 0.0001000000 NO + MAX gradient 0.0003323259 0.0003000000 NO + RMS step 0.0009907697 0.0020000000 YES + MAX step 0.0017769116 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0007 Max(Angles) 0.10 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3122 0.000227 -0.0007 1.3115 + 2. B(O 2,O 1) 1.2917 -0.000332 0.0005 1.2922 + 3. B(H 3,N 0) 1.0339 -0.000013 0.0000 1.0339 + 4. A(O 1,N 0,H 3) 101.81 -0.000295 0.10 101.91 + 5. A(N 0,O 1,O 2) 116.52 0.000130 -0.02 116.51 + 6. D(O 2,O 1,N 0,H 3) 124.62 -0.070839 -0.00 124.62 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.161 %) +Internal coordinates : 0.000 s ( 2.974 %) +B/P matrices and projection : 0.000 s (11.648 %) +Hessian update/contruction : 0.000 s (29.492 %) +Making the step : 0.000 s ( 5.328 %) +Converting the step to Cartesian: 0.000 s ( 3.717 %) +Storing new data : 0.000 s ( 3.098 %) +Checking convergence : 0.000 s ( 1.363 %) +Final printing : 0.000 s (32.094 %) +Total time : 0.001 s + +Time for energy+gradient : 8.765 s +Time for complete geometry iter : 9.553 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 5 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.114733 -0.709033 -0.235063 + O -0.199424 0.564153 -0.256168 + O 0.710638 1.389402 0.144499 + H -0.644655 -1.106678 0.343023 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.216814 -1.339879 -0.444204 + 1 O 8.0000 0 15.999 -0.376856 1.066095 -0.484087 + 2 O 8.0000 0 15.999 1.342911 2.625589 0.273064 + 3 H 1.0000 0 1.008 -1.218221 -2.091318 0.648220 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.311542446512 0.00000000 0.00000000 + O 2 1 0 1.292200105764 116.50502171 0.00000000 + H 1 2 3 1.033912354066 101.91264668 124.61538461 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.478456036920 0.00000000 0.00000000 + O 2 1 0 2.441904310119 116.50502171 0.00000000 + H 1 2 3 1.953811195663 101.91264668 124.61538461 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1668 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.570388605799 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.844e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22306 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5342288617224540 0.00e+00 2.67e-05 2.85e-04 5.71e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5342299564439941 -1.09e-06 2.43e-05 3.75e-04 1.05e-04 0.0 + 3 -205.5342292244577607 7.32e-07 1.95e-05 2.68e-04 3.76e-04 0.0 + 4 -205.5342300727607494 -8.48e-07 1.64e-05 2.71e-04 7.30e-05 0.0 + 5 -205.5342296583822304 4.14e-07 1.12e-05 1.99e-04 2.51e-04 0.0 + 6 -205.5342301490643990 -4.91e-07 1.12e-06 8.59e-06 4.02e-06 0.0 + 7 -205.5342301499381961 -8.74e-10 3.10e-07 3.38e-06 1.97e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.53423014993820 Eh -5592.87074 eV + +Components: +Nuclear Repulsion : 69.57038860579887 Eh 1893.10652 eV +Electronic Energy : -275.10461875573708 Eh -7485.97726 eV +One Electron Energy: -418.85470922382615 Eh -11397.61608 eV +Two Electron Energy: 143.75009046808907 Eh 3911.63883 eV + +Virial components: +Potential Energy : -410.36740774146972 Eh -11166.66487 eV +Kinetic Energy : 204.83317759153149 Eh 5573.79413 eV +Virial Ratio : 2.00342255374178 + +DFT components: +N(Alpha) : 11.999997808029 electrons +N(Beta) : 11.999997808029 electrons +N(Total) : 23.999995616059 electrons +E(X) : -23.334175364208 Eh +E(C) : -0.803988155589 Eh +E(XC) : -24.138163519798 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 8.7380e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.3798e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.0966e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.8109e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.9670e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.9893e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 4.1 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 45.2 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000361238 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007171023 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.527420365062 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003562 -0.000005789 0.000001275 + 2 O : -0.000000373 0.000000648 -0.000000320 + 3 O : 0.000003542 0.000008049 0.000000556 + 4 H : 0.000000393 -0.000002908 -0.000001511 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000117056 +RMS gradient ... 0.0000033791 +MAX gradient ... 0.0000080491 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.028604223 -0.007409188 -0.022154335 + 2 O : 0.019649799 0.004224432 -0.038629322 + 3 O : -0.011350745 -0.002320159 0.030271600 + 4 H : 0.020305169 0.005504915 0.030512056 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000090916 0.0000207045 -0.0000281638 + +Norm of the Cartesian gradient ... 0.0753941577 +RMS gradient ... 0.0217644186 +MAX gradient ... 0.0386293216 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.143 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.007 sec ( 4.7%) +RI-J Coulomb gradient .... 0.061 sec ( 42.6%) +XC gradient .... 0.019 sec ( 13.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.527420365 Eh +Current gradient norm .... 0.075394158 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999965 +Lowest eigenvalues of augmented Hessian: + -0.000000028 0.184189663 0.353598152 0.407627757 0.511506334 +Length of the computed step .... 0.000265269 +The final length of the internal step .... 0.000265269 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0001082955 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0000710516 RMS(Int)= 0.0001082959 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000014 +Previously predicted energy change .... -0.000000592 +Actually observed energy change .... -0.000000633 +Ratio of predicted to observed change .... 1.068975976 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000006328 0.0000050000 YES + RMS gradient 0.0000477577 0.0001000000 YES + MAX gradient 0.0000909629 0.0003000000 YES + RMS step 0.0001082955 0.0020000000 YES + MAX step 0.0001843290 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.01 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3115 -0.000002 -0.0000 1.3115 + 2. B(O 2,O 1) 1.2922 -0.000091 0.0001 1.2923 + 3. B(H 3,N 0) 1.0339 0.000028 -0.0000 1.0339 + 4. A(O 1,N 0,H 3) 101.91 0.000011 0.00 101.92 + 5. A(N 0,O 1,O 2) 116.51 0.000067 -0.01 116.50 + 6. D(O 2,O 1,N 0,H 3) 124.62 -0.070844 0.00 124.62 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.386 %) +Internal coordinates : 0.000 s ( 2.807 %) +B/P matrices and projection : 0.000 s (14.825 %) +Hessian update/contruction : 0.000 s (36.930 %) +Making the step : 0.000 s ( 4.825 %) +Converting the step to Cartesian: 0.000 s ( 3.421 %) +Storing new data : 0.000 s ( 2.982 %) +Checking convergence : 0.000 s ( 1.053 %) +Final printing : 0.000 s (22.982 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 5 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.114727 -0.708990 -0.235021 + O -0.199497 0.564153 -0.256223 + O 0.710689 1.389380 0.144521 + H -0.644627 -1.106699 0.343015 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.216803 -1.339797 -0.444126 + 1 O 8.0000 0 15.999 -0.376994 1.066095 -0.484192 + 2 O 8.0000 0 15.999 1.343007 2.625547 0.273106 + 3 H 1.0000 0 1.008 -1.218169 -2.091358 0.648205 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.311517889961 0.00000000 0.00000000 + O 2 1 0 1.292297648489 116.49564208 0.00000000 + H 1 2 3 1.033884787311 101.91658454 124.61538461 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.478409631765 0.00000000 0.00000000 + O 2 1 0 2.442088639155 116.49564208 0.00000000 + H 1 2 3 1.953759102045 101.91658454 124.61538461 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1668 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.569217255945 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.845e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22306 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.5692172559 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5342303888427864 0.00e+00 3.73e-06 3.34e-05 7.39e-06 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5342304093622943 -2.05e-08 4.07e-06 6.68e-05 1.43e-05 0.1 + 3 -205.5342303826789134 2.67e-08 3.27e-06 4.68e-05 7.05e-05 0.0 + 4 -205.5342304131900733 -3.05e-08 1.05e-06 1.54e-05 5.39e-06 0.0 + 5 -205.5342304117746721 1.42e-09 6.81e-07 1.18e-05 1.59e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.53423041177467 Eh -5592.87075 eV + +Components: +Nuclear Repulsion : 69.56921725594459 Eh 1893.07464 eV +Electronic Energy : -275.10344766771925 Eh -7485.94539 eV +One Electron Energy: -418.85267516890502 Eh -11397.56073 eV +Two Electron Energy: 143.74922750118577 Eh 3911.61534 eV + +Virial components: +Potential Energy : -410.36725792058616 Eh -11166.66079 eV +Kinetic Energy : 204.83302750881148 Eh 5573.79004 eV +Virial Ratio : 2.00342329023542 + +DFT components: +N(Alpha) : 11.999997808552 electrons +N(Beta) : 11.999997808552 electrons +N(Total) : 23.999995617105 electrons +E(X) : -23.334152579192 Eh +E(C) : -0.803984889390 Eh +E(XC) : -24.138137468582 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -1.4154e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.1820e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 6.8052e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.0714e-05 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.5923e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.2620e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.187032 -522.1057 + 1 2.0000 -19.037394 -518.0338 + 2 2.0000 -14.254314 -387.8796 + 3 2.0000 -1.249791 -34.0085 + 4 2.0000 -0.965277 -26.2665 + 5 2.0000 -0.704820 -19.1791 + 6 2.0000 -0.561728 -15.2854 + 7 2.0000 -0.514846 -14.0097 + 8 2.0000 -0.506565 -13.7843 + 9 2.0000 -0.335289 -9.1237 + 10 2.0000 -0.271819 -7.3966 + 11 2.0000 -0.259731 -7.0676 + 12 0.0000 -0.204844 -5.5741 + 13 0.0000 0.050408 1.3717 + 14 0.0000 0.085911 2.3377 + 15 0.0000 0.135840 3.6964 + 16 0.0000 0.225302 6.1308 + 17 0.0000 0.267430 7.2771 + 18 0.0000 0.314977 8.5710 + 19 0.0000 0.332007 9.0344 + 20 0.0000 0.338573 9.2130 + 21 0.0000 0.381970 10.3939 + 22 0.0000 0.397953 10.8289 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.347829 + 1 O : 0.203579 + 2 O : -0.133640 + 3 H : 0.277889 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.893523 s : 3.893523 + pz : 1.079002 p : 3.402713 + px : 1.503390 + py : 0.820321 + dz2 : 0.004759 d : 0.051592 + dxz : 0.010855 + dyz : 0.012524 + dx2y2 : 0.012222 + dxy : 0.011232 + + 1 O s : 3.760011 s : 3.760011 + pz : 1.381886 p : 3.913247 + px : 1.453115 + py : 1.078245 + dz2 : 0.009208 d : 0.123163 + dxz : 0.012602 + dyz : 0.038830 + dx2y2 : 0.048007 + dxy : 0.014516 + + 2 O s : 3.941690 s : 3.941690 + pz : 1.276520 p : 4.169873 + px : 1.435125 + py : 1.458229 + dz2 : 0.003277 d : 0.022077 + dxz : 0.005184 + dyz : 0.004701 + dx2y2 : 0.002751 + dxy : 0.006164 + + 3 H s : 0.691634 s : 0.691634 + pz : 0.011122 p : 0.030477 + px : 0.012671 + py : 0.006684 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.097771 + 1 O : -0.187647 + 2 O : 0.003103 + 3 H : 0.282315 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.359535 s : 3.359535 + pz : 1.021638 p : 3.431076 + px : 1.445060 + py : 0.964378 + dz2 : 0.031710 d : 0.307161 + dxz : 0.020628 + dyz : 0.066040 + dx2y2 : 0.074352 + dxy : 0.114430 + + 1 O s : 3.373031 s : 3.373031 + pz : 1.287227 p : 4.043646 + px : 1.471582 + py : 1.284837 + dz2 : 0.062961 d : 0.770970 + dxz : 0.048973 + dyz : 0.189526 + dx2y2 : 0.226376 + dxy : 0.243134 + + 2 O s : 3.599521 s : 3.599521 + pz : 1.233585 p : 4.138007 + px : 1.428687 + py : 1.475735 + dz2 : 0.036375 d : 0.259368 + dxz : 0.042467 + dyz : 0.036435 + dx2y2 : 0.075567 + dxy : 0.068525 + + 3 H s : 0.640862 s : 0.640862 + pz : 0.027496 p : 0.076823 + px : 0.035880 + py : 0.013447 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3478 7.0000 -0.3478 2.6366 2.6366 0.0000 + 1 O 7.7964 8.0000 0.2036 2.5890 2.5890 0.0000 + 2 O 8.1336 8.0000 -0.1336 1.7017 1.7017 -0.0000 + 3 H 0.7221 1.0000 0.2779 0.9073 0.9073 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3458 B( 0-N , 2-O ) : 0.4323 B( 0-N , 3-H ) : 0.8585 +B( 1-O , 2-O ) : 1.2319 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 3 sec + +Total time .... 3.934 sec +Sum of individual times .... 3.920 sec ( 99.6%) + +SCF preparation .... 1.209 sec ( 30.7%) +Fock matrix formation .... 0.133 sec ( 3.4%) + Startup .... 0.008 sec ( 5.7% of F) + Split-RI-J .... 0.018 sec ( 13.1% of F) + XC integration .... 0.082 sec ( 61.4% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.005 sec ( 6.7% of XC) + Density eval. .... 0.008 sec ( 9.5% of XC) + XC-Functional eval. .... 0.005 sec ( 5.5% of XC) + XC-Potential eval. .... 0.008 sec ( 9.5% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.008 sec ( 0.2%) +Total Energy calculation .... 0.011 sec ( 0.3%) +Population analysis .... 2.513 sec ( 63.9%) +Orbital Transformation .... 0.006 sec ( 0.2%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.010 sec ( 0.2%) +SOSCF solution .... 0.029 sec ( 0.7%) +Finished LeanSCF after 6.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 45.5 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000361238 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007171269 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.527420380269 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.034.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.034.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.367219 0.812285 -0.190259 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5342304117746721 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.032544507 0.940190694 -0.223465695 +Nuclear contribution : -0.785710237 -1.431640950 0.416851330 + ----------------------------------------- +Total Dipole Moment : -0.753165730 -0.491450257 0.193385635 + ----------------------------------------- +Magnitude (a.u.) : 0.919880414 +Magnitude (Debye) : 2.338150196 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.042664 0.421387 0.380739 +Rotational constants in MHz : 91216.780749 12632.867790 11414.281361 + +Dipole components along the rotational axes: +x,y,z [a.u.] : -0.660545 -0.460125 0.445135 +x,y,z [Debye]: -1.678972 -1.169545 1.131444 + + + +Dipole moment calculation done in 1.0 sec + +Maximum memory used throughout the entire PROP-calculation: 23.8 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 35 * + * * + * Dihedral ( 2, 1, 0, 3) : 133.84615385 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.3118 0.668691 + 2. B(O 2,O 1) 1.2951 0.717613 + 3. B(H 3,N 0) 1.0373 0.396359 + 4. A(O 1,N 0,H 3) 101.8739 0.355671 + 5. A(N 0,O 1,O 2) 116.3684 0.439920 + 6. D(O 2,O 1,N 0,H 3) 133.8462 0.034617 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.129424 -0.703377 -0.203861 + O -0.205783 0.564804 -0.212034 + O 0.724328 1.407704 0.107063 + H -0.666677 -1.131286 0.305124 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.244576 -1.329191 -0.385242 + 1 O 8.0000 0 15.999 -0.388873 1.067324 -0.400686 + 2 O 8.0000 0 15.999 1.368781 2.660175 0.202320 + 3 H 1.0000 0 1.008 -1.259837 -2.137821 0.576600 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.311517889961 0.00000000 0.00000000 + O 2 1 0 1.292297648489 116.49564208 0.00000000 + H 1 2 3 1.033884787311 101.91658454 124.61538461 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.478409631765 0.00000000 0.00000000 + O 2 1 0 2.442088639155 116.49564208 0.00000000 + H 1 2 3 1.953759102045 101.91658454 124.61538461 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1667 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.458394903442 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.880e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22307 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.4583949034 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.5 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5401809919149798 0.00e+00 4.03e-04 3.56e-03 2.63e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.066) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5414121287408591 -1.23e-03 4.79e-04 4.55e-03 2.03e-02 0.700 0.1 + ***Turning on AO-DIIS*** + 3 -205.5424311387480145 -1.02e-03 3.68e-04 3.44e-03 1.44e-02 0.700 0.0 + 4 -205.5431439629115005 -7.13e-04 9.22e-04 8.64e-03 1.02e-02 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5448034845866516 -1.66e-03 7.33e-05 5.57e-04 6.60e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -205.5448081965109566 -4.71e-06 1.96e-04 3.30e-03 6.56e-04 0.0 + 7 -205.5447575632286146 5.06e-05 1.58e-04 2.14e-03 2.86e-03 0.0 + 8 -205.5448168516191174 -5.93e-05 7.86e-05 1.25e-03 3.80e-04 0.0 + 9 -205.5448077488740921 9.10e-06 5.10e-05 9.30e-04 1.08e-03 0.0 + 10 -205.5448185446934133 -1.08e-05 7.73e-06 7.66e-05 3.39e-05 0.0 + 11 -205.5448185604405182 -1.57e-08 2.45e-06 2.67e-05 1.96e-05 0.0 + 12 -205.5448185670369128 -6.60e-09 3.04e-07 2.54e-06 2.28e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 12 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.54481856703691 Eh -5593.15886 eV + +Components: +Nuclear Repulsion : 69.45839490344216 Eh 1890.05901 eV +Electronic Energy : -275.00321347047907 Eh -7483.21788 eV +One Electron Energy: -418.65593261453887 Eh -11392.20710 eV +Two Electron Energy: 143.65271914405983 Eh 3908.98922 eV + +Virial components: +Potential Energy : -410.35416899910734 Eh -11166.30462 eV +Kinetic Energy : 204.80935043207043 Eh 5573.14576 eV +Virial Ratio : 2.00359098905111 + +DFT components: +N(Alpha) : 11.999999510588 electrons +N(Beta) : 11.999999510588 electrons +N(Total) : 23.999999021176 electrons +E(X) : -23.331567525036 Eh +E(C) : -0.803713091128 Eh +E(XC) : -24.135280616164 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 6.5964e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.5405e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.0357e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.5967e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.2753e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 7.3710e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.187871 -522.1285 + 1 2.0000 -19.032023 -517.8877 + 2 2.0000 -14.259940 -388.0327 + 3 2.0000 -1.247593 -33.9487 + 4 2.0000 -0.964433 -26.2435 + 5 2.0000 -0.703924 -19.1547 + 6 2.0000 -0.561423 -15.2771 + 7 2.0000 -0.513992 -13.9864 + 8 2.0000 -0.506364 -13.7789 + 9 2.0000 -0.333629 -9.0785 + 10 2.0000 -0.272156 -7.4057 + 11 2.0000 -0.264125 -7.1872 + 12 0.0000 -0.198285 -5.3956 + 13 0.0000 0.048076 1.3082 + 14 0.0000 0.083327 2.2675 + 15 0.0000 0.134326 3.6552 + 16 0.0000 0.223024 6.0688 + 17 0.0000 0.269499 7.3334 + 18 0.0000 0.311793 8.4843 + 19 0.0000 0.329436 8.9644 + 20 0.0000 0.341977 9.3057 + 21 0.0000 0.380552 10.3553 + 22 0.0000 0.400361 10.8944 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.330803 + 1 O : 0.207829 + 2 O : -0.152322 + 3 H : 0.275295 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.895728 s : 3.895728 + pz : 1.082123 p : 3.381395 + px : 1.473890 + py : 0.825383 + dz2 : 0.005439 d : 0.053680 + dxz : 0.010985 + dyz : 0.012637 + dx2y2 : 0.012508 + dxy : 0.012111 + + 1 O s : 3.759489 s : 3.759489 + pz : 1.385192 p : 3.907116 + px : 1.452576 + py : 1.069348 + dz2 : 0.007639 d : 0.125565 + dxz : 0.012395 + dyz : 0.039623 + dx2y2 : 0.049832 + dxy : 0.016077 + + 2 O s : 3.943795 s : 3.943795 + pz : 1.315900 p : 4.185337 + px : 1.431083 + py : 1.438354 + dz2 : 0.002812 d : 0.023190 + dxz : 0.006283 + dyz : 0.004427 + dx2y2 : 0.002992 + dxy : 0.006676 + + 3 H s : 0.694843 s : 0.694843 + pz : 0.009953 p : 0.029862 + px : 0.013038 + py : 0.006871 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.086650 + 1 O : -0.188027 + 2 O : -0.007232 + 3 H : 0.281909 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.365142 s : 3.365142 + pz : 1.020043 p : 3.412936 + px : 1.425734 + py : 0.967159 + dz2 : 0.032909 d : 0.308571 + dxz : 0.018595 + dyz : 0.065011 + dx2y2 : 0.073471 + dxy : 0.118584 + + 1 O s : 3.374101 s : 3.374101 + pz : 1.285695 p : 4.042391 + px : 1.476909 + py : 1.279787 + dz2 : 0.062494 d : 0.771535 + dxz : 0.042282 + dyz : 0.188533 + dx2y2 : 0.230490 + dxy : 0.247736 + + 2 O s : 3.600729 s : 3.600729 + pz : 1.260663 p : 4.148192 + px : 1.429548 + py : 1.457981 + dz2 : 0.034264 d : 0.258311 + dxz : 0.038554 + dyz : 0.035221 + dx2y2 : 0.078383 + dxy : 0.071888 + + 3 H s : 0.642719 s : 0.642719 + pz : 0.024271 p : 0.075372 + px : 0.037071 + py : 0.014030 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3308 7.0000 -0.3308 2.6631 2.6631 0.0000 + 1 O 7.7922 8.0000 0.2078 2.6036 2.6036 0.0000 + 2 O 8.1523 8.0000 -0.1523 1.7136 1.7136 0.0000 + 3 H 0.7247 1.0000 0.2753 0.9090 0.9090 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3555 B( 0-N , 2-O ) : 0.4432 B( 0-N , 3-H ) : 0.8644 +B( 1-O , 2-O ) : 1.2369 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 4 sec + +Total time .... 4.699 sec +Sum of individual times .... 4.674 sec ( 99.5%) + +SCF preparation .... 1.414 sec ( 30.1%) +Fock matrix formation .... 0.312 sec ( 6.6%) + Startup .... 0.014 sec ( 4.4% of F) + Split-RI-J .... 0.044 sec ( 14.1% of F) + XC integration .... 0.197 sec ( 63.2% of F) + Basis function eval. .... 0.015 sec ( 7.5% of XC) + Density eval. .... 0.022 sec ( 11.2% of XC) + XC-Functional eval. .... 0.010 sec ( 5.2% of XC) + XC-Potential eval. .... 0.019 sec ( 9.8% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.029 sec ( 0.6%) +Total Energy calculation .... 0.025 sec ( 0.5%) +Population analysis .... 2.765 sec ( 58.8%) +Orbital Transformation .... 0.014 sec ( 0.3%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.070 sec ( 1.5%) +SOSCF solution .... 0.044 sec ( 0.9%) +Finished LeanSCF after 7.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 45.9 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360780 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007174082 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.538005265365 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003642 -0.000005899 0.000001141 + 2 O : -0.000000390 0.000000646 -0.000000262 + 3 O : 0.000003711 0.000008339 0.000000383 + 4 H : 0.000000321 -0.000003086 -0.000001262 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000120281 +RMS gradient ... 0.0000034722 +MAX gradient ... 0.0000083392 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.018294373 -0.010632658 -0.020441326 + 2 O : 0.008744380 0.008846260 -0.035663070 + 3 O : -0.004344252 0.000267260 0.027578653 + 4 H : 0.013894246 0.001519138 0.028525742 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000058728 -0.0000037999 0.0000214742 + +Norm of the Cartesian gradient ... 0.0638808438 +RMS gradient ... 0.0184408112 +MAX gradient ... 0.0356630696 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.125 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 4.0%) +RI-J Coulomb gradient .... 0.059 sec ( 47.0%) +XC gradient .... 0.019 sec ( 15.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.538005265 Eh +Current gradient norm .... 0.063880844 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999843295 +Lowest eigenvalues of augmented Hessian: + -0.000166309 0.354899030 0.391465421 0.439023456 0.668186603 +Length of the computed step .... 0.017705476 +The final length of the internal step .... 0.017705476 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0072282302 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0068417753 RMS(Int)= 0.0072235268 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0039909116 0.0001000000 NO + MAX gradient 0.0077344929 0.0003000000 NO + RMS step 0.0072282302 0.0020000000 NO + MAX step 0.0115740180 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0061 Max(Angles) 0.55 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3118 0.007734 -0.0061 1.3056 + 2. B(O 2,O 1) 1.2951 0.003850 -0.0029 1.2923 + 3. B(H 3,N 0) 1.0373 0.002709 -0.0037 1.0336 + 4. A(O 1,N 0,H 3) 101.87 0.003406 -0.55 101.32 + 5. A(N 0,O 1,O 2) 116.37 -0.001409 0.18 116.55 + 6. D(O 2,O 1,N 0,H 3) 133.85 -0.060622 0.00 133.85 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.380 %) +Internal coordinates : 0.000 s ( 3.463 %) +B/P matrices and projection : 0.000 s (13.276 %) +Hessian update/contruction : 0.000 s (32.323 %) +Making the step : 0.000 s ( 5.772 %) +Converting the step to Cartesian: 0.000 s ( 4.618 %) +Storing new data : 0.000 s ( 3.896 %) +Checking convergence : 0.000 s ( 0.144 %) +Final printing : 0.000 s (26.984 %) +Total time : 0.001 s + +Time for energy+gradient : 12.500 s +Time for complete geometry iter : 13.370 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.130388 -0.702711 -0.205516 + O -0.204857 0.559144 -0.209598 + O 0.720556 1.403737 0.107044 + H -0.664794 -1.122327 0.304362 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.246397 -1.327931 -0.388369 + 1 O 8.0000 0 15.999 -0.387123 1.056629 -0.396083 + 2 O 8.0000 0 15.999 1.361653 2.652679 0.202283 + 3 H 1.0000 0 1.008 -1.256279 -2.120890 0.575162 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.305635113666 0.00000000 0.00000000 + O 2 1 0 1.292280042236 116.55222961 0.00000000 + H 1 2 3 1.033619258039 101.32425278 133.84615409 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.467292795660 0.00000000 0.00000000 + O 2 1 0 2.442055368158 116.55222961 0.00000000 + H 1 2 3 1.953257324441 101.32425278 133.84615409 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1667 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.693834746746 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.845e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22308 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 1.3 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5448727808331455 0.00e+00 1.69e-04 1.14e-03 3.30e-04 0.6 + *** Restarting incremental Fock matrix formation *** + 2 -205.5449197991666210 -4.70e-05 2.01e-04 2.20e-03 5.25e-04 0.4 + 3 -205.5448686551814035 5.11e-05 1.45e-04 2.56e-03 2.74e-03 0.1 + 4 -205.5449239993280912 -5.53e-05 1.22e-04 2.03e-03 5.78e-04 0.2 + 5 -205.5449056340814309 1.84e-05 7.85e-05 1.46e-03 1.56e-03 0.2 + 6 -205.5449275563060496 -2.19e-05 3.07e-05 5.37e-04 1.02e-04 0.2 + 7 -205.5449274707409586 8.56e-08 1.66e-05 2.97e-04 1.12e-04 0.3 + 8 -205.5449278187093682 -3.48e-07 5.08e-07 6.53e-06 2.62e-06 0.3 + 9 -205.5449278186617335 4.76e-11 1.91e-07 2.13e-06 2.03e-06 0.2 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.54492781866173 Eh -5593.16184 eV + +Components: +Nuclear Repulsion : 69.69383474674562 Eh 1896.46566 eV +Electronic Energy : -275.23876256540734 Eh -7489.62749 eV +One Electron Energy: -419.10431383013838 Eh -11404.40817 eV +Two Electron Energy: 143.86555126473107 Eh 3914.78067 eV + +Virial components: +Potential Energy : -410.38146671221313 Eh -11167.04743 eV +Kinetic Energy : 204.83653889355139 Eh 5573.88559 eV +Virial Ratio : 2.00345831329184 + +DFT components: +N(Alpha) : 11.999999543323 electrons +N(Beta) : 11.999999543323 electrons +N(Total) : 23.999999086647 electrons +E(X) : -23.338934040688 Eh +E(C) : -0.804190387722 Eh +E(XC) : -24.143124428410 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -4.7635e-11 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.1303e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.9144e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.9650e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.0310e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.3171e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 4 sec +Finished LeanSCF after 6.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 46.1 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360943 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007182530 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.538106231961 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003636 -0.000005848 0.000001150 + 2 O : -0.000000393 0.000000620 -0.000000249 + 3 O : 0.000003655 0.000008238 0.000000386 + 4 H : 0.000000373 -0.000003010 -0.000001287 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000118983 +RMS gradient ... 0.0000034348 +MAX gradient ... 0.0000082379 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.020112721 -0.007744938 -0.019837218 + 2 O : 0.011063612 0.005472968 -0.035118719 + 3 O : -0.006551485 -0.001973508 0.027277117 + 4 H : 0.015600594 0.004245478 0.027678819 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000059022 -0.0000004072 0.0000199134 + +Norm of the Cartesian gradient ... 0.0637344460 +RMS gradient ... 0.0183985498 +MAX gradient ... 0.0351187185 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.358 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.006 sec ( 1.8%) +RI-J Coulomb gradient .... 0.060 sec ( 16.9%) +XC gradient .... 0.021 sec ( 5.8%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.538106232 Eh +Current gradient norm .... 0.063734446 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999972007 +Lowest eigenvalues of augmented Hessian: + -0.000021432 0.334797274 0.378058547 0.442424805 0.574510330 +Length of the computed step .... 0.007482492 +The final length of the internal step .... 0.007482492 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0030547146 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0020882466 RMS(Int)= 0.0030532247 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000010717 +Previously predicted energy change .... -0.000083181 +Actually observed energy change .... -0.000100967 +Ratio of predicted to observed change .... 1.213822149 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0001009666 0.0000050000 NO + RMS gradient 0.0011881646 0.0001000000 NO + MAX gradient 0.0022459259 0.0003000000 NO + RMS step 0.0030547146 0.0020000000 NO + MAX step 0.0051639597 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0027 Max(Angles) 0.30 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3056 0.002246 -0.0027 1.3029 + 2. B(O 2,O 1) 1.2923 0.000703 -0.0009 1.2914 + 3. B(H 3,N 0) 1.0336 -0.000070 -0.0001 1.0335 + 4. A(O 1,N 0,H 3) 101.32 0.000001 -0.04 101.28 + 5. A(N 0,O 1,O 2) 116.55 -0.001711 0.30 116.85 + 6. D(O 2,O 1,N 0,H 3) 133.85 -0.061391 0.00 133.85 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.051 %) +Internal coordinates : 0.000 s ( 0.019 %) +B/P matrices and projection : 0.000 s ( 0.082 %) +Hessian update/contruction : 0.111 s (97.684 %) +Making the step : 0.000 s ( 0.048 %) +Converting the step to Cartesian: 0.000 s ( 0.033 %) +Storing new data : 0.000 s ( 0.026 %) +Checking convergence : 0.000 s ( 0.010 %) +Final printing : 0.002 s ( 2.044 %) +Total time : 0.113 s + +Time for energy+gradient : 14.057 s +Time for complete geometry iter : 15.205 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.129958 -0.702637 -0.206375 + O -0.202849 0.557076 -0.208364 + O 0.719329 1.404452 0.106715 + H -0.665146 -1.121046 0.304316 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.245585 -1.327792 -0.389993 + 1 O 8.0000 0 15.999 -0.383329 1.052721 -0.393751 + 2 O 8.0000 0 15.999 1.359334 2.654029 0.201662 + 3 H 1.0000 0 1.008 -1.256943 -2.118470 0.575074 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.302935819563 0.00000000 0.00000000 + O 2 1 0 1.291406983028 116.84810270 0.00000000 + H 1 2 3 1.033470419820 101.28371155 133.84615409 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.462191869049 0.00000000 0.00000000 + O 2 1 0 2.440405525356 116.84810270 0.00000000 + H 1 2 3 1.952976060968 101.28371155 133.84615409 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1667 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.760344692925 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.831e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22308 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.8 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5449120025809862 0.00e+00 1.02e-04 7.84e-04 2.30e-04 0.6 + *** Restarting incremental Fock matrix formation *** + 2 -205.5449282798494437 -1.63e-05 6.74e-05 6.49e-04 2.01e-04 0.5 + 3 -205.5449296363908047 -1.36e-06 6.40e-05 9.06e-04 2.34e-04 0.2 + 4 -205.5449263461696319 3.29e-06 5.35e-05 7.07e-04 6.44e-04 0.2 + 5 -205.5449297737421830 -3.43e-06 4.45e-05 5.69e-04 2.31e-04 0.1 + 6 -205.5449278502613879 1.92e-06 3.40e-05 3.53e-04 5.09e-04 0.2 + 7 -205.5449303306992306 -2.48e-06 6.77e-06 9.62e-05 2.64e-05 0.3 + 8 -205.5449303329401687 -2.24e-09 3.31e-06 4.26e-05 2.48e-05 0.2 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.54493033294017 Eh -5593.16191 eV + +Components: +Nuclear Repulsion : 69.76034469292472 Eh 1898.27549 eV +Electronic Energy : -275.30527502586494 Eh -7491.43739 eV +One Electron Energy: -419.23119973155173 Eh -11407.86091 eV +Two Electron Energy: 143.92592470568681 Eh 3916.42352 eV + +Virial components: +Potential Energy : -410.38847006492620 Eh -11167.23800 eV +Kinetic Energy : 204.84353973198603 Eh 5574.07610 eV +Virial Ratio : 2.00342403085727 + +DFT components: +N(Alpha) : 11.999999573393 electrons +N(Beta) : 11.999999573393 electrons +N(Total) : 23.999999146787 electrons +E(X) : -23.341240609544 Eh +E(C) : -0.804345021118 Eh +E(XC) : -24.145585630663 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.2409e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.2576e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.3090e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.2781e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.4763e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 4.2367e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 4 sec +Finished LeanSCF after 7.1 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 46.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360953 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007173616 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.538117669537 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003636 -0.000005846 0.000001151 + 2 O : -0.000000390 0.000000614 -0.000000246 + 3 O : 0.000003649 0.000008237 0.000000386 + 4 H : 0.000000377 -0.000003005 -0.000001291 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000118933 +RMS gradient ... 0.0000034333 +MAX gradient ... 0.0000082367 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.021243277 -0.006281317 -0.019974836 + 2 O : 0.013179271 0.003914126 -0.034999482 + 3 O : -0.007622705 -0.002048313 0.027201097 + 4 H : 0.015686711 0.004415504 0.027773221 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000011712 0.0000023443 0.0000045893 + +Norm of the Cartesian gradient ... 0.0643647841 +RMS gradient ... 0.0185805127 +MAX gradient ... 0.0349994821 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.492 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.006 sec ( 1.2%) +RI-J Coulomb gradient .... 0.058 sec ( 11.8%) +XC gradient .... 0.018 sec ( 3.7%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.538117670 Eh +Current gradient norm .... 0.064364784 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999998962 +Lowest eigenvalues of augmented Hessian: + -0.000000827 0.339286982 0.378573182 0.411462520 0.558807418 +Length of the computed step .... 0.001440597 +The final length of the internal step .... 0.001440597 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0005881213 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0003692487 RMS(Int)= 0.0005881437 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000413 +Previously predicted energy change .... -0.000010717 +Actually observed energy change .... -0.000011438 +Ratio of predicted to observed change .... 1.067263765 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000114376 0.0000050000 NO + RMS gradient 0.0002406550 0.0001000000 NO + MAX gradient 0.0003960188 0.0003000000 NO + RMS step 0.0005881213 0.0020000000 YES + MAX step 0.0010445270 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0005 Max(Angles) 0.06 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3029 0.000396 -0.0005 1.3024 + 2. B(O 2,O 1) 1.2914 -0.000150 0.0001 1.2915 + 3. B(H 3,N 0) 1.0335 -0.000132 0.0001 1.0336 + 4. A(O 1,N 0,H 3) 101.28 -0.000388 0.06 101.34 + 5. A(N 0,O 1,O 2) 116.85 -0.000020 0.01 116.86 + 6. D(O 2,O 1,N 0,H 3) 133.85 -0.061669 -0.00 133.85 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.083 %) +Internal coordinates : 0.000 s ( 0.027 %) +B/P matrices and projection : 0.000 s ( 0.110 %) +Hessian update/contruction : 0.002 s ( 2.319 %) +Making the step : 0.000 s ( 0.048 %) +Converting the step to Cartesian: 0.000 s ( 0.036 %) +Storing new data : 0.000 s ( 0.034 %) +Checking convergence : 0.000 s ( 0.012 %) +Final printing : 0.083 s (97.328 %) +Total time : 0.085 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.129751 -0.702260 -0.206244 + O -0.202697 0.557045 -0.208453 + O 0.719430 1.404552 0.106675 + H -0.665192 -1.121493 0.304314 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.245194 -1.327079 -0.389744 + 1 O 8.0000 0 15.999 -0.383042 1.052662 -0.393920 + 2 O 8.0000 0 15.999 1.359526 2.654219 0.201586 + 3 H 1.0000 0 1.008 -1.257031 -2.119314 0.575070 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.302449964138 0.00000000 0.00000000 + O 2 1 0 1.291469681773 116.86125580 0.00000000 + H 1 2 3 1.033614930030 101.34355854 133.84615409 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.461273735357 0.00000000 0.00000000 + O 2 1 0 2.440524008813 116.86125580 0.00000000 + H 1 2 3 1.953249145690 101.34355854 133.84615409 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1667 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.767429307137 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.831e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.001 sec +Total time needed ... 0.003 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22308 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5577 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.7674293071 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.3 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 1.3 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5449289716568160 0.00e+00 1.55e-05 2.31e-04 2.77e-05 1.2 + *** Restarting incremental Fock matrix formation *** + 2 -205.5449292506111760 -2.79e-07 9.76e-06 9.57e-05 3.62e-05 0.6 + 3 -205.5449292051168868 4.55e-08 5.86e-06 9.33e-05 8.30e-05 0.2 + 4 -205.5449292625260114 -5.74e-08 1.01e-05 1.36e-04 4.95e-05 0.4 + 5 -205.5449290963485964 1.66e-07 7.31e-06 1.13e-04 1.35e-04 0.2 + 6 -205.5449292836640893 -1.87e-07 1.53e-06 2.37e-05 4.72e-06 0.4 + 7 -205.5449292837542998 -9.02e-11 6.83e-07 1.12e-05 4.62e-06 0.4 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.54492928375430 Eh -5593.16188 eV + +Components: +Nuclear Repulsion : 69.76742930713736 Eh 1898.46827 eV +Electronic Energy : -275.31235859089168 Eh -7491.63014 eV +One Electron Energy: -419.24338254320389 Eh -11408.19242 eV +Two Electron Energy: 143.93102395231219 Eh 3916.56228 eV + +Virial components: +Potential Energy : -410.38889780345619 Eh -11167.24964 eV +Kinetic Energy : 204.84396851970192 Eh 5574.08776 eV +Virial Ratio : 2.00342192532745 + +DFT components: +N(Alpha) : 11.999999574154 electrons +N(Beta) : 11.999999574154 electrons +N(Total) : 23.999999148309 electrons +E(X) : -23.341241244201 Eh +E(C) : -0.804354539036 Eh +E(XC) : -24.145595783236 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 9.0211e-11 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.1243e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 6.8334e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.4681e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.6229e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 5.4467e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.188452 -522.1443 + 1 2.0000 -19.031157 -517.8641 + 2 2.0000 -14.259160 -388.0115 + 3 2.0000 -1.252383 -34.0791 + 4 2.0000 -0.968985 -26.3674 + 5 2.0000 -0.702347 -19.1118 + 6 2.0000 -0.563845 -15.3430 + 7 2.0000 -0.516364 -14.0510 + 8 2.0000 -0.507587 -13.8121 + 9 2.0000 -0.333976 -9.0879 + 10 2.0000 -0.272514 -7.4155 + 11 2.0000 -0.263075 -7.1586 + 12 0.0000 -0.196563 -5.3487 + 13 0.0000 0.052570 1.4305 + 14 0.0000 0.083836 2.2813 + 15 0.0000 0.140927 3.8348 + 16 0.0000 0.224348 6.1048 + 17 0.0000 0.268775 7.3137 + 18 0.0000 0.311711 8.4821 + 19 0.0000 0.330068 8.9816 + 20 0.0000 0.340944 9.2776 + 21 0.0000 0.381551 10.3825 + 22 0.0000 0.400116 10.8877 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.331550 + 1 O : 0.211396 + 2 O : -0.155107 + 3 H : 0.275260 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.894497 s : 3.894497 + pz : 1.081334 p : 3.382658 + px : 1.474845 + py : 0.826479 + dz2 : 0.005545 d : 0.054395 + dxz : 0.011044 + dyz : 0.012968 + dx2y2 : 0.012739 + dxy : 0.012098 + + 1 O s : 3.753895 s : 3.753895 + pz : 1.381914 p : 3.907184 + px : 1.457365 + py : 1.067905 + dz2 : 0.007685 d : 0.127525 + dxz : 0.012386 + dyz : 0.040645 + dx2y2 : 0.050351 + dxy : 0.016458 + + 2 O s : 3.942703 s : 3.942703 + pz : 1.315031 p : 4.189080 + px : 1.440436 + py : 1.433612 + dz2 : 0.002800 d : 0.023324 + dxz : 0.006308 + dyz : 0.004554 + dx2y2 : 0.002911 + dxy : 0.006750 + + 3 H s : 0.694549 s : 0.694549 + pz : 0.010101 p : 0.030191 + px : 0.013161 + py : 0.006929 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.084491 + 1 O : -0.191203 + 2 O : -0.006074 + 3 H : 0.281768 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.358795 s : 3.358795 + pz : 1.018354 p : 3.414376 + px : 1.424341 + py : 0.971681 + dz2 : 0.033059 d : 0.311320 + dxz : 0.018687 + dyz : 0.065747 + dx2y2 : 0.074217 + dxy : 0.119610 + + 1 O s : 3.367816 s : 3.367816 + pz : 1.282226 p : 4.043933 + px : 1.480511 + py : 1.281196 + dz2 : 0.062946 d : 0.779454 + dxz : 0.041809 + dyz : 0.191719 + dx2y2 : 0.232424 + dxy : 0.250557 + + 2 O s : 3.598016 s : 3.598016 + pz : 1.258787 p : 4.149669 + px : 1.436289 + py : 1.454594 + dz2 : 0.034193 d : 0.258389 + dxz : 0.037922 + dyz : 0.035552 + dx2y2 : 0.078485 + dxy : 0.072238 + + 3 H s : 0.642302 s : 0.642302 + pz : 0.024620 p : 0.075930 + px : 0.037330 + py : 0.013980 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3315 7.0000 -0.3315 2.6613 2.6613 -0.0000 + 1 O 7.7886 8.0000 0.2114 2.6052 2.6052 -0.0000 + 2 O 8.1551 8.0000 -0.1551 1.7115 1.7115 -0.0000 + 3 H 0.7247 1.0000 0.2753 0.9093 0.9093 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3567 B( 0-N , 2-O ) : 0.4400 B( 0-N , 3-H ) : 0.8646 +B( 1-O , 2-O ) : 1.2377 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 8 sec + +Total time .... 8.460 sec +Sum of individual times .... 7.851 sec ( 92.8%) + +SCF preparation .... 1.466 sec ( 17.3%) +Fock matrix formation .... 2.483 sec ( 29.4%) + Startup .... 0.487 sec ( 19.6% of F) + Split-RI-J .... 0.034 sec ( 1.4% of F) + XC integration .... 0.471 sec ( 19.0% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.010 sec ( 2.2% of XC) + Density eval. .... 0.012 sec ( 2.6% of XC) + XC-Functional eval. .... 0.009 sec ( 1.9% of XC) + XC-Potential eval. .... 0.012 sec ( 2.6% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.211 sec ( 2.5%) +Total Energy calculation .... 0.018 sec ( 0.2%) +Population analysis .... 3.034 sec ( 35.9%) +Orbital Transformation .... 0.069 sec ( 0.8%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.175 sec ( 2.1%) +SOSCF solution .... 0.395 sec ( 4.7%) +Finished LeanSCF after 11.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 46.6 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360950 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007171973 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.538118261566 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.035.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.035.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.378408 0.820661 -0.169243 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5449292837542998 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.028990316 0.890859177 -0.195093060 +Nuclear contribution : -0.810601927 -1.449677847 0.370023916 + ----------------------------------------- +Total Dipole Moment : -0.781611611 -0.558818670 0.174930857 + ----------------------------------------- +Magnitude (a.u.) : 0.976624708 +Magnitude (Debye) : 2.482382731 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.156565 0.422471 0.380729 +Rotational constants in MHz : 94631.428050 12665.349237 11413.979681 + +Dipole components along the rotational axes: +x,y,z [a.u.] : -0.742583 -0.512912 0.373213 +x,y,z [Debye]: -1.887496 -1.303718 0.948631 + + + +Dipole moment calculation done in 0.9 sec + +Maximum memory used throughout the entire PROP-calculation: 24.3 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 36 * + * * + * Dihedral ( 2, 1, 0, 3) : 143.07692308 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.3026 0.691342 + 2. B(O 2,O 1) 1.2944 0.719799 + 3. B(H 3,N 0) 1.0369 0.396752 + 4. A(O 1,N 0,H 3) 101.3223 0.357750 + 5. A(N 0,O 1,O 2) 116.7319 0.442819 + 6. D(O 2,O 1,N 0,H 3) 143.0769 0.037253 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.142293 -0.697300 -0.174449 + O -0.206721 0.557657 -0.162130 + O 0.730376 1.420389 0.068251 + H -0.684657 -1.142903 0.264620 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.268896 -1.317706 -0.329661 + 1 O 8.0000 0 15.999 -0.390646 1.053820 -0.306382 + 2 O 8.0000 0 15.999 1.380211 2.684146 0.128975 + 3 H 1.0000 0 1.008 -1.293814 -2.159773 0.500060 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.302449964138 0.00000000 0.00000000 + O 2 1 0 1.291469681773 116.86125580 0.00000000 + H 1 2 3 1.033614930030 101.34355854 133.84615409 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.461273735357 0.00000000 0.00000000 + O 2 1 0 2.440524008813 116.86125580 0.00000000 + H 1 2 3 1.953249145690 101.34355854 133.84615409 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1667 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.659477039916 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.853e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.6594770399 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.5 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5492763668949010 0.00e+00 3.96e-04 3.79e-03 2.71e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.073) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5505210649031937 -1.24e-03 4.69e-04 4.76e-03 2.05e-02 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.5515465287288066 -1.03e-03 3.59e-04 3.62e-03 1.46e-02 0.700 0.0 + 4 -205.5522637377022193 -7.17e-04 8.93e-04 9.09e-03 1.03e-02 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5539322244947584 -1.67e-03 6.64e-05 5.37e-04 5.51e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 6 -205.5539363842420926 -4.16e-06 1.88e-04 3.01e-03 6.19e-04 0.0 + 7 -205.5538899609034047 4.64e-05 1.44e-04 2.18e-03 3.25e-03 0.0 + 8 -205.5539442105082344 -5.42e-05 4.62e-05 5.41e-04 1.86e-04 0.0 + 9 -205.5539427845633327 1.43e-06 2.23e-05 4.25e-04 5.58e-04 0.0 + 10 -205.5539447474434951 -1.96e-06 1.49e-05 1.19e-04 4.87e-05 0.0 + 11 -205.5539447797875710 -3.23e-08 5.84e-06 4.99e-05 3.39e-05 0.0 + 12 -205.5539448065803754 -2.68e-08 4.13e-07 3.91e-06 3.05e-06 0.0 + 13 -205.5539448073232052 -7.43e-10 1.64e-07 1.58e-06 1.69e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 13 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.55394480732321 Eh -5593.40720 eV + +Components: +Nuclear Repulsion : 69.65947703991604 Eh 1895.53074 eV +Electronic Energy : -275.21342184723926 Eh -7488.93794 eV +One Electron Energy: -419.04870952462142 Eh -11402.89510 eV +Two Electron Energy: 143.83528767738218 Eh 3913.95716 eV + +Virial components: +Potential Energy : -410.37477608536585 Eh -11166.86537 eV +Kinetic Energy : 204.82083127804268 Eh 5573.45817 eV +Virial Ratio : 2.00357929183622 + +DFT components: +N(Alpha) : 11.999997929735 electrons +N(Beta) : 11.999997929735 electrons +N(Total) : 23.999995859470 electrons +E(X) : -23.338414124272 Eh +E(C) : -0.804090145873 Eh +E(XC) : -24.142504270145 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 7.4283e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.5813e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.6367e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.5071e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.6930e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 4.2701e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.189383 -522.1697 + 1 2.0000 -19.026774 -517.7448 + 2 2.0000 -14.263848 -388.1390 + 3 2.0000 -1.250469 -34.0270 + 4 2.0000 -0.968101 -26.3434 + 5 2.0000 -0.701528 -19.0896 + 6 2.0000 -0.563631 -15.3372 + 7 2.0000 -0.516217 -14.0470 + 8 2.0000 -0.506957 -13.7950 + 9 2.0000 -0.332387 -9.0447 + 10 2.0000 -0.276850 -7.5335 + 11 2.0000 -0.262924 -7.1545 + 12 0.0000 -0.190986 -5.1970 + 13 0.0000 0.050069 1.3624 + 14 0.0000 0.081684 2.2227 + 15 0.0000 0.139280 3.7900 + 16 0.0000 0.222098 6.0436 + 17 0.0000 0.270937 7.3726 + 18 0.0000 0.307774 8.3749 + 19 0.0000 0.327557 8.9133 + 20 0.0000 0.347085 9.4447 + 21 0.0000 0.380091 10.3428 + 22 0.0000 0.401472 10.9246 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.316863 + 1 O : 0.214845 + 2 O : -0.170962 + 3 H : 0.272980 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.894937 s : 3.894937 + pz : 1.084650 p : 3.365488 + px : 1.450417 + py : 0.830421 + dz2 : 0.006284 d : 0.056438 + dxz : 0.010957 + dyz : 0.013048 + dx2y2 : 0.013110 + dxy : 0.013039 + + 1 O s : 3.753673 s : 3.753673 + pz : 1.384842 p : 3.900816 + px : 1.455327 + py : 1.060647 + dz2 : 0.006320 d : 0.130666 + dxz : 0.012178 + dyz : 0.041698 + dx2y2 : 0.052105 + dxy : 0.018366 + + 2 O s : 3.944422 s : 3.944422 + pz : 1.352834 p : 4.202162 + px : 1.433372 + py : 1.415956 + dz2 : 0.002352 d : 0.024378 + dxz : 0.007258 + dyz : 0.004574 + dx2y2 : 0.003141 + dxy : 0.007052 + + 3 H s : 0.697362 s : 0.697362 + pz : 0.009005 p : 0.029658 + px : 0.013563 + py : 0.007089 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.075706 + 1 O : -0.191168 + 2 O : -0.014917 + 3 H : 0.281791 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.363275 s : 3.363275 + pz : 1.017856 p : 3.399952 + px : 1.408747 + py : 0.973349 + dz2 : 0.034564 d : 0.312480 + dxz : 0.016390 + dyz : 0.064585 + dx2y2 : 0.073547 + dxy : 0.123394 + + 1 O s : 3.369123 s : 3.369123 + pz : 1.281375 p : 4.042203 + px : 1.483367 + py : 1.277461 + dz2 : 0.062762 d : 0.779842 + dxz : 0.036061 + dyz : 0.191079 + dx2y2 : 0.235242 + dxy : 0.254697 + + 2 O s : 3.599423 s : 3.599423 + pz : 1.286242 p : 4.158253 + px : 1.433666 + py : 1.438346 + dz2 : 0.032504 d : 0.257241 + dxz : 0.034684 + dyz : 0.034656 + dx2y2 : 0.080417 + dxy : 0.074980 + + 3 H s : 0.643610 s : 0.643610 + pz : 0.021578 p : 0.074600 + px : 0.038518 + py : 0.014503 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3169 7.0000 -0.3169 2.6844 2.6844 -0.0000 + 1 O 7.7852 8.0000 0.2148 2.6208 2.6208 -0.0000 + 2 O 8.1710 8.0000 -0.1710 1.7227 1.7227 -0.0000 + 3 H 0.7270 1.0000 0.2730 0.9109 0.9109 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3666 B( 0-N , 2-O ) : 0.4485 B( 0-N , 3-H ) : 0.8692 +B( 1-O , 2-O ) : 1.2433 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 5 sec + +Total time .... 5.051 sec +Sum of individual times .... 5.035 sec ( 99.7%) + +SCF preparation .... 1.437 sec ( 28.4%) +Fock matrix formation .... 0.324 sec ( 6.4%) + Startup .... 0.014 sec ( 4.4% of F) + Split-RI-J .... 0.047 sec ( 14.5% of F) + XC integration .... 0.211 sec ( 65.3% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.016 sec ( 7.4% of XC) + Density eval. .... 0.021 sec ( 9.8% of XC) + XC-Functional eval. .... 0.012 sec ( 5.9% of XC) + XC-Potential eval. .... 0.021 sec ( 10.0% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.026 sec ( 0.5%) +Total Energy calculation .... 0.026 sec ( 0.5%) +Population analysis .... 3.095 sec ( 61.3%) +Orbital Transformation .... 0.013 sec ( 0.3%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.067 sec ( 1.3%) +SOSCF solution .... 0.047 sec ( 0.9%) +Finished LeanSCF after 7.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 46.9 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360538 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007175995 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.547129350184 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003702 -0.000005940 0.000001016 + 2 O : -0.000000403 0.000000611 -0.000000187 + 3 O : 0.000003794 0.000008488 0.000000213 + 4 H : 0.000000311 -0.000003160 -0.000001042 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000121753 +RMS gradient ... 0.0000035147 +MAX gradient ... 0.0000084879 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.011679906 -0.008412895 -0.017729955 + 2 O : 0.003428876 0.007018355 -0.030181696 + 3 O : -0.001170491 0.000875443 0.023314706 + 4 H : 0.009421521 0.000519097 0.024596946 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000174597 -0.0000179657 0.0000188182 + +Norm of the Cartesian gradient ... 0.0522805302 +RMS gradient ... 0.0150920891 +MAX gradient ... 0.0301816964 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.256 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.004 sec ( 1.8%) +RI-J Coulomb gradient .... 0.056 sec ( 21.9%) +XC gradient .... 0.017 sec ( 6.6%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.3 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.547129350 Eh +Current gradient norm .... 0.052280530 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999883724 +Lowest eigenvalues of augmented Hessian: + -0.000129334 0.356988586 0.391990910 0.441897139 0.690919817 +Length of the computed step .... 0.015250968 +The final length of the internal step .... 0.015250968 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0062261818 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0058123751 RMS(Int)= 0.0062229428 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0036005158 0.0001000000 NO + MAX gradient 0.0069328413 0.0003000000 NO + RMS step 0.0062261818 0.0020000000 NO + MAX step 0.0100333508 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0053 Max(Angles) 0.41 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.3026 0.006933 -0.0053 1.2973 + 2. B(O 2,O 1) 1.2944 0.003886 -0.0029 1.2915 + 3. B(H 3,N 0) 1.0369 0.002680 -0.0036 1.0333 + 4. A(O 1,N 0,H 3) 101.32 0.002527 -0.41 100.92 + 5. A(N 0,O 1,O 2) 116.73 -0.001023 0.13 116.86 + 6. D(O 2,O 1,N 0,H 3) 143.08 -0.050303 0.00 143.08 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 4.956 %) +Internal coordinates : 0.000 s ( 1.652 %) +B/P matrices and projection : 0.000 s ( 6.763 %) +Hessian update/contruction : 0.000 s (22.561 %) +Making the step : 0.000 s ( 2.891 %) +Converting the step to Cartesian: 0.000 s ( 2.065 %) +Storing new data : 0.000 s ( 1.755 %) +Checking convergence : 0.000 s ( 0.052 %) +Final printing : 0.001 s (57.253 %) +Total time : 0.002 s + +Time for energy+gradient : 14.192 s +Time for complete geometry iter : 15.139 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.142958 -0.696450 -0.175444 + O -0.205772 0.553047 -0.160530 + O 0.726956 1.416604 0.068274 + H -0.682850 -1.135358 0.263992 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.270151 -1.316099 -0.331540 + 1 O 8.0000 0 15.999 -0.388852 1.045107 -0.303357 + 2 O 8.0000 0 15.999 1.373749 2.676994 0.129019 + 3 H 1.0000 0 1.008 -1.290400 -2.145515 0.498872 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.297334166755 0.00000000 0.00000000 + O 2 1 0 1.291535566473 116.86457589 0.00000000 + H 1 2 3 1.033296873176 100.91690632 143.07692300 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.451606279346 0.00000000 0.00000000 + O 2 1 0 2.440648512853 116.86457589 0.00000000 + H 1 2 3 1.952648105340 100.91690632 143.07692300 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1668 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.878257771354 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.820e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22305 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.3 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 1.1 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5539892564652860 0.00e+00 1.47e-04 1.20e-03 2.47e-04 0.8 + *** Restarting incremental Fock matrix formation *** + 2 -205.5540224383107670 -3.32e-05 1.72e-04 2.15e-03 4.87e-04 0.4 + 3 -205.5539807277905879 4.17e-05 1.27e-04 2.31e-03 2.78e-03 0.2 + 4 -205.5540247927356745 -4.41e-05 1.06e-04 1.78e-03 5.85e-04 0.2 + 5 -205.5540102363236201 1.46e-05 6.94e-05 1.28e-03 1.71e-03 0.4 + 6 -205.5540274295653944 -1.72e-05 2.49e-05 4.45e-04 9.06e-05 0.1 + 7 -205.5540273650391327 6.45e-08 1.36e-05 2.45e-04 1.01e-04 0.3 + 8 -205.5540276036295495 -2.39e-07 3.78e-07 4.24e-06 1.86e-06 0.2 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.55402760362955 Eh -5593.40945 eV + +Components: +Nuclear Repulsion : 69.87825777135407 Eh 1901.48406 eV +Electronic Energy : -275.43228537498362 Eh -7494.89352 eV +One Electron Energy: -419.46550819023685 Eh -11414.23677 eV +Two Electron Energy: 144.03322281525323 Eh 3919.34325 eV + +Virial components: +Potential Energy : -410.40040993028686 Eh -11167.56290 eV +Kinetic Energy : 204.84638232665733 Eh 5574.15345 eV +Virial Ratio : 2.00345451683810 + +DFT components: +N(Alpha) : 11.999997892983 electrons +N(Beta) : 11.999997892983 electrons +N(Total) : 23.999995785966 electrons +E(X) : -23.345311164119 Eh +E(C) : -0.804529413503 Eh +E(XC) : -24.149840577621 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.3859e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 4.2387e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.7771e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.7404e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.8602e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.9595e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 4 sec +Finished LeanSCF after 7.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 47.1 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360687 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007181590 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.547206700667 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003697 -0.000005896 0.000001023 + 2 O : -0.000000404 0.000000591 -0.000000179 + 3 O : 0.000003744 0.000008395 0.000000215 + 4 H : 0.000000357 -0.000003091 -0.000001060 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000120568 +RMS gradient ... 0.0000034805 +MAX gradient ... 0.0000083952 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.013636963 -0.005730570 -0.017108607 + 2 O : 0.005759271 0.004098692 -0.029857373 + 3 O : -0.003297871 -0.001341353 0.023106752 + 4 H : 0.011175564 0.002973230 0.023859228 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000120244 -0.0000193429 0.0000178299 + +Norm of the Cartesian gradient ... 0.0519859125 +RMS gradient ... 0.0150070403 +MAX gradient ... 0.0298573728 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.421 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.006 sec ( 1.3%) +RI-J Coulomb gradient .... 0.065 sec ( 15.4%) +XC gradient .... 0.019 sec ( 4.4%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.4 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.547206701 Eh +Current gradient norm .... 0.051985913 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999981266 +Lowest eigenvalues of augmented Hessian: + -0.000015221 0.356230844 0.372595314 0.446353075 0.583631831 +Length of the computed step .... 0.006121184 +The final length of the internal step .... 0.006121184 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0024989628 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0015711492 RMS(Int)= 0.0024981422 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000007611 +Previously predicted energy change .... -0.000064682 +Actually observed energy change .... -0.000077350 +Ratio of predicted to observed change .... 1.195858787 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000773505 0.0000050000 NO + RMS gradient 0.0010291604 0.0001000000 NO + MAX gradient 0.0019146629 0.0003000000 NO + RMS step 0.0024989628 0.0020000000 NO + MAX step 0.0041527092 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0022 Max(Angles) 0.23 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2973 0.001915 -0.0022 1.2951 + 2. B(O 2,O 1) 1.2915 0.000816 -0.0010 1.2906 + 3. B(H 3,N 0) 1.0333 -0.000047 -0.0002 1.0331 + 4. A(O 1,N 0,H 3) 100.92 -0.000249 0.02 100.94 + 5. A(N 0,O 1,O 2) 116.86 -0.001400 0.23 117.10 + 6. D(O 2,O 1,N 0,H 3) 143.08 -0.050845 0.00 143.08 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.076 %) +Internal coordinates : 0.000 s ( 0.028 %) +B/P matrices and projection : 0.000 s ( 0.188 %) +Hessian update/contruction : 0.080 s (95.591 %) +Making the step : 0.000 s ( 0.076 %) +Converting the step to Cartesian: 0.000 s ( 0.052 %) +Storing new data : 0.000 s ( 0.041 %) +Checking convergence : 0.000 s ( 0.013 %) +Final printing : 0.003 s ( 3.932 %) +Total time : 0.083 s + +Time for energy+gradient : 14.207 s +Time for complete geometry iter : 15.242 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.142505 -0.696220 -0.175900 + O -0.203979 0.551606 -0.159821 + O 0.725899 1.417049 0.068049 + H -0.683132 -1.134591 0.263963 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.269295 -1.315665 -0.332402 + 1 O 8.0000 0 15.999 -0.385465 1.042384 -0.302017 + 2 O 8.0000 0 15.999 1.371750 2.677834 0.128594 + 3 H 1.0000 0 1.008 -1.290933 -2.144066 0.498818 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.295136647674 0.00000000 0.00000000 + O 2 1 0 1.290577126813 117.09870753 0.00000000 + H 1 2 3 1.033114064769 100.93722402 143.07692300 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.447453570108 0.00000000 0.00000000 + O 2 1 0 2.438837324380 117.09870753 0.00000000 + H 1 2 3 1.952302647516 100.93722402 143.07692300 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.939203032863 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.806e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.5 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.9 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5540163548974135 0.00e+00 8.34e-05 7.23e-04 1.74e-04 0.7 + *** Restarting incremental Fock matrix formation *** + 2 -205.5540262425650724 -9.89e-06 5.04e-05 5.49e-04 1.55e-04 0.5 + 3 -205.5540269159579623 -6.73e-07 2.92e-05 3.84e-04 1.99e-04 0.2 + 4 -205.5540264261539676 4.90e-07 2.79e-05 4.37e-04 2.83e-04 0.2 + 5 -205.5540267260630856 -3.00e-07 3.53e-05 4.05e-04 2.67e-04 0.1 + 6 -205.5540260185446471 7.08e-07 2.86e-05 3.59e-04 3.90e-04 0.3 + 7 -205.5540272459925575 -1.23e-06 7.82e-06 1.14e-04 4.22e-05 0.3 + 8 -205.5540272595937097 -1.36e-08 3.68e-06 3.84e-05 2.49e-05 0.1 + 9 -205.5540272784762976 -1.89e-08 3.23e-07 3.33e-06 2.79e-06 0.0 + 10 -205.5540272787605147 -2.84e-10 7.25e-08 7.33e-07 6.78e-07 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 10 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.55402727876051 Eh -5593.40945 eV + +Components: +Nuclear Repulsion : 69.93920303286293 Eh 1903.14247 eV +Electronic Energy : -275.49323031162351 Eh -7496.55191 eV +One Electron Energy: -419.58079656988031 Eh -11417.37392 eV +Two Electron Energy: 144.08756625825683 Eh 3920.82201 eV + +Virial components: +Potential Energy : -410.40678822316772 Eh -11167.73646 eV +Kinetic Energy : 204.85276094440718 Eh 5574.32702 eV +Virial Ratio : 2.00342327011420 + +DFT components: +N(Alpha) : 11.999997827849 electrons +N(Beta) : 11.999997827849 electrons +N(Total) : 23.999995655698 electrons +E(X) : -23.347273166701 Eh +E(C) : -0.804664024436 Eh +E(XC) : -24.151937191136 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.8422e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.3302e-07 Tolerance : 1.0000e-07 + Last RMS-Density change ... 7.2523e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.0747e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 6.7786e-07 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 8.9380e-07 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 4 sec +Finished LeanSCF after 6.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 47.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360696 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007173083 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.547214891308 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003697 -0.000005894 0.000001024 + 2 O : -0.000000401 0.000000588 -0.000000177 + 3 O : 0.000003738 0.000008393 0.000000215 + 4 H : 0.000000360 -0.000003087 -0.000001062 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000120512 +RMS gradient ... 0.0000034789 +MAX gradient ... 0.0000083926 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.014722491 -0.004399381 -0.017135074 + 2 O : 0.007785264 0.002903128 -0.029823371 + 3 O : -0.004344376 -0.001533509 0.023047565 + 4 H : 0.011281603 0.003029762 0.023910880 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000079931 -0.0000183272 0.0000183172 + +Norm of the Cartesian gradient ... 0.0524288915 +RMS gradient ... 0.0151349173 +MAX gradient ... 0.0298233710 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.124 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.0%) +RI-J Coulomb gradient .... 0.061 sec ( 48.9%) +XC gradient .... 0.019 sec ( 15.2%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.5 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.547214891 Eh +Current gradient norm .... 0.052428891 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999224 +Lowest eigenvalues of augmented Hessian: + -0.000000597 0.335459960 0.403548854 0.412411736 0.567835538 +Length of the computed step .... 0.001246078 +The final length of the internal step .... 0.001246078 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0005087092 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0003471141 RMS(Int)= 0.0005087262 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000299 +Previously predicted energy change .... -0.000007611 +Actually observed energy change .... -0.000008191 +Ratio of predicted to observed change .... 1.076208988 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000081906 0.0000050000 NO + RMS gradient 0.0002008866 0.0001000000 NO + MAX gradient 0.0003484068 0.0003000000 NO + RMS step 0.0005087092 0.0020000000 YES + MAX step 0.0009849516 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0004 Max(Angles) 0.06 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2951 0.000313 -0.0004 1.2948 + 2. B(O 2,O 1) 1.2906 -0.000088 0.0000 1.2906 + 3. B(H 3,N 0) 1.0331 -0.000120 0.0001 1.0332 + 4. A(O 1,N 0,H 3) 100.94 -0.000348 0.06 100.99 + 5. A(N 0,O 1,O 2) 117.10 0.000021 0.00 117.10 + 6. D(O 2,O 1,N 0,H 3) 143.08 -0.051018 -0.00 143.08 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.565 %) +Internal coordinates : 0.000 s ( 3.274 %) +B/P matrices and projection : 0.000 s (16.518 %) +Hessian update/contruction : 0.000 s (29.018 %) +Making the step : 0.000 s ( 5.655 %) +Converting the step to Cartesian: 0.000 s ( 5.060 %) +Storing new data : 0.000 s ( 3.571 %) +Checking convergence : 0.000 s ( 1.637 %) +Final printing : 0.000 s (23.810 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.142313 -0.695862 -0.175762 + O -0.203886 0.551652 -0.159917 + O 0.726010 1.417076 0.068018 + H -0.683145 -1.135023 0.263953 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.268933 -1.314988 -0.332142 + 1 O 8.0000 0 15.999 -0.385289 1.042471 -0.302199 + 2 O 8.0000 0 15.999 1.371960 2.677886 0.128535 + 3 H 1.0000 0 1.008 -1.290957 -2.144882 0.498799 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.294757082335 0.00000000 0.00000000 + O 2 1 0 1.290589010189 117.10369026 0.00000000 + H 1 2 3 1.033243719347 100.99365758 143.07692300 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.446736295568 0.00000000 0.00000000 + O 2 1 0 2.438859780706 117.10369026 0.00000000 + H 1 2 3 1.952547659160 100.99365758 143.07692300 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.945899802142 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.806e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.9458998021 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5540261648216926 0.00e+00 1.32e-05 2.05e-04 2.40e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5540263563910059 -1.92e-07 8.28e-06 9.16e-05 3.45e-05 0.0 + 3 -205.5540263295907550 2.68e-08 3.94e-06 6.03e-05 8.96e-05 0.0 + 4 -205.5540263768293983 -4.72e-08 5.97e-06 8.18e-05 2.64e-05 0.0 + 5 -205.5540263127307128 6.41e-08 4.68e-06 7.29e-05 1.12e-04 0.0 + 6 -205.5540263812403339 -6.85e-08 1.35e-06 2.08e-05 4.14e-06 0.0 + 7 -205.5540263813913668 -1.51e-10 6.31e-07 1.02e-05 4.27e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.55402638139137 Eh -5593.40942 eV + +Components: +Nuclear Repulsion : 69.94589980214155 Eh 1903.32470 eV +Electronic Energy : -275.49992618353292 Eh -7496.73412 eV +One Electron Energy: -419.59361196866388 Eh -11417.72265 eV +Two Electron Energy: 144.09368578513093 Eh 3920.98853 eV + +Virial components: +Potential Energy : -410.40721282018217 Eh -11167.74802 eV +Kinetic Energy : 204.85318643879080 Eh 5574.33860 eV +Virial Ratio : 2.00342118155340 + +DFT components: +N(Alpha) : 11.999997829040 electrons +N(Beta) : 11.999997829040 electrons +N(Total) : 23.999995658079 electrons +E(X) : -23.347407784587 Eh +E(C) : -0.804675144103 Eh +E(XC) : -24.152082928690 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.5103e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.0204e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 6.3127e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.9276e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.2715e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 5.8198e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.189913 -522.1841 + 1 2.0000 -19.025992 -517.7236 + 2 2.0000 -14.263032 -388.1168 + 3 2.0000 -1.254995 -34.1501 + 4 2.0000 -0.972035 -26.4504 + 5 2.0000 -0.700171 -19.0526 + 6 2.0000 -0.565934 -15.3998 + 7 2.0000 -0.518652 -14.1132 + 8 2.0000 -0.507875 -13.8200 + 9 2.0000 -0.332516 -9.0482 + 10 2.0000 -0.277036 -7.5385 + 11 2.0000 -0.262141 -7.1332 + 12 0.0000 -0.189321 -5.1517 + 13 0.0000 0.054345 1.4788 + 14 0.0000 0.082519 2.2455 + 15 0.0000 0.144864 3.9420 + 16 0.0000 0.223328 6.0771 + 17 0.0000 0.270367 7.3571 + 18 0.0000 0.307411 8.3651 + 19 0.0000 0.328490 8.9387 + 20 0.0000 0.346283 9.4228 + 21 0.0000 0.380833 10.3630 + 22 0.0000 0.401318 10.9204 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.317228 + 1 O : 0.218054 + 2 O : -0.173402 + 3 H : 0.272576 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.893306 s : 3.893306 + pz : 1.084374 p : 3.366903 + px : 1.451310 + py : 0.831219 + dz2 : 0.006370 d : 0.057019 + dxz : 0.010980 + dyz : 0.013314 + dx2y2 : 0.013292 + dxy : 0.013063 + + 1 O s : 3.748860 s : 3.748860 + pz : 1.382247 p : 3.900576 + px : 1.458714 + py : 1.059615 + dz2 : 0.006388 d : 0.132510 + dxz : 0.012208 + dyz : 0.042598 + dx2y2 : 0.052592 + dxy : 0.018725 + + 2 O s : 3.943371 s : 3.943371 + pz : 1.352911 p : 4.205442 + px : 1.440161 + py : 1.412371 + dz2 : 0.002370 d : 0.024589 + dxz : 0.007274 + dyz : 0.004696 + dx2y2 : 0.003125 + dxy : 0.007124 + + 3 H s : 0.697455 s : 0.697455 + pz : 0.009127 p : 0.029969 + px : 0.013692 + py : 0.007151 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.073780 + 1 O : -0.193648 + 2 O : -0.013848 + 3 H : 0.281276 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.357468 s : 3.357468 + pz : 1.016693 p : 3.401504 + px : 1.407772 + py : 0.977038 + dz2 : 0.034642 d : 0.314808 + dxz : 0.016444 + dyz : 0.065247 + dx2y2 : 0.074162 + dxy : 0.124313 + + 1 O s : 3.363542 s : 3.363542 + pz : 1.278690 p : 4.043380 + px : 1.486051 + py : 1.278638 + dz2 : 0.063109 d : 0.786727 + dxz : 0.035865 + dyz : 0.193767 + dx2y2 : 0.236948 + dxy : 0.257038 + + 2 O s : 3.596618 s : 3.596618 + pz : 1.285414 p : 4.159573 + px : 1.438394 + py : 1.435765 + dz2 : 0.032507 d : 0.257657 + dxz : 0.034298 + dyz : 0.035000 + dx2y2 : 0.080576 + dxy : 0.075276 + + 3 H s : 0.643539 s : 0.643539 + pz : 0.021868 p : 0.075185 + px : 0.038801 + py : 0.014516 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3172 7.0000 -0.3172 2.6834 2.6834 0.0000 + 1 O 7.7819 8.0000 0.2181 2.6225 2.6225 0.0000 + 2 O 8.1734 8.0000 -0.1734 1.7211 1.7211 0.0000 + 3 H 0.7274 1.0000 0.2726 0.9113 0.9113 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3678 B( 0-N , 2-O ) : 0.4459 B( 0-N , 3-H ) : 0.8697 +B( 1-O , 2-O ) : 1.2442 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 4 sec + +Total time .... 4.275 sec +Sum of individual times .... 4.258 sec ( 99.6%) + +SCF preparation .... 1.324 sec ( 31.0%) +Fock matrix formation .... 0.176 sec ( 4.1%) + Startup .... 0.009 sec ( 4.9% of F) + Split-RI-J .... 0.025 sec ( 14.2% of F) + XC integration .... 0.116 sec ( 66.1% of F) + Basis function eval. .... 0.008 sec ( 6.5% of XC) + Density eval. .... 0.010 sec ( 8.8% of XC) + XC-Functional eval. .... 0.006 sec ( 5.1% of XC) + XC-Potential eval. .... 0.010 sec ( 8.8% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.011 sec ( 0.3%) +Total Energy calculation .... 0.015 sec ( 0.3%) +Population analysis .... 2.679 sec ( 62.7%) +Orbital Transformation .... 0.006 sec ( 0.1%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.010 sec ( 0.2%) +SOSCF solution .... 0.038 sec ( 0.9%) +Finished LeanSCF after 7.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 47.6 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360694 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007171777 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.547215299268 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.036.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.036.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.388220 0.828301 -0.147363 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5540263813913668 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.026883731 0.850760441 -0.161535540 +Nuclear contribution : -0.832349407 -1.466165248 0.321203788 + ----------------------------------------- +Total Dipole Moment : -0.805465676 -0.615404807 0.159668248 + ----------------------------------------- +Magnitude (a.u.) : 1.026153975 +Magnitude (Debye) : 2.608276122 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.258831 0.423865 0.380681 +Rotational constants in MHz : 97697.310115 12707.161298 11412.542195 + +Dipole components along the rotational axes: +x,y,z [a.u.] : -0.811790 -0.552192 0.298451 +x,y,z [Debye]: -2.063407 -1.403560 0.758602 + + + +Dipole moment calculation done in 0.8 sec + +Maximum memory used throughout the entire PROP-calculation: 24.8 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 37 * + * * + * Dihedral ( 2, 1, 0, 3) : 152.30769231 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2949 0.711158 + 2. B(O 2,O 1) 1.2936 0.722131 + 3. B(H 3,N 0) 1.0364 0.397293 + 4. A(O 1,N 0,H 3) 100.9906 0.359558 + 5. A(N 0,O 1,O 2) 116.9713 0.445351 + 6. D(O 2,O 1,N 0,H 3) 152.3077 0.039659 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.152955 -0.691755 -0.143561 + O -0.205601 0.552127 -0.111787 + O 0.733954 1.430159 0.028876 + H -0.700015 -1.152687 0.222763 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.289042 -1.307228 -0.271291 + 1 O 8.0000 0 15.999 -0.388529 1.043370 -0.211246 + 2 O 8.0000 0 15.999 1.386971 2.702609 0.054569 + 3 H 1.0000 0 1.008 -1.322837 -2.178264 0.420962 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.294757082335 0.00000000 0.00000000 + O 2 1 0 1.290589010189 117.10369026 0.00000000 + H 1 2 3 1.033243719347 100.99365758 143.07692300 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.446736295568 0.00000000 0.00000000 + O 2 1 0 2.438859780706 117.10369026 0.00000000 + H 1 2 3 1.952547659160 100.99365758 143.07692300 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1668 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.841056540281 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.804e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22305 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.8410565403 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5565350042608657 0.00e+00 3.88e-04 3.95e-03 2.77e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.077) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5577959849414924 -1.26e-03 4.59e-04 4.89e-03 2.08e-02 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.5588321869108768 -1.04e-03 3.50e-04 3.74e-03 1.48e-02 0.700 0.0 + 4 -205.5595569666980964 -7.25e-04 8.69e-04 9.41e-03 1.04e-02 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5612426008652847 -1.69e-03 6.29e-05 5.19e-04 5.23e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 6 -205.5612465430930911 -3.94e-06 1.82e-04 2.71e-03 6.24e-04 0.0 + 7 -205.5612041588931902 4.24e-05 1.36e-04 2.19e-03 3.48e-03 0.0 + 8 -205.5612536214420061 -4.95e-05 3.90e-05 3.40e-04 1.24e-04 0.0 + 9 -205.5612538775969256 -2.56e-07 9.84e-06 1.43e-04 9.16e-05 0.0 + 10 -205.5612539232694758 -4.57e-08 1.19e-05 9.56e-05 1.28e-04 0.0 + 11 -205.5612539696310250 -4.64e-08 6.97e-06 6.39e-05 4.14e-05 0.0 + 12 -205.5612540046137724 -3.50e-08 9.88e-07 1.10e-05 9.44e-06 0.0 + 13 -205.5612540061758864 -1.56e-09 5.02e-07 5.87e-06 2.65e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 13 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56125400617589 Eh -5593.60609 eV + +Components: +Nuclear Repulsion : 69.84105654028146 Eh 1900.47177 eV +Electronic Energy : -275.40231054645733 Eh -7494.07786 eV +One Electron Energy: -419.40206486035441 Eh -11412.51039 eV +Two Electron Energy: 143.99975431389709 Eh 3918.43252 eV + +Virial components: +Potential Energy : -410.39293872684550 Eh -11167.35960 eV +Kinetic Energy : 204.83168472066964 Eh 5573.75351 eV +Virial Ratio : 2.00356179897901 + +DFT components: +N(Alpha) : 11.999996933308 electrons +N(Beta) : 11.999996933308 electrons +N(Total) : 23.999993866615 electrons +E(X) : -23.344427985625 Eh +E(C) : -0.804419466229 Eh +E(XC) : -24.148847451854 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.5621e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.8732e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 5.0211e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.2323e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.6462e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.3360e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.190764 -522.2072 + 1 2.0000 -19.022550 -517.6299 + 2 2.0000 -14.266831 -388.2202 + 3 2.0000 -1.253264 -34.1031 + 4 2.0000 -0.971098 -26.4249 + 5 2.0000 -0.699500 -19.0344 + 6 2.0000 -0.565705 -15.3936 + 7 2.0000 -0.518826 -14.1180 + 8 2.0000 -0.507064 -13.7979 + 9 2.0000 -0.331083 -9.0092 + 10 2.0000 -0.281568 -7.6618 + 11 2.0000 -0.261082 -7.1044 + 12 0.0000 -0.184893 -5.0312 + 13 0.0000 0.051779 1.4090 + 14 0.0000 0.080694 2.1958 + 15 0.0000 0.143184 3.8962 + 16 0.0000 0.221292 6.0217 + 17 0.0000 0.272634 7.4188 + 18 0.0000 0.303330 8.2540 + 19 0.0000 0.326888 8.8951 + 20 0.0000 0.353385 9.6161 + 21 0.0000 0.379644 10.3306 + 22 0.0000 0.401511 10.9257 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.304226 + 1 O : 0.220326 + 2 O : -0.186519 + 3 H : 0.270419 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.892578 s : 3.892578 + pz : 1.087593 p : 3.352810 + px : 1.430921 + py : 0.834296 + dz2 : 0.007061 d : 0.058838 + dxz : 0.010721 + dyz : 0.013347 + dx2y2 : 0.013726 + dxy : 0.013983 + + 1 O s : 3.748664 s : 3.748664 + pz : 1.384727 p : 3.895098 + px : 1.456526 + py : 1.053845 + dz2 : 0.005331 d : 0.135912 + dxz : 0.012034 + dyz : 0.043678 + dx2y2 : 0.054188 + dxy : 0.020680 + + 2 O s : 3.944961 s : 3.944961 + pz : 1.385553 p : 4.216060 + px : 1.432938 + py : 1.397569 + dz2 : 0.002014 d : 0.025498 + dxz : 0.007955 + dyz : 0.004944 + dx2y2 : 0.003321 + dxy : 0.007263 + + 3 H s : 0.700064 s : 0.700064 + pz : 0.008146 p : 0.029516 + px : 0.014088 + py : 0.007282 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.067126 + 1 O : -0.193376 + 2 O : -0.021125 + 3 H : 0.281627 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.361073 s : 3.361073 + pz : 1.016977 p : 3.390232 + px : 1.395225 + py : 0.978030 + dz2 : 0.036228 d : 0.315821 + dxz : 0.014159 + dyz : 0.064085 + dx2y2 : 0.073727 + dxy : 0.127622 + + 1 O s : 3.364996 s : 3.364996 + pz : 1.278599 p : 4.041678 + px : 1.487119 + py : 1.275960 + dz2 : 0.062961 d : 0.786701 + dxz : 0.031602 + dyz : 0.193473 + dx2y2 : 0.238403 + dxy : 0.260263 + + 2 O s : 3.598168 s : 3.598168 + pz : 1.310383 p : 4.166493 + px : 1.434293 + py : 1.421817 + dz2 : 0.031222 d : 0.256465 + dxz : 0.031926 + dyz : 0.034485 + dx2y2 : 0.081590 + dxy : 0.077243 + + 3 H s : 0.644378 s : 0.644378 + pz : 0.019128 p : 0.073995 + px : 0.039912 + py : 0.014954 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3042 7.0000 -0.3042 2.7027 2.7027 -0.0000 + 1 O 7.7797 8.0000 0.2203 2.6378 2.6378 -0.0000 + 2 O 8.1865 8.0000 -0.1865 1.7312 1.7312 -0.0000 + 3 H 0.7296 1.0000 0.2704 0.9129 0.9129 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3772 B( 0-N , 2-O ) : 0.4523 B( 0-N , 3-H ) : 0.8732 +B( 1-O , 2-O ) : 1.2499 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 4 sec + +Total time .... 4.610 sec +Sum of individual times .... 4.587 sec ( 99.5%) + +SCF preparation .... 1.562 sec ( 33.9%) +Fock matrix formation .... 0.333 sec ( 7.2%) + Startup .... 0.014 sec ( 4.3% of F) + Split-RI-J .... 0.048 sec ( 14.3% of F) + XC integration .... 0.221 sec ( 66.4% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.013 sec ( 6.0% of XC) + Density eval. .... 0.019 sec ( 8.7% of XC) + XC-Functional eval. .... 0.012 sec ( 5.4% of XC) + XC-Potential eval. .... 0.017 sec ( 7.9% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.022 sec ( 0.5%) +Total Energy calculation .... 0.027 sec ( 0.6%) +Population analysis .... 2.513 sec ( 54.5%) +Orbital Transformation .... 0.014 sec ( 0.3%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.068 sec ( 1.5%) +SOSCF solution .... 0.048 sec ( 1.0%) +Finished LeanSCF after 7.3 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 48.0 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360344 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007176756 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.554437594152 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.0 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003750 -0.000005970 0.000000889 + 2 O : -0.000000409 0.000000586 -0.000000117 + 3 O : 0.000003854 0.000008598 0.000000044 + 4 H : 0.000000306 -0.000003215 -0.000000816 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000122841 +RMS gradient ... 0.0000035461 +MAX gradient ... 0.0000085984 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.006274120 -0.005844373 -0.014233331 + 2 O : -0.000500108 0.004905082 -0.023465788 + 3 O : 0.001236420 0.001408923 0.018113024 + 4 H : 0.005537808 -0.000469632 0.019586094 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000170703 -0.0000097139 0.0000216804 + +Norm of the Cartesian gradient ... 0.0399644912 +RMS gradient ... 0.0115367549 +MAX gradient ... 0.0234657884 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.108 sec + +Densities .... 0.000 sec ( 0.4%) +One electron gradient .... 0.005 sec ( 4.2%) +RI-J Coulomb gradient .... 0.049 sec ( 45.2%) +XC gradient .... 0.014 sec ( 13.4%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.554437594 Eh +Current gradient norm .... 0.039964491 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999914332 +Lowest eigenvalues of augmented Hessian: + -0.000096262 0.358814818 0.392671063 0.444403208 0.710781140 +Length of the computed step .... 0.013090346 +The final length of the internal step .... 0.013090346 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0053441115 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0049754016 RMS(Int)= 0.0053416839 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000001 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0031294450 0.0001000000 NO + MAX gradient 0.0057280564 0.0003000000 NO + RMS step 0.0053441115 0.0020000000 NO + MAX step 0.0080582476 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0043 Max(Angles) 0.32 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2949 0.005728 -0.0043 1.2907 + 2. B(O 2,O 1) 1.2936 0.003825 -0.0028 1.2908 + 3. B(H 3,N 0) 1.0364 0.002574 -0.0035 1.0330 + 4. A(O 1,N 0,H 3) 100.99 0.002021 -0.32 100.67 + 5. A(N 0,O 1,O 2) 116.97 -0.000777 0.10 117.07 + 6. D(O 2,O 1,N 0,H 3) 152.31 -0.038782 -0.00 152.31 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (11.548 %) +Internal coordinates : 0.000 s ( 3.808 %) +B/P matrices and projection : 0.000 s (17.568 %) +Hessian update/contruction : 0.000 s (25.799 %) +Making the step : 0.000 s ( 6.511 %) +Converting the step to Cartesian: 0.000 s ( 5.283 %) +Storing new data : 0.000 s ( 4.177 %) +Checking convergence : 0.000 s ( 0.123 %) +Final printing : 0.000 s (24.939 %) +Total time : 0.001 s + +Time for energy+gradient : 12.732 s +Time for complete geometry iter : 13.539 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.153478 -0.691079 -0.144171 + O -0.204701 0.548431 -0.110789 + O 0.730861 1.426699 0.028970 + H -0.698345 -1.146207 0.222282 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.290031 -1.305949 -0.272443 + 1 O 8.0000 0 15.999 -0.386829 1.036384 -0.209362 + 2 O 8.0000 0 15.999 1.381127 2.696070 0.054745 + 3 H 1.0000 0 1.008 -1.319682 -2.166017 0.420053 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.290654875624 0.00000000 0.00000000 + O 2 1 0 1.290799385451 117.07146292 0.00000000 + H 1 2 3 1.032972500190 100.66786900 152.30769249 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.438984248339 0.00000000 0.00000000 + O 2 1 0 2.439257332336 117.07146292 0.00000000 + H 1 2 3 1.952035129231 100.66786900 152.30769249 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.034381843979 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.772e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5612879837225080 0.00e+00 1.28e-04 1.20e-03 2.38e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5613110525463583 -2.31e-05 1.41e-04 1.86e-03 4.26e-04 0.0 + 3 -205.5612821862653448 2.89e-05 1.05e-04 1.94e-03 2.56e-03 0.0 + 4 -205.5613124641500065 -3.03e-05 8.73e-05 1.43e-03 5.06e-04 0.0 + 5 -205.5613030515933985 9.41e-06 5.63e-05 1.03e-03 1.52e-03 0.0 + 6 -205.5613142114723644 -1.12e-05 2.15e-05 3.89e-04 7.96e-05 0.0 + 7 -205.5613141547387102 5.67e-08 1.19e-05 2.16e-04 9.14e-05 0.0 + 8 -205.5613143390051789 -1.84e-07 3.11e-07 2.87e-06 1.47e-06 0.0 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56131433900518 Eh -5593.60774 eV + +Components: +Nuclear Repulsion : 70.03438184397871 Eh 1905.73242 eV +Electronic Energy : -275.59569618298389 Eh -7499.34015 eV +One Electron Energy: -419.77014841123361 Eh -11422.52645 eV +Two Electron Energy: 144.17445222824972 Eh 3923.18630 eV + +Virial components: +Potential Energy : -410.41598131823116 Eh -11167.98662 eV +Kinetic Energy : 204.85466697922598 Eh 5574.37888 eV +Virial Ratio : 2.00344950578964 + +DFT components: +N(Alpha) : 11.999996881680 electrons +N(Beta) : 11.999996881680 electrons +N(Total) : 23.999993763361 electrons +E(X) : -23.350581637318 Eh +E(C) : -0.804806247960 Eh +E(XC) : -24.155387885278 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.8427e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.8741e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.1118e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.3730e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.4688e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.2393e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 4.3 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 48.1 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360477 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007180575 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.554494240241 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.0 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003747 -0.000005932 0.000000894 + 2 O : -0.000000410 0.000000571 -0.000000112 + 3 O : 0.000003809 0.000008516 0.000000047 + 4 H : 0.000000348 -0.000003154 -0.000000829 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000121792 +RMS gradient ... 0.0000035158 +MAX gradient ... 0.0000085162 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.008196780 -0.003633824 -0.013658223 + 2 O : 0.001670982 0.002576542 -0.023341654 + 3 O : -0.000745432 -0.000687274 0.018022247 + 4 H : 0.007271231 0.001744556 0.018977629 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000163611 -0.0000176890 0.0000209127 + +Norm of the Cartesian gradient ... 0.0395360162 +RMS gradient ... 0.0114130648 +MAX gradient ... 0.0233416537 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.104 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.005 sec ( 4.7%) +RI-J Coulomb gradient .... 0.049 sec ( 47.5%) +XC gradient .... 0.014 sec ( 13.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 24.9 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.554494240 Eh +Current gradient norm .... 0.039536016 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999988183 +Lowest eigenvalues of augmented Hessian: + -0.000009954 0.365983330 0.370715503 0.453235053 0.598983365 +Length of the computed step .... 0.004861571 +The final length of the internal step .... 0.004861571 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0019847281 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0012243818 RMS(Int)= 0.0019842212 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000004977 +Previously predicted energy change .... -0.000048139 +Actually observed energy change .... -0.000056646 +Ratio of predicted to observed change .... 1.176711599 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000566461 0.0000050000 NO + RMS gradient 0.0008482554 0.0001000000 NO + MAX gradient 0.0014182567 0.0003000000 NO + RMS step 0.0019847281 0.0020000000 YES + MAX step 0.0032597036 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0016 Max(Angles) 0.19 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2907 0.001418 -0.0016 1.2891 + 2. B(O 2,O 1) 1.2908 0.000945 -0.0010 1.2898 + 3. B(H 3,N 0) 1.0330 -0.000032 -0.0002 1.0328 + 4. A(O 1,N 0,H 3) 100.67 -0.000281 0.03 100.70 + 5. A(N 0,O 1,O 2) 117.07 -0.001154 0.19 117.26 + 6. D(O 2,O 1,N 0,H 3) 152.31 -0.039135 0.00 152.31 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 7.474 %) +Internal coordinates : 0.000 s ( 3.093 %) +B/P matrices and projection : 0.000 s (16.237 %) +Hessian update/contruction : 0.000 s (37.887 %) +Making the step : 0.000 s ( 5.670 %) +Converting the step to Cartesian: 0.000 s ( 4.253 %) +Storing new data : 0.000 s ( 3.608 %) +Checking convergence : 0.000 s ( 1.418 %) +Final printing : 0.000 s (19.716 %) +Total time : 0.001 s + +Time for energy+gradient : 9.692 s +Time for complete geometry iter : 10.586 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.153124 -0.690940 -0.144429 + O -0.203148 0.547475 -0.110411 + O 0.729909 1.426961 0.028851 + H -0.698593 -1.145652 0.222282 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.289363 -1.305687 -0.272931 + 1 O 8.0000 0 15.999 -0.383895 1.034577 -0.208647 + 2 O 8.0000 0 15.999 1.379328 2.696566 0.054520 + 3 H 1.0000 0 1.008 -1.320149 -2.164969 0.420052 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.289091749853 0.00000000 0.00000000 + O 2 1 0 1.289762174336 117.25823018 0.00000000 + H 1 2 3 1.032793286475 100.70064951 152.30769249 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.436030368719 0.00000000 0.00000000 + O 2 1 0 2.437297287385 117.25823018 0.00000000 + H 1 2 3 1.951696464391 100.70064951 152.30769249 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.085708449247 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.759e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5613058129745809 0.00e+00 6.66e-05 6.45e-04 1.55e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5613117511669543 -5.94e-06 3.75e-05 4.14e-04 1.29e-04 0.0 + 3 -205.5613120582101487 -3.07e-07 2.71e-05 3.09e-04 1.71e-04 0.0 + 4 -205.5613115486593188 5.10e-07 2.66e-05 3.54e-04 3.68e-04 0.0 + 5 -205.5613120150033524 -4.66e-07 2.35e-05 3.12e-04 1.86e-04 0.0 + 6 -205.5613116382912722 3.77e-07 1.93e-05 2.42e-04 3.28e-04 0.0 + 7 -205.5613122803926558 -6.42e-07 5.61e-06 8.03e-05 2.76e-05 0.0 + 8 -205.5613122850866148 -4.69e-09 2.66e-06 2.59e-05 1.91e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56131228508661 Eh -5593.60768 eV + +Components: +Nuclear Repulsion : 70.08570844924672 Eh 1907.12908 eV +Electronic Energy : -275.64702073433335 Eh -7500.73676 eV +One Electron Energy: -419.86838689291011 Eh -11425.19965 eV +Two Electron Energy: 144.22136615857676 Eh 3924.46289 eV + +Virial components: +Potential Energy : -410.42138392805100 Eh -11168.13363 eV +Kinetic Energy : 204.86007164296441 Eh 5574.52595 eV +Virial Ratio : 2.00342302253679 + +DFT components: +N(Alpha) : 11.999996835015 electrons +N(Beta) : 11.999996835015 electrons +N(Total) : 23.999993670030 electrons +E(X) : -23.352343537993 Eh +E(C) : -0.804921353527 Eh +E(XC) : -24.157264891520 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 4.6940e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.5869e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.6605e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 8.6824e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.9080e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.7681e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 4.1 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 48.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360484 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007173206 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.554499563719 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003747 -0.000005931 0.000000895 + 2 O : -0.000000407 0.000000569 -0.000000111 + 3 O : 0.000003803 0.000008513 0.000000046 + 4 H : 0.000000351 -0.000003152 -0.000000831 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000121737 +RMS gradient ... 0.0000035142 +MAX gradient ... 0.0000085129 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.009121878 -0.002626889 -0.013616196 + 2 O : 0.003460039 0.001814984 -0.023387647 + 3 O : -0.001713705 -0.000944321 0.018005564 + 4 H : 0.007375543 0.001756226 0.018998279 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000198289 -0.0000210062 0.0000210522 + +Norm of the Cartesian gradient ... 0.0398020664 +RMS gradient ... 0.0114898669 +MAX gradient ... 0.0233876469 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.108 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 4.2%) +RI-J Coulomb gradient .... 0.052 sec ( 47.6%) +XC gradient .... 0.016 sec ( 14.7%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 25.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.554499564 Eh +Current gradient norm .... 0.039802066 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999577 +Lowest eigenvalues of augmented Hessian: + -0.000000322 0.340202304 0.412057461 0.415900400 0.581567687 +Length of the computed step .... 0.000919816 +The final length of the internal step .... 0.000919816 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0003755131 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0002621024 RMS(Int)= 0.0003755261 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000161 +Previously predicted energy change .... -0.000004977 +Actually observed energy change .... -0.000005323 +Ratio of predicted to observed change .... 1.069553270 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000053235 0.0000050000 NO + RMS gradient 0.0001447801 0.0001000000 NO + MAX gradient 0.0002549661 0.0003000000 YES + RMS step 0.0003755131 0.0020000000 YES + MAX step 0.0007319864 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0002 Max(Angles) 0.04 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2891 0.000210 -0.0002 1.2888 + 2. B(O 2,O 1) 1.2898 0.000062 -0.0001 1.2897 + 3. B(H 3,N 0) 1.0328 -0.000110 0.0001 1.0329 + 4. A(O 1,N 0,H 3) 100.70 -0.000255 0.04 100.74 + 5. A(N 0,O 1,O 2) 117.26 0.000023 0.00 117.26 + 6. D(O 2,O 1,N 0,H 3) 152.31 -0.039235 -0.00 152.31 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.907 %) +Internal coordinates : 0.000 s ( 3.560 %) +B/P matrices and projection : 0.000 s (16.254 %) +Hessian update/contruction : 0.000 s (24.768 %) +Making the step : 0.000 s ( 5.728 %) +Converting the step to Cartesian: 0.000 s ( 4.954 %) +Storing new data : 0.000 s ( 3.406 %) +Checking convergence : 0.000 s ( 1.548 %) +Final printing : 0.000 s (29.412 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.152992 -0.690660 -0.144339 + O -0.203071 0.547562 -0.110470 + O 0.729966 1.426916 0.028825 + H -0.698595 -1.145975 0.222276 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.289114 -1.305158 -0.272761 + 1 O 8.0000 0 15.999 -0.383749 1.034743 -0.208758 + 2 O 8.0000 0 15.999 1.379436 2.696481 0.054472 + 3 H 1.0000 0 1.008 -1.320154 -2.165579 0.420040 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.288845340361 0.00000000 0.00000000 + O 2 1 0 1.289661107035 117.26033828 0.00000000 + H 1 2 3 1.032918063693 100.74258925 152.30769249 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.435564722263 0.00000000 0.00000000 + O 2 1 0 2.437106297867 117.26033828 0.00000000 + H 1 2 3 1.951932259160 100.74258925 152.30769249 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.092708491897 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.758e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.0927084919 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5613115087958533 0.00e+00 9.59e-06 1.58e-04 1.27e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5613116004302867 -9.16e-08 6.75e-06 8.19e-05 3.05e-05 0.0 + 3 -205.5613115590955715 4.13e-08 4.81e-06 7.66e-05 8.66e-05 0.0 + 4 -205.5613116014958166 -4.24e-08 7.09e-06 9.92e-05 4.20e-05 0.0 + 5 -205.5613115094011221 9.21e-08 5.06e-06 8.07e-05 1.29e-04 0.0 + 6 -205.5613116133899041 -1.04e-07 8.07e-07 1.35e-05 3.06e-06 0.0 + 7 -205.5613116134422569 -5.24e-11 3.86e-07 6.29e-06 2.95e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56131161344226 Eh -5593.60766 eV + +Components: +Nuclear Repulsion : 70.09270849189718 Eh 1907.31956 eV +Electronic Energy : -275.65402010533944 Eh -7500.92723 eV +One Electron Energy: -419.88066011881358 Eh -11425.53362 eV +Two Electron Energy: 144.22664001347417 Eh 3924.60640 eV + +Virial components: +Potential Energy : -410.42184272949191 Eh -11168.14612 eV +Kinetic Energy : 204.86053111604969 Eh 5574.53846 eV +Virial Ratio : 2.00342076872287 + +DFT components: +N(Alpha) : 11.999996835985 electrons +N(Beta) : 11.999996835985 electrons +N(Total) : 23.999993671971 electrons +E(X) : -23.352364092283 Eh +E(C) : -0.804931021203 Eh +E(XC) : -24.157295113486 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 5.2353e-11 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.2894e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.8586e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.3359e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.9509e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.2544e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.191241 -522.2202 + 1 2.0000 -19.021960 -517.6138 + 2 2.0000 -14.266003 -388.1977 + 3 2.0000 -1.257330 -34.2137 + 4 2.0000 -0.974408 -26.5150 + 5 2.0000 -0.698353 -19.0031 + 6 2.0000 -0.567700 -15.4479 + 7 2.0000 -0.521078 -14.1792 + 8 2.0000 -0.507782 -13.8174 + 9 2.0000 -0.331168 -9.0115 + 10 2.0000 -0.281723 -7.6661 + 11 2.0000 -0.260503 -7.0887 + 12 0.0000 -0.183403 -4.9907 + 13 0.0000 0.055778 1.5178 + 14 0.0000 0.081658 2.2220 + 15 0.0000 0.147688 4.0188 + 16 0.0000 0.222319 6.0496 + 17 0.0000 0.272243 7.4081 + 18 0.0000 0.302909 8.2426 + 19 0.0000 0.327817 8.9203 + 20 0.0000 0.352847 9.6014 + 21 0.0000 0.380132 10.3439 + 22 0.0000 0.401377 10.9220 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.304443 + 1 O : 0.223115 + 2 O : -0.188469 + 3 H : 0.269797 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.890981 s : 3.890981 + pz : 1.087885 p : 3.354179 + px : 1.431499 + py : 0.834795 + dz2 : 0.007125 d : 0.059283 + dxz : 0.010730 + dyz : 0.013541 + dx2y2 : 0.013880 + dxy : 0.014007 + + 1 O s : 3.744635 s : 3.744635 + pz : 1.382693 p : 3.894618 + px : 1.458917 + py : 1.053008 + dz2 : 0.005397 d : 0.137632 + dxz : 0.012083 + dyz : 0.044464 + dx2y2 : 0.054661 + dxy : 0.021027 + + 2 O s : 3.944027 s : 3.944027 + pz : 1.385586 p : 4.218676 + px : 1.438178 + py : 1.394912 + dz2 : 0.002047 d : 0.025765 + dxz : 0.007976 + dyz : 0.005065 + dx2y2 : 0.003342 + dxy : 0.007335 + + 3 H s : 0.700398 s : 0.700398 + pz : 0.008251 p : 0.029806 + px : 0.014219 + py : 0.007336 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.065482 + 1 O : -0.195333 + 2 O : -0.020054 + 3 H : 0.280869 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.356301 s : 3.356301 + pz : 1.016444 p : 3.391703 + px : 1.394517 + py : 0.980741 + dz2 : 0.036253 d : 0.317479 + dxz : 0.014194 + dyz : 0.064581 + dx2y2 : 0.074209 + dxy : 0.128242 + + 1 O s : 3.360272 s : 3.360272 + pz : 1.276522 p : 4.042520 + px : 1.489172 + py : 1.276826 + dz2 : 0.063219 d : 0.792541 + dxz : 0.031558 + dyz : 0.195716 + dx2y2 : 0.239940 + dxy : 0.262108 + + 2 O s : 3.595321 s : 3.595321 + pz : 1.309658 p : 4.167543 + px : 1.437930 + py : 1.419954 + dz2 : 0.031260 d : 0.257190 + dxz : 0.031711 + dyz : 0.034842 + dx2y2 : 0.081846 + dxy : 0.077530 + + 3 H s : 0.644553 s : 0.644553 + pz : 0.019382 p : 0.074578 + px : 0.040215 + py : 0.014982 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.3044 7.0000 -0.3044 2.7024 2.7024 0.0000 + 1 O 7.7769 8.0000 0.2231 2.6396 2.6396 0.0000 + 2 O 8.1885 8.0000 -0.1885 1.7304 1.7304 0.0000 + 3 H 0.7302 1.0000 0.2698 0.9134 0.9134 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3781 B( 0-N , 2-O ) : 0.4504 B( 0-N , 3-H ) : 0.8738 +B( 1-O , 2-O ) : 1.2509 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 4 sec + +Total time .... 4.206 sec +Sum of individual times .... 4.191 sec ( 99.6%) + +SCF preparation .... 1.349 sec ( 32.1%) +Fock matrix formation .... 0.172 sec ( 4.1%) + Startup .... 0.009 sec ( 5.1% of F) + Split-RI-J .... 0.023 sec ( 13.1% of F) + XC integration .... 0.116 sec ( 67.4% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.007 sec ( 6.1% of XC) + Density eval. .... 0.009 sec ( 8.1% of XC) + XC-Functional eval. .... 0.006 sec ( 5.0% of XC) + XC-Potential eval. .... 0.010 sec ( 8.2% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.010 sec ( 0.2%) +Total Energy calculation .... 0.014 sec ( 0.3%) +Population analysis .... 2.594 sec ( 61.7%) +Orbital Transformation .... 0.006 sec ( 0.1%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.010 sec ( 0.2%) +SOSCF solution .... 0.035 sec ( 0.8%) +Finished LeanSCF after 6.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 48.6 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360485 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007172332 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.554499766064 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.037.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.037.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.396675 0.834484 -0.124765 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5613116134422569 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.026828249 0.819687146 -0.123100178 +Nuclear contribution : -0.851069648 -1.479511283 0.270789022 + ----------------------------------------- +Total Dipole Moment : -0.824241399 -0.659824136 0.147688844 + ----------------------------------------- +Magnitude (a.u.) : 1.066092758 +Magnitude (Debye) : 2.709792441 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.344797 0.425230 0.380594 +Rotational constants in MHz : 100274.478012 12748.060192 11409.926201 + +Dipole components along the rotational axes: +x,y,z [a.u.] : -0.866186 -0.580099 0.223070 +x,y,z [Debye]: -2.201671 -1.474494 0.566999 + + + +Dipole moment calculation done in 1.0 sec + +Maximum memory used throughout the entire PROP-calculation: 25.3 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 38 * + * * + * Dihedral ( 2, 1, 0, 3) : 161.53846154 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2890 0.726772 + 2. B(O 2,O 1) 1.2928 0.724597 + 3. B(H 3,N 0) 1.0360 0.397769 + 4. A(O 1,N 0,H 3) 100.7546 0.360965 + 5. A(N 0,O 1,O 2) 117.1240 0.447383 + 6. D(O 2,O 1,N 0,H 3) 161.5385 0.041621 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.161992 -0.687580 -0.111962 + O -0.202379 0.547782 -0.060877 + O 0.734615 1.437067 -0.010778 + H -0.712936 -1.159425 0.179909 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.306120 -1.299339 -0.211577 + 1 O 8.0000 0 15.999 -0.382440 1.035158 -0.115042 + 2 O 8.0000 0 15.999 1.388222 2.715663 -0.020367 + 3 H 1.0000 0 1.008 -1.347254 -2.190995 0.339978 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.288845340361 0.00000000 0.00000000 + O 2 1 0 1.289661107035 117.26033828 0.00000000 + H 1 2 3 1.032918063693 100.74258925 152.30769249 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.435564722263 0.00000000 0.00000000 + O 2 1 0 2.437106297867 117.26033828 0.00000000 + H 1 2 3 1.951932259160 100.74258925 152.30769249 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1669 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 69.991138807398 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.737e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22312 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 69.9911388074 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5618038086155366 0.00e+00 3.83e-04 4.03e-03 2.81e-02 0.700 0.1 +Warning: op=0 Small HOMO/LUMO gap ( 0.080) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5630836934558374 -1.28e-03 4.50e-04 4.96e-03 2.11e-02 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.5641340389447578 -1.05e-03 3.42e-04 3.81e-03 1.50e-02 0.700 0.0 + 4 -205.5648688425005162 -7.35e-04 8.51e-04 9.59e-03 1.06e-02 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5665776742661137 -1.71e-03 6.21e-05 5.09e-04 5.20e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 6 -205.5665814653702910 -3.79e-06 1.84e-04 2.56e-03 6.66e-04 0.0 + 7 -205.5665374989449674 4.40e-05 1.35e-04 2.29e-03 3.79e-03 0.0 + 8 -205.5665882341501174 -5.07e-05 4.00e-05 3.57e-04 1.20e-04 0.0 + 9 -205.5665884019421128 -1.68e-07 1.10e-05 1.96e-04 1.92e-04 0.0 + 10 -205.5665884883767376 -8.64e-08 1.69e-05 1.39e-04 1.60e-04 0.0 + 11 -205.5665885964867812 -1.08e-07 7.78e-06 6.57e-05 5.32e-05 0.0 + 12 -205.5665886336987001 -3.72e-08 1.16e-06 1.56e-05 1.13e-05 0.0 + 13 -205.5665886350377605 -1.34e-09 6.45e-07 7.21e-06 3.23e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 13 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56658863503776 Eh -5593.75126 eV + +Components: +Nuclear Repulsion : 69.99113880739763 Eh 1904.55571 eV +Electronic Energy : -275.55772744243541 Eh -7498.30697 eV +One Electron Energy: -419.69306321851730 Eh -11420.42885 eV +Two Electron Energy: 144.13533577608189 Eh 3922.12188 eV + +Virial components: +Potential Energy : -410.40795350338419 Eh -11167.76817 eV +Kinetic Energy : 204.84136486834643 Eh 5574.01692 eV +Virial Ratio : 2.00354041659094 + +DFT components: +N(Alpha) : 11.999999770930 electrons +N(Beta) : 11.999999770930 electrons +N(Total) : 23.999999541860 electrons +E(X) : -23.349275508041 Eh +E(C) : -0.804690153880 Eh +E(XC) : -24.153965661921 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.3391e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.2066e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 6.4507e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.2021e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.2298e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.7867e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.191886 -522.2378 + 1 2.0000 -19.019438 -517.5452 + 2 2.0000 -14.268936 -388.2775 + 3 2.0000 -1.255697 -34.1692 + 4 2.0000 -0.973405 -26.4877 + 5 2.0000 -0.697886 -18.9904 + 6 2.0000 -0.567388 -15.4394 + 7 2.0000 -0.521214 -14.1830 + 8 2.0000 -0.507007 -13.7964 + 9 2.0000 -0.329993 -8.9796 + 10 2.0000 -0.285231 -7.7615 + 11 2.0000 -0.259597 -7.0640 + 12 0.0000 -0.180269 -4.9054 + 13 0.0000 0.053238 1.4487 + 14 0.0000 0.080079 2.1791 + 15 0.0000 0.146058 3.9744 + 16 0.0000 0.220675 6.0049 + 17 0.0000 0.274501 7.4696 + 18 0.0000 0.299222 8.1422 + 19 0.0000 0.326804 8.8928 + 20 0.0000 0.359985 9.7957 + 21 0.0000 0.379638 10.3305 + 22 0.0000 0.400284 10.8923 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.293472 + 1 O : 0.224259 + 2 O : -0.198706 + 3 H : 0.267919 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.889763 s : 3.889763 + pz : 1.091121 p : 3.342976 + px : 1.414773 + py : 0.837083 + dz2 : 0.007684 d : 0.060732 + dxz : 0.010360 + dyz : 0.013531 + dx2y2 : 0.014346 + dxy : 0.014812 + + 1 O s : 3.744515 s : 3.744515 + pz : 1.384584 p : 3.890636 + px : 1.457348 + py : 1.048705 + dz2 : 0.004760 d : 0.140590 + dxz : 0.011990 + dyz : 0.045280 + dx2y2 : 0.055826 + dxy : 0.022734 + + 2 O s : 3.945623 s : 3.945623 + pz : 1.410413 p : 4.226653 + px : 1.432838 + py : 1.383402 + dz2 : 0.001886 d : 0.026431 + dxz : 0.008264 + dyz : 0.005401 + dx2y2 : 0.003512 + dxy : 0.007367 + + 3 H s : 0.702655 s : 0.702655 + pz : 0.007423 p : 0.029427 + px : 0.014577 + py : 0.007426 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.060884 + 1 O : -0.194918 + 2 O : -0.025686 + 3 H : 0.281487 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.359169 s : 3.359169 + pz : 1.017376 p : 3.383329 + px : 1.384606 + py : 0.981347 + dz2 : 0.037684 d : 0.318386 + dxz : 0.012158 + dyz : 0.063565 + dx2y2 : 0.074040 + dxy : 0.130940 + + 1 O s : 3.361813 s : 3.361813 + pz : 1.277344 p : 4.041142 + px : 1.488795 + py : 1.275003 + dz2 : 0.062938 d : 0.791962 + dxz : 0.029174 + dyz : 0.195787 + dx2y2 : 0.239956 + dxy : 0.264107 + + 2 O s : 3.597005 s : 3.597005 + pz : 1.329884 p : 4.172689 + px : 1.433886 + py : 1.408919 + dz2 : 0.030361 d : 0.255991 + dxz : 0.030343 + dyz : 0.034769 + dx2y2 : 0.081915 + dxy : 0.078603 + + 3 H s : 0.644968 s : 0.644968 + pz : 0.017055 p : 0.073544 + px : 0.041195 + py : 0.015294 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2935 7.0000 -0.2935 2.7171 2.7171 0.0000 + 1 O 7.7757 8.0000 0.2243 2.6526 2.6526 0.0000 + 2 O 8.1987 8.0000 -0.1987 1.7385 1.7385 0.0000 + 3 H 0.7321 1.0000 0.2679 0.9147 0.9147 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3859 B( 0-N , 2-O ) : 0.4549 B( 0-N , 3-H ) : 0.8763 +B( 1-O , 2-O ) : 1.2559 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 4 sec + +Total time .... 4.553 sec +Sum of individual times .... 4.540 sec ( 99.7%) + +SCF preparation .... 1.292 sec ( 28.4%) +Fock matrix formation .... 0.282 sec ( 6.2%) + Startup .... 0.020 sec ( 7.1% of F) + Split-RI-J .... 0.040 sec ( 14.4% of F) + XC integration .... 0.176 sec ( 62.6% of F) + Basis function eval. .... 0.013 sec ( 7.3% of XC) + Density eval. .... 0.019 sec ( 10.5% of XC) + XC-Functional eval. .... 0.011 sec ( 6.3% of XC) + XC-Potential eval. .... 0.019 sec ( 10.9% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.033 sec ( 0.7%) +Total Energy calculation .... 0.024 sec ( 0.5%) +Population analysis .... 2.790 sec ( 61.3%) +Orbital Transformation .... 0.013 sec ( 0.3%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.064 sec ( 1.4%) +SOSCF solution .... 0.043 sec ( 1.0%) +Finished LeanSCF after 7.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 49.0 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360210 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007178108 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.559770736727 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003789 -0.000005988 0.000000761 + 2 O : -0.000000411 0.000000567 -0.000000050 + 3 O : 0.000003887 0.000008671 -0.000000122 + 4 H : 0.000000313 -0.000003251 -0.000000589 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000123535 +RMS gradient ... 0.0000035661 +MAX gradient ... 0.0000086711 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.002033294 -0.003423491 -0.010110579 + 2 O : -0.002945981 0.002846551 -0.015859038 + 3 O : 0.002700752 0.001767971 0.012246326 + 4 H : 0.002278523 -0.001191031 0.013723291 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000462332 0.0000068116 -0.0000121617 + +Norm of the Cartesian gradient ... 0.0272341761 +RMS gradient ... 0.0078618295 +MAX gradient ... 0.0158590375 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.132 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.006 sec ( 4.2%) +RI-J Coulomb gradient .... 0.061 sec ( 46.6%) +XC gradient .... 0.019 sec ( 14.4%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 25.3 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.559770737 Eh +Current gradient norm .... 0.027234176 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999938709 +Lowest eigenvalues of augmented Hessian: + -0.000068050 0.360239832 0.393286500 0.446411072 0.716344879 +Length of the computed step .... 0.011072156 +The final length of the internal step .... 0.011072156 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0045201886 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0041307275 RMS(Int)= 0.0045182553 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0026229732 0.0001000000 NO + MAX gradient 0.0043507129 0.0003000000 NO + RMS step 0.0045201886 0.0020000000 NO + MAX step 0.0063099291 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0033 Max(Angles) 0.25 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2890 0.004351 -0.0032 1.2858 + 2. B(O 2,O 1) 1.2928 0.003648 -0.0027 1.2901 + 3. B(H 3,N 0) 1.0360 0.002482 -0.0033 1.0327 + 4. A(O 1,N 0,H 3) 100.75 0.001558 -0.25 100.51 + 5. A(N 0,O 1,O 2) 117.12 -0.000675 0.09 117.21 + 6. D(O 2,O 1,N 0,H 3) 161.54 -0.026376 0.00 161.54 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.580 %) +Internal coordinates : 0.000 s ( 3.866 %) +B/P matrices and projection : 0.000 s (19.664 %) +Hessian update/contruction : 0.000 s (23.193 %) +Making the step : 0.000 s ( 8.571 %) +Converting the step to Cartesian: 0.000 s ( 5.378 %) +Storing new data : 0.000 s ( 3.866 %) +Checking convergence : 0.000 s ( 0.168 %) +Final printing : 0.000 s (25.210 %) +Total time : 0.001 s + +Time for energy+gradient : 12.993 s +Time for complete geometry iter : 14.049 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.162309 -0.687211 -0.112271 + O -0.201531 0.544967 -0.060365 + O 0.731913 1.434092 -0.010621 + H -0.711398 -1.154003 0.179548 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.306719 -1.298641 -0.212161 + 1 O 8.0000 0 15.999 -0.380838 1.029837 -0.114072 + 2 O 8.0000 0 15.999 1.383114 2.710042 -0.020070 + 3 H 1.0000 0 1.008 -1.344348 -2.180751 0.339297 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.285821018544 0.00000000 0.00000000 + O 2 1 0 1.290091347955 117.21062915 0.00000000 + H 1 2 3 1.032674622339 100.50684901 161.53846140 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.429849582287 0.00000000 0.00000000 + O 2 1 0 2.437919335376 117.21062915 0.00000000 + H 1 2 3 1.951472221672 100.50684901 161.53846140 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.153684894190 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.707e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22311 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.5 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5666123047685971 0.00e+00 1.10e-04 1.15e-03 2.14e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5666279242873031 -1.56e-05 1.09e-04 1.45e-03 3.54e-04 0.0 + 3 -205.5666106447873460 1.73e-05 8.10e-05 1.51e-03 2.16e-03 0.0 + 4 -205.5666287824969629 -1.81e-05 6.80e-05 1.06e-03 3.87e-04 0.0 + 5 -205.5666237857880390 5.00e-06 4.22e-05 7.63e-04 1.17e-03 0.0 + 6 -205.5666297966369882 -6.01e-06 1.90e-05 3.48e-04 6.65e-05 0.0 + 7 -205.5666297428508926 5.38e-08 1.08e-05 1.98e-04 7.98e-05 0.0 + 8 -205.5666298926425100 -1.50e-07 2.76e-07 2.57e-06 1.43e-06 0.0 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56662989264251 Eh -5593.75238 eV + +Components: +Nuclear Repulsion : 70.15368489418981 Eh 1908.97882 eV +Electronic Energy : -275.72031478683232 Eh -7502.73120 eV +One Electron Energy: -420.00219354414111 Eh -11428.84072 eV +Two Electron Energy: 144.28187875730876 Eh 3926.10952 eV + +Virial components: +Potential Energy : -410.42776695690122 Eh -11168.30732 eV +Kinetic Energy : 204.86113706425868 Eh 5574.55494 eV +Virial Ratio : 2.00344376116668 + +DFT components: +N(Alpha) : 11.999999782549 electrons +N(Beta) : 11.999999782549 electrons +N(Total) : 23.999999565097 electrons +E(X) : -23.354556312152 Eh +E(C) : -0.805016654018 Eh +E(XC) : -24.159572966170 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.4979e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.5672e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.7601e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.9376e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.4288e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.2129e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 4.6 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 49.1 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360321 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007179727 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.559810486421 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003787 -0.000005958 0.000000764 + 2 O : -0.000000411 0.000000556 -0.000000047 + 3 O : 0.000003848 0.000008602 -0.000000119 + 4 H : 0.000000350 -0.000003200 -0.000000598 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000122652 +RMS gradient ... 0.0000035407 +MAX gradient ... 0.0000086017 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.003958528 -0.001871090 -0.009593877 + 2 O : -0.000979896 0.001196698 -0.015900805 + 3 O : 0.000912760 -0.000093234 0.012264822 + 4 H : 0.004025664 0.000767626 0.013229860 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000518699 0.0000080780 -0.0000167783 + +Norm of the Cartesian gradient ... 0.0266370679 +RMS gradient ... 0.0076894592 +MAX gradient ... 0.0159008050 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.139 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.006 sec ( 4.4%) +RI-J Coulomb gradient .... 0.068 sec ( 49.3%) +XC gradient .... 0.020 sec ( 14.7%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 25.4 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.559810486 Eh +Current gradient norm .... 0.026637068 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999992338 +Lowest eigenvalues of augmented Hessian: + -0.000006597 0.367742677 0.370504745 0.460870928 0.602953723 +Length of the computed step .... 0.003914692 +The final length of the internal step .... 0.003914692 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0015981664 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0009790325 RMS(Int)= 0.0015978318 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000003299 +Previously predicted energy change .... -0.000034029 +Actually observed energy change .... -0.000039750 +Ratio of predicted to observed change .... 1.168103758 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000397497 0.0000050000 NO + RMS gradient 0.0006999560 0.0001000000 NO + MAX gradient 0.0010688456 0.0003000000 NO + RMS step 0.0015981664 0.0020000000 YES + MAX step 0.0025972632 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0011 Max(Angles) 0.15 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2858 0.000932 -0.0010 1.2848 + 2. B(O 2,O 1) 1.2901 0.001069 -0.0011 1.2890 + 3. B(H 3,N 0) 1.0327 -0.000017 -0.0002 1.0325 + 4. A(O 1,N 0,H 3) 100.51 -0.000245 0.03 100.54 + 5. A(N 0,O 1,O 2) 117.21 -0.000931 0.15 117.36 + 6. D(O 2,O 1,N 0,H 3) 161.54 -0.026567 0.00 161.54 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 8.754 %) +Internal coordinates : 0.000 s ( 3.030 %) +B/P matrices and projection : 0.000 s (15.152 %) +Hessian update/contruction : 0.000 s (35.017 %) +Making the step : 0.000 s ( 6.622 %) +Converting the step to Cartesian: 0.000 s ( 4.153 %) +Storing new data : 0.000 s ( 3.367 %) +Checking convergence : 0.000 s ( 1.459 %) +Final printing : 0.000 s (22.222 %) +Total time : 0.001 s + +Time for energy+gradient : 10.134 s +Time for complete geometry iter : 11.018 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.162067 -0.687187 -0.112404 + O -0.200209 0.544379 -0.060222 + O 0.731038 1.434194 -0.010646 + H -0.711604 -1.153543 0.179564 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.306262 -1.298595 -0.212412 + 1 O 8.0000 0 15.999 -0.378340 1.028727 -0.113802 + 2 O 8.0000 0 15.999 1.381462 2.710235 -0.020119 + 3 H 1.0000 0 1.008 -1.344736 -2.179880 0.339326 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.284804003078 0.00000000 0.00000000 + O 2 1 0 1.288972406277 117.35944136 0.00000000 + H 1 2 3 1.032488622526 100.53774563 161.53846140 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.427927701584 0.00000000 0.00000000 + O 2 1 0 2.435804842045 117.35944136 0.00000000 + H 1 2 3 1.951120732964 100.53774563 161.53846140 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.196944576088 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.694e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22310 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5666232402972469 0.00e+00 5.38e-05 5.69e-04 1.33e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5666269663234402 -3.73e-06 3.06e-05 2.98e-04 1.06e-04 0.0 + 3 -205.5666267422793112 2.24e-07 2.89e-05 3.21e-04 3.66e-04 0.0 + 4 -205.5666267943381627 -5.21e-08 3.24e-05 4.89e-04 2.31e-04 0.0 + 5 -205.5666270753134768 -2.81e-07 1.13e-05 2.16e-04 1.86e-04 0.0 + 6 -205.5666271287169593 -5.34e-08 1.37e-05 2.18e-04 1.59e-04 0.0 + 7 -205.5666272388358493 -1.10e-07 6.81e-06 1.14e-04 4.55e-05 0.0 + 8 -205.5666272710951148 -3.23e-08 2.13e-06 1.69e-05 1.79e-05 0.0 + 9 -205.5666272762665017 -5.17e-09 7.02e-07 7.87e-06 3.97e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56662727626650 Eh -5593.75231 eV + +Components: +Nuclear Repulsion : 70.19694457608766 Eh 1910.15597 eV +Electronic Energy : -275.76357185235418 Eh -7503.90828 eV +One Electron Energy: -420.08401843451747 Eh -11431.06729 eV +Two Electron Energy: 144.32044658216330 Eh 3927.15900 eV + +Virial components: +Potential Energy : -410.43226479950317 Eh -11168.42972 eV +Kinetic Energy : 204.86563752323664 Eh 5574.67741 eV +Virial Ratio : 2.00342170488670 + +DFT components: +N(Alpha) : 11.999999792552 electrons +N(Beta) : 11.999999792552 electrons +N(Total) : 23.999999585103 electrons +E(X) : -23.355927461522 Eh +E(C) : -0.805111785622 Eh +E(XC) : -24.161039247144 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 5.1714e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.8694e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 7.0167e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 7.4953e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.9717e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.0842e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 4.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 49.3 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360329 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007173586 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.559814018965 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003787 -0.000005956 0.000000765 + 2 O : -0.000000408 0.000000556 -0.000000046 + 3 O : 0.000003843 0.000008598 -0.000000119 + 4 H : 0.000000353 -0.000003198 -0.000000599 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000122592 +RMS gradient ... 0.0000035389 +MAX gradient ... 0.0000085976 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.004712457 -0.001160824 -0.009517669 + 2 O : 0.000594830 0.000833237 -0.016001090 + 3 O : -0.000008387 -0.000437924 0.012289142 + 4 H : 0.004126014 0.000765511 0.013229617 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000539924 0.0000079359 -0.0000196981 + +Norm of the Cartesian gradient ... 0.0267408186 +RMS gradient ... 0.0077194094 +MAX gradient ... 0.0160010898 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.132 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.006 sec ( 4.3%) +RI-J Coulomb gradient .... 0.062 sec ( 47.3%) +XC gradient .... 0.019 sec ( 14.4%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 25.5 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.559814019 Eh +Current gradient norm .... 0.026740819 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999793 +Lowest eigenvalues of augmented Hessian: + -0.000000168 0.347333575 0.409900134 0.425273893 0.580123816 +Length of the computed step .... 0.000643900 +The final length of the internal step .... 0.000643900 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0002628710 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001852544 RMS(Int)= 0.0002628762 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000084 +Previously predicted energy change .... -0.000003299 +Actually observed energy change .... -0.000003533 +Ratio of predicted to observed change .... 1.070910638 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000035325 0.0000050000 YES + RMS gradient 0.0001082140 0.0001000000 NO + MAX gradient 0.0001694260 0.0003000000 YES + RMS step 0.0002628710 0.0020000000 YES + MAX step 0.0004806463 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0002 Max(Angles) 0.03 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2848 0.000066 -0.0001 1.2847 + 2. B(O 2,O 1) 1.2890 0.000164 -0.0002 1.2888 + 3. B(H 3,N 0) 1.0325 -0.000099 0.0001 1.0326 + 4. A(O 1,N 0,H 3) 100.54 -0.000169 0.03 100.57 + 5. A(N 0,O 1,O 2) 117.36 0.000022 0.00 117.36 + 6. D(O 2,O 1,N 0,H 3) 161.54 -0.026615 -0.00 161.54 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 9.306 %) +Internal coordinates : 0.000 s ( 3.333 %) +B/P matrices and projection : 0.000 s (16.528 %) +Hessian update/contruction : 0.000 s (28.194 %) +Making the step : 0.000 s ( 6.667 %) +Converting the step to Cartesian: 0.000 s ( 5.000 %) +Storing new data : 0.000 s ( 3.611 %) +Checking convergence : 0.000 s ( 1.528 %) +Final printing : 0.000 s (25.556 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.161996 -0.687009 -0.112358 + O -0.200145 0.544501 -0.060250 + O 0.731051 1.434119 -0.010662 + H -0.711610 -1.153768 0.179562 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.306127 -1.298258 -0.212326 + 1 O 8.0000 0 15.999 -0.378220 1.028958 -0.113856 + 2 O 8.0000 0 15.999 1.381487 2.710092 -0.020148 + 3 H 1.0000 0 1.008 -1.344747 -2.180305 0.339323 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.284708964872 0.00000000 0.00000000 + O 2 1 0 1.288800655614 117.35963992 0.00000000 + H 1 2 3 1.032602092571 100.56528463 161.53846140 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.427748105402 0.00000000 0.00000000 + O 2 1 0 2.435480280328 117.35963992 0.00000000 + H 1 2 3 1.951335160274 100.56528463 161.53846140 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1677 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.202607975983 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.693e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22310 +Total number of batches ... 351 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5578 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.2026079760 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5666268162987649 0.00e+00 6.45e-06 9.90e-05 9.51e-06 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -205.5666268614609749 -4.52e-08 6.95e-06 1.04e-04 2.89e-05 0.0 + 3 -205.5666267719498137 8.95e-08 5.67e-06 9.42e-05 1.57e-04 0.0 + 4 -205.5666268649727044 -9.30e-08 3.79e-06 6.69e-05 2.63e-05 0.0 + 5 -205.5666268382487942 2.67e-08 2.70e-06 4.98e-05 8.40e-05 0.0 + 6 -205.5666268689707294 -3.07e-08 3.85e-07 6.38e-06 1.49e-06 0.0 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 6 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56662686897073 Eh -5593.75230 eV + +Components: +Nuclear Repulsion : 70.20260797598290 Eh 1910.31008 eV +Electronic Energy : -275.76923484495364 Eh -7504.06238 eV +One Electron Energy: -420.09505026650140 Eh -11431.36748 eV +Two Electron Energy: 144.32581542154776 Eh 3927.30510 eV + +Virial components: +Potential Energy : -410.43258969016847 Eh -11168.43856 eV +Kinetic Energy : 204.86596282119777 Eh 5574.68626 eV +Virial Ratio : 2.00342010960788 + +DFT components: +N(Alpha) : 11.999999792886 electrons +N(Beta) : 11.999999792886 electrons +N(Total) : 23.999999585771 electrons +E(X) : -23.356047059843 Eh +E(C) : -0.805122470533 Eh +E(XC) : -24.161169530376 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.0722e-08 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.3752e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.8525e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.2453e-05 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.4902e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.8584e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.192277 -522.2484 + 1 2.0000 -19.019067 -517.5351 + 2 2.0000 -14.268086 -388.2544 + 3 2.0000 -1.259162 -34.2636 + 4 2.0000 -0.976116 -26.5615 + 5 2.0000 -0.696972 -18.9656 + 6 2.0000 -0.569012 -15.4836 + 7 2.0000 -0.523135 -14.2352 + 8 2.0000 -0.507582 -13.8120 + 9 2.0000 -0.330072 -8.9817 + 10 2.0000 -0.285412 -7.7665 + 11 2.0000 -0.259166 -7.0523 + 12 0.0000 -0.179015 -4.8712 + 13 0.0000 0.056891 1.5481 + 14 0.0000 0.081141 2.2080 + 15 0.0000 0.149562 4.0698 + 16 0.0000 0.221471 6.0265 + 17 0.0000 0.274266 7.4632 + 18 0.0000 0.298875 8.1328 + 19 0.0000 0.327581 8.9139 + 20 0.0000 0.359715 9.7883 + 21 0.0000 0.379869 10.3368 + 22 0.0000 0.400137 10.8883 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.293683 + 1 O : 0.226638 + 2 O : -0.200097 + 3 H : 0.267142 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.888297 s : 3.888297 + pz : 1.091933 p : 3.344363 + px : 1.415119 + py : 0.837311 + dz2 : 0.007723 d : 0.061024 + dxz : 0.010359 + dyz : 0.013657 + dx2y2 : 0.014474 + dxy : 0.014811 + + 1 O s : 3.741189 s : 3.741189 + pz : 1.383032 p : 3.890019 + px : 1.459039 + py : 1.047948 + dz2 : 0.004817 d : 0.142154 + dxz : 0.012048 + dyz : 0.045953 + dx2y2 : 0.056284 + dxy : 0.023052 + + 2 O s : 3.944840 s : 3.944840 + pz : 1.409999 p : 4.228527 + px : 1.437075 + py : 1.381453 + dz2 : 0.001926 d : 0.026730 + dxz : 0.008295 + dyz : 0.005519 + dx2y2 : 0.003551 + dxy : 0.007438 + + 3 H s : 0.703156 s : 0.703156 + pz : 0.007517 p : 0.029701 + px : 0.014711 + py : 0.007473 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.059533 + 1 O : -0.196442 + 2 O : -0.024554 + 3 H : 0.280529 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.355421 s : 3.355421 + pz : 1.017424 p : 3.384774 + px : 1.384215 + py : 0.983135 + dz2 : 0.037670 d : 0.319337 + dxz : 0.012167 + dyz : 0.063882 + dx2y2 : 0.074402 + dxy : 0.131216 + + 1 O s : 3.357952 s : 3.357952 + pz : 1.275764 p : 4.041699 + px : 1.490376 + py : 1.275559 + dz2 : 0.063128 d : 0.796791 + dxz : 0.029210 + dyz : 0.197626 + dx2y2 : 0.241339 + dxy : 0.265489 + + 2 O s : 3.594216 s : 3.594216 + pz : 1.328868 p : 4.173400 + px : 1.436909 + py : 1.407622 + dz2 : 0.030413 d : 0.256938 + dxz : 0.030247 + dyz : 0.035124 + dx2y2 : 0.082259 + dxy : 0.078895 + + 3 H s : 0.645334 s : 0.645334 + pz : 0.017287 p : 0.074137 + px : 0.041516 + py : 0.015334 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2937 7.0000 -0.2937 2.7172 2.7172 -0.0000 + 1 O 7.7734 8.0000 0.2266 2.6542 2.6542 0.0000 + 2 O 8.2001 8.0000 -0.2001 1.7383 1.7383 0.0000 + 3 H 0.7329 1.0000 0.2671 0.9153 0.9153 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3864 B( 0-N , 2-O ) : 0.4537 B( 0-N , 3-H ) : 0.8770 +B( 1-O , 2-O ) : 1.2570 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 4 sec + +Total time .... 4.578 sec +Sum of individual times .... 4.564 sec ( 99.7%) + +SCF preparation .... 1.270 sec ( 27.7%) +Fock matrix formation .... 0.144 sec ( 3.1%) + Startup .... 0.008 sec ( 5.4% of F) + Split-RI-J .... 0.021 sec ( 14.7% of F) + XC integration .... 0.093 sec ( 64.8% of F) + Basis function eval. .... 0.006 sec ( 6.5% of XC) + Density eval. .... 0.009 sec ( 9.7% of XC) + XC-Functional eval. .... 0.005 sec ( 5.3% of XC) + XC-Potential eval. .... 0.008 sec ( 8.9% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.009 sec ( 0.2%) +Total Energy calculation .... 0.012 sec ( 0.3%) +Population analysis .... 3.074 sec ( 67.1%) +Orbital Transformation .... 0.006 sec ( 0.1%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.019 sec ( 0.4%) +SOSCF solution .... 0.030 sec ( 0.7%) +Finished LeanSCF after 7.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 49.6 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360330 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007173081 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.559814118185 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.038.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.038.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.403797 0.838887 -0.101588 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5666268689707294 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.029021228 0.797422925 -0.080635182 +Nuclear contribution : -0.866838022 -1.489008662 0.219113658 + ----------------------------------------- +Total Dipole Moment : -0.837816794 -0.691585737 0.138478476 + ----------------------------------------- +Magnitude (a.u.) : 1.095173091 +Magnitude (Debye) : 2.783708773 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.410547 0.426346 0.380506 +Rotational constants in MHz : 102245.625713 12781.532419 11407.294865 + +Dipole components along the rotational axes: +x,y,z [a.u.] : 0.905107 -0.598540 -0.148104 +x,y,z [Debye]: 2.300599 -1.521368 -0.376451 + + + +Dipole moment calculation done in 1.0 sec + +Maximum memory used throughout the entire PROP-calculation: 25.8 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 39 * + * * + * Dihedral ( 2, 1, 0, 3) : 170.76923077 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2848 0.737900 + 2. B(O 2,O 1) 1.2920 0.726891 + 3. B(H 3,N 0) 1.0356 0.398231 + 4. A(O 1,N 0,H 3) 100.5888 0.361974 + 5. A(N 0,O 1,O 2) 117.2191 0.448875 + 6. D(O 2,O 1,N 0,H 3) 170.7692 0.043056 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.169605 -0.685107 -0.079958 + O -0.196924 0.544341 -0.009631 + O 0.732140 1.441231 -0.050446 + H -0.723528 -1.162621 0.136327 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.320506 -1.294665 -0.151099 + 1 O 8.0000 0 15.999 -0.372133 1.028656 -0.018199 + 2 O 8.0000 0 15.999 1.383544 2.723531 -0.095330 + 3 H 1.0000 0 1.008 -1.367270 -2.197035 0.257621 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.284708964872 0.00000000 0.00000000 + O 2 1 0 1.288800655614 117.35963992 0.00000000 + H 1 2 3 1.032602092571 100.56528463 161.53846140 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.427748105402 0.00000000 0.00000000 + O 2 1 0 2.435480280328 117.35963992 0.00000000 + H 1 2 3 1.951335160274 100.56528463 161.53846140 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 552 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1669 + la=0 lb=0: 145 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.104582756293 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.675e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.1 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.1045827563 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.5 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5649874661983461 0.00e+00 3.81e-04 4.03e-03 2.83e-02 0.700 0.0 +Warning: op=0 Small HOMO/LUMO gap ( 0.081) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5662855363130745 -1.30e-03 4.45e-04 4.94e-03 2.14e-02 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.5673502753683408 -1.06e-03 3.39e-04 3.81e-03 1.52e-02 0.700 0.0 + 4 -205.5680952718284686 -7.45e-04 8.41e-04 9.61e-03 1.07e-02 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5698279273050559 -1.73e-03 6.35e-05 6.08e-04 5.87e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 6 -205.5698314683328078 -3.54e-06 1.97e-04 2.64e-03 7.56e-04 0.0 + 7 -205.5697766718398896 5.48e-05 1.44e-04 2.55e-03 4.38e-03 0.0 + 8 -205.5698385632188376 -6.19e-05 3.52e-05 2.96e-04 1.16e-04 0.0 + 9 -205.5698385839344553 -2.07e-08 1.15e-05 2.13e-04 2.53e-04 0.0 + 10 -205.5698387767162387 -1.93e-07 1.76e-05 1.42e-04 1.39e-04 0.0 + 11 -205.5698388628768782 -8.62e-08 7.60e-06 5.98e-05 5.30e-05 0.0 + 12 -205.5698389049722152 -4.21e-08 1.17e-06 1.60e-05 8.77e-06 0.0 + 13 -205.5698389060652005 -1.09e-09 6.16e-07 7.12e-06 3.33e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 13 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56983890606520 Eh -5593.83970 eV + +Components: +Nuclear Repulsion : 70.10458275629284 Eh 1907.64268 eV +Electronic Energy : -275.67442166235804 Eh -7501.48238 eV +One Electron Energy: -419.91219716786588 Eh -11426.39179 eV +Two Electron Energy: 144.23777550550784 Eh 3924.90941 eV + +Virial components: +Potential Energy : -410.41952328796060 Eh -11168.08300 eV +Kinetic Energy : 204.84968438189537 Eh 5574.24330 eV +Virial Ratio : 2.00351552664747 + +DFT components: +N(Alpha) : 12.000000611149 electrons +N(Beta) : 12.000000611149 electrons +N(Total) : 24.000001222298 electrons +E(X) : -23.352867429903 Eh +E(C) : -0.804895727161 Eh +E(XC) : -24.157763157063 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.0930e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 7.1243e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 6.1622e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.8676e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.3331e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.5832e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.192630 -522.2580 + 1 2.0000 -19.017478 -517.4919 + 2 2.0000 -14.270168 -388.3110 + 3 2.0000 -1.257574 -34.2203 + 4 2.0000 -0.975050 -26.5325 + 5 2.0000 -0.696756 -18.9597 + 6 2.0000 -0.568588 -15.4721 + 7 2.0000 -0.523002 -14.2316 + 8 2.0000 -0.506960 -13.7951 + 9 2.0000 -0.329259 -8.9596 + 10 2.0000 -0.287548 -7.8246 + 11 2.0000 -0.258632 -7.0377 + 12 0.0000 -0.177285 -4.8242 + 13 0.0000 0.054435 1.4813 + 14 0.0000 0.079754 2.1702 + 15 0.0000 0.148058 4.0289 + 16 0.0000 0.220362 5.9963 + 17 0.0000 0.276138 7.5141 + 18 0.0000 0.296096 8.0572 + 19 0.0000 0.326961 8.8971 + 20 0.0000 0.365272 9.9396 + 21 0.0000 0.380510 10.3542 + 22 0.0000 0.398034 10.8311 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.285950 + 1 O : 0.226755 + 2 O : -0.206819 + 3 H : 0.266013 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.887414 s : 3.887414 + pz : 1.095409 p : 3.336546 + px : 1.402258 + py : 0.838878 + dz2 : 0.008108 d : 0.061990 + dxz : 0.009924 + dyz : 0.013599 + dx2y2 : 0.014938 + dxy : 0.015421 + + 1 O s : 3.741457 s : 3.741457 + pz : 1.384202 p : 3.887840 + px : 1.458440 + py : 1.045198 + dz2 : 0.004689 d : 0.143948 + dxz : 0.012107 + dyz : 0.046237 + dx2y2 : 0.056637 + dxy : 0.024277 + + 2 O s : 3.946202 s : 3.946202 + pz : 1.425296 p : 4.233545 + px : 1.434795 + py : 1.373454 + dz2 : 0.002034 d : 0.027072 + dxz : 0.008110 + dyz : 0.005805 + dx2y2 : 0.003731 + dxy : 0.007391 + + 3 H s : 0.704598 s : 0.704598 + pz : 0.006870 p : 0.029388 + px : 0.015008 + py : 0.007510 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.056977 + 1 O : -0.195957 + 2 O : -0.028455 + 3 H : 0.281389 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.357644 s : 3.357644 + pz : 1.018951 p : 3.379187 + px : 1.376691 + py : 0.983544 + dz2 : 0.038734 d : 0.320146 + dxz : 0.010565 + dyz : 0.063142 + dx2y2 : 0.074533 + dxy : 0.133174 + + 1 O s : 3.359538 s : 3.359538 + pz : 1.277641 p : 4.040824 + px : 1.488739 + py : 1.274444 + dz2 : 0.062646 d : 0.795595 + dxz : 0.028923 + dyz : 0.198094 + dx2y2 : 0.239875 + dxy : 0.266057 + + 2 O s : 3.596054 s : 3.596054 + pz : 1.342773 p : 4.176637 + px : 1.433957 + py : 1.399907 + dz2 : 0.029892 d : 0.255763 + dxz : 0.029955 + dyz : 0.035549 + dx2y2 : 0.081374 + dxy : 0.078993 + + 3 H s : 0.645335 s : 0.645335 + pz : 0.015468 p : 0.073276 + px : 0.042326 + py : 0.015482 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2859 7.0000 -0.2859 2.7264 2.7264 0.0000 + 1 O 7.7732 8.0000 0.2268 2.6629 2.6629 0.0000 + 2 O 8.2068 8.0000 -0.2068 1.7435 1.7435 0.0000 + 3 H 0.7340 1.0000 0.2660 0.9161 0.9161 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3917 B( 0-N , 2-O ) : 0.4563 B( 0-N , 3-H ) : 0.8783 +B( 1-O , 2-O ) : 1.2603 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 4 sec + +Total time .... 4.793 sec +Sum of individual times .... 4.778 sec ( 99.7%) + +SCF preparation .... 1.447 sec ( 30.2%) +Fock matrix formation .... 0.297 sec ( 6.2%) + Startup .... 0.015 sec ( 5.1% of F) + Split-RI-J .... 0.043 sec ( 14.3% of F) + XC integration .... 0.190 sec ( 64.0% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.015 sec ( 7.7% of XC) + Density eval. .... 0.019 sec ( 10.2% of XC) + XC-Functional eval. .... 0.011 sec ( 6.0% of XC) + XC-Potential eval. .... 0.019 sec ( 9.8% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.032 sec ( 0.7%) +Total Energy calculation .... 0.026 sec ( 0.5%) +Population analysis .... 2.848 sec ( 59.4%) +Orbital Transformation .... 0.013 sec ( 0.3%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.069 sec ( 1.4%) +SOSCF solution .... 0.047 sec ( 1.0%) +Finished LeanSCF after 7.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 50.0 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360143 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007179584 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.563019464971 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003820 -0.000005993 0.000000631 + 2 O : -0.000000409 0.000000554 0.000000016 + 3 O : 0.000003893 0.000008708 -0.000000284 + 4 H : 0.000000336 -0.000003269 -0.000000363 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000123846 +RMS gradient ... 0.0000035751 +MAX gradient ... 0.0000087078 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.000847012 -0.001444089 -0.005448090 + 2 O : -0.003632743 0.001054847 -0.007767948 + 3 O : 0.002986355 0.001862541 0.006012858 + 4 H : -0.000200624 -0.001473299 0.007203180 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000284204 -0.0000131674 -0.0000048455 + +Norm of the Cartesian gradient ... 0.0144835617 +RMS gradient ... 0.0041810441 +MAX gradient ... 0.0077679484 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.124 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 4.1%) +RI-J Coulomb gradient .... 0.059 sec ( 47.6%) +XC gradient .... 0.017 sec ( 13.9%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 25.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.563019465 Eh +Current gradient norm .... 0.014483562 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999959069 +Lowest eigenvalues of augmented Hessian: + -0.000043964 0.361263846 0.393870957 0.447881820 0.718439927 +Length of the computed step .... 0.009048059 +The final length of the internal step .... 0.009048059 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0036938546 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0031962410 RMS(Int)= 0.0036924441 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0020778577 0.0001000000 NO + MAX gradient 0.0032504232 0.0003000000 NO + RMS step 0.0036938546 0.0020000000 NO + MAX step 0.0059799322 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0032 Max(Angles) 0.17 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2848 0.002881 -0.0021 1.2828 + 2. B(O 2,O 1) 1.2920 0.003250 -0.0024 1.2896 + 3. B(H 3,N 0) 1.0356 0.002356 -0.0032 1.0324 + 4. A(O 1,N 0,H 3) 100.59 0.001050 -0.17 100.42 + 5. A(N 0,O 1,O 2) 117.22 -0.000624 0.08 117.30 + 6. D(O 2,O 1,N 0,H 3) 170.77 -0.013369 0.00 170.77 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (11.538 %) +Internal coordinates : 0.000 s ( 4.006 %) +B/P matrices and projection : 0.000 s (20.353 %) +Hessian update/contruction : 0.000 s (25.801 %) +Making the step : 0.000 s ( 6.410 %) +Converting the step to Cartesian: 0.000 s ( 4.968 %) +Storing new data : 0.000 s ( 4.006 %) +Checking convergence : 0.000 s ( 0.160 %) +Final printing : 0.000 s (22.596 %) +Total time : 0.001 s + +Time for energy+gradient : 13.482 s +Time for complete geometry iter : 14.270 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.169620 -0.685058 -0.080033 + O -0.196193 0.542432 -0.009504 + O 0.729973 1.438877 -0.050244 + H -0.722108 -1.158408 0.136073 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.320535 -1.294572 -0.151240 + 1 O 8.0000 0 15.999 -0.370751 1.025048 -0.017960 + 2 O 8.0000 0 15.999 1.379449 2.719084 -0.094947 + 3 H 1.0000 0 1.008 -1.364586 -2.189073 0.257140 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.282780304971 0.00000000 0.00000000 + O 2 1 0 1.289595641646 117.29890453 0.00000000 + H 1 2 3 1.032443916393 100.42225062 170.76923088 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.424103466384 0.00000000 0.00000000 + O 2 1 0 2.436982586210 117.29890453 0.00000000 + H 1 2 3 1.951036250615 100.42225062 170.76923088 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.230590466621 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.649e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5698527387905017 0.00e+00 9.18e-05 9.86e-04 1.71e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5698626190692551 -9.88e-06 7.79e-05 1.13e-03 2.66e-04 0.0 + 3 -205.5698541808617108 8.44e-06 5.74e-05 1.06e-03 1.62e-03 0.0 + 4 -205.5698631401748173 -8.96e-06 4.80e-05 6.57e-04 2.41e-04 0.0 + 5 -205.5698613680872029 1.77e-06 2.72e-05 4.77e-04 7.12e-04 0.0 + 6 -205.5698635992374363 -2.23e-06 1.70e-05 3.18e-04 6.91e-05 0.0 + 7 -205.5698635420368134 5.72e-08 1.01e-05 1.90e-04 7.44e-05 0.0 + 8 -205.5698636722698609 -1.30e-07 2.57e-07 2.63e-06 1.56e-06 0.0 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56986367226986 Eh -5593.84038 eV + +Components: +Nuclear Repulsion : 70.23059046662078 Eh 1911.07152 eV +Electronic Energy : -275.80045413889070 Eh -7504.91190 eV +One Electron Energy: -420.15137341195111 Eh -11432.90011 eV +Two Electron Energy: 144.35091927306044 Eh 3927.98821 eV + +Virial components: +Potential Energy : -410.43536070230846 Eh -11168.51396 eV +Kinetic Energy : 204.86549703003857 Eh 5574.67359 eV +Virial Ratio : 2.00343819067848 + +DFT components: +N(Alpha) : 12.000000641374 electrons +N(Beta) : 12.000000641374 electrons +N(Total) : 24.000001282749 electrons +E(X) : -23.357107178443 Eh +E(C) : -0.805151763458 Eh +E(XC) : -24.162258941900 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.3023e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.6297e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.5678e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.4351e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.5554e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.5397e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 4.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 50.2 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360225 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007178737 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.563045160618 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003819 -0.000005972 0.000000633 + 2 O : -0.000000408 0.000000547 0.000000017 + 3 O : 0.000003862 0.000008654 -0.000000281 + 4 H : 0.000000366 -0.000003229 -0.000000369 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000123161 +RMS gradient ... 0.0000035554 +MAX gradient ... 0.0000086536 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.001084310 -0.000649434 -0.005013829 + 2 O : -0.001940232 0.000134752 -0.007936399 + 3 O : 0.001465556 0.000342385 0.006126309 + 4 H : 0.001558986 0.000172297 0.006823919 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000321361 -0.0000138541 -0.0000080599 + +Norm of the Cartesian gradient ... 0.0135028816 +RMS gradient ... 0.0038979462 +MAX gradient ... 0.0079363992 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.120 sec + +Densities .... 0.000 sec ( 0.2%) +One electron gradient .... 0.005 sec ( 3.8%) +RI-J Coulomb gradient .... 0.054 sec ( 45.4%) +XC gradient .... 0.019 sec ( 16.1%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 25.9 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.563045161 Eh +Current gradient norm .... 0.013502882 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999995072 +Lowest eigenvalues of augmented Hessian: + -0.000004317 0.363213662 0.372322449 0.468419893 0.595951558 +Length of the computed step .... 0.003139577 +The final length of the internal step .... 0.003139577 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0012817271 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0007685014 RMS(Int)= 0.0012815297 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000002158 +Previously predicted energy change .... -0.000021984 +Actually observed energy change .... -0.000025696 +Ratio of predicted to observed change .... 1.168856340 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000256956 0.0000050000 NO + RMS gradient 0.0005735936 0.0001000000 NO + MAX gradient 0.0010968006 0.0003000000 NO + RMS step 0.0012817271 0.0020000000 YES + MAX step 0.0021254379 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0011 Max(Angles) 0.11 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2828 0.000494 -0.0006 1.2822 + 2. B(O 2,O 1) 1.2896 0.001097 -0.0011 1.2885 + 3. B(H 3,N 0) 1.0324 0.000001 -0.0002 1.0322 + 4. A(O 1,N 0,H 3) 100.42 -0.000185 0.02 100.45 + 5. A(N 0,O 1,O 2) 117.30 -0.000702 0.11 117.41 + 6. D(O 2,O 1,N 0,H 3) 170.77 -0.013440 0.00 170.77 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 1.085 %) +Internal coordinates : 0.000 s ( 0.422 %) +B/P matrices and projection : 0.000 s ( 1.768 %) +Hessian update/contruction : 0.005 s (91.982 %) +Making the step : 0.000 s ( 0.764 %) +Converting the step to Cartesian: 0.000 s ( 0.563 %) +Storing new data : 0.000 s ( 0.462 %) +Checking convergence : 0.000 s ( 0.201 %) +Final printing : 0.000 s ( 2.713 %) +Total time : 0.005 s + +Time for energy+gradient : 10.148 s +Time for complete geometry iter : 11.007 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.169469 -0.685124 -0.080074 + O -0.195139 0.542139 -0.009533 + O 0.729210 1.438846 -0.050193 + H -0.722248 -1.158017 0.136092 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.320249 -1.294698 -0.151318 + 1 O 8.0000 0 15.999 -0.368759 1.024495 -0.018014 + 2 O 8.0000 0 15.999 1.378008 2.719024 -0.094852 + 3 H 1.0000 0 1.008 -1.364851 -2.188334 0.257177 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.282221135364 0.00000000 0.00000000 + O 2 1 0 1.288470908330 117.41187841 0.00000000 + H 1 2 3 1.032237010490 100.44670409 170.76923088 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.423046788963 0.00000000 0.00000000 + O 2 1 0 2.434857148269 117.41187841 0.00000000 + H 1 2 3 1.950645255123 100.44670409 170.76923088 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1680 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.265764557595 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.637e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.4 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5698586457972397 0.00e+00 4.27e-05 4.78e-04 1.04e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5698609911384551 -2.35e-06 2.72e-05 3.87e-04 9.39e-05 0.0 + 3 -205.5698602922037708 6.99e-07 2.02e-05 3.09e-04 5.17e-04 0.0 + 4 -205.5698610964837485 -8.04e-07 1.94e-05 3.22e-04 7.05e-05 0.0 + 5 -205.5698610907756461 5.71e-09 8.28e-06 1.20e-04 8.38e-05 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56986109077565 Eh -5593.84031 eV + +Components: +Nuclear Repulsion : 70.26576455759471 Eh 1912.02866 eV +Electronic Energy : -275.83562564837035 Eh -7505.86896 eV +One Electron Energy: -420.22135533502802 Eh -11434.80441 eV +Two Electron Energy: 144.38572968665767 Eh 3928.93545 eV + +Virial components: +Potential Energy : -410.43925664406748 Eh -11168.61997 eV +Kinetic Energy : 204.86939555329184 Eh 5574.77967 eV +Virial Ratio : 2.00341908334133 + +DFT components: +N(Alpha) : 12.000000650585 electrons +N(Beta) : 12.000000650585 electrons +N(Total) : 24.000001301171 electrons +E(X) : -23.358588756725 Eh +E(C) : -0.805236141998 Eh +E(XC) : -24.163824898723 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -5.7081e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.2045e-04 Tolerance : 1.0000e-07 + Last RMS-Density change ... 8.2813e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.2822e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 8.3817e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.0418e-04 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 4.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 50.4 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360233 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007173902 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.563047421847 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.0 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003820 -0.000005970 0.000000633 + 2 O : -0.000000405 0.000000548 0.000000017 + 3 O : 0.000003856 0.000008649 -0.000000280 + 4 H : 0.000000369 -0.000003227 -0.000000369 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000123098 +RMS gradient ... 0.0000035535 +MAX gradient ... 0.0000086488 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.001656507 -0.000307433 -0.004932173 + 2 O : -0.000688315 0.000112230 -0.008071015 + 3 O : 0.000670472 0.000014938 0.006195104 + 4 H : 0.001674350 0.000180265 0.006808084 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000262112 -0.0000115511 0.0000362168 + +Norm of the Cartesian gradient ... 0.0134464695 +RMS gradient ... 0.0038816614 +MAX gradient ... 0.0080710153 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.093 sec + +Densities .... 0.000 sec ( 0.3%) +One electron gradient .... 0.004 sec ( 4.6%) +RI-J Coulomb gradient .... 0.045 sec ( 48.0%) +XC gradient .... 0.013 sec ( 13.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 26.0 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.563047422 Eh +Current gradient norm .... 0.013446470 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999713 +Lowest eigenvalues of augmented Hessian: + -0.000000251 0.345437763 0.405441452 0.430610087 0.546863665 +Length of the computed step .... 0.000757434 +The final length of the internal step .... 0.000757434 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0003092211 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001843024 RMS(Int)= 0.0003092200 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000126 +Previously predicted energy change .... -0.000002158 +Actually observed energy change .... -0.000002261 +Ratio of predicted to observed change .... 1.047610789 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000022612 0.0000050000 YES + RMS gradient 0.0001386063 0.0001000000 NO + MAX gradient 0.0002978664 0.0003000000 YES + RMS step 0.0003092211 0.0020000000 YES + MAX step 0.0006327978 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0003 Max(Angles) 0.02 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2822 0.000020 -0.0001 1.2822 + 2. B(O 2,O 1) 1.2885 0.000298 -0.0003 1.2881 + 3. B(H 3,N 0) 1.0322 -0.000102 0.0001 1.0323 + 4. A(O 1,N 0,H 3) 100.45 -0.000109 0.02 100.47 + 5. A(N 0,O 1,O 2) 117.41 0.000063 -0.00 117.41 + 6. D(O 2,O 1,N 0,H 3) 170.77 -0.013455 -0.00 170.77 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.758 %) +Internal coordinates : 0.000 s ( 3.880 %) +B/P matrices and projection : 0.000 s (15.168 %) +Hessian update/contruction : 0.000 s (26.279 %) +Making the step : 0.000 s ( 5.996 %) +Converting the step to Cartesian: 0.000 s ( 4.762 %) +Storing new data : 0.000 s ( 3.704 %) +Checking convergence : 0.000 s ( 2.116 %) +Final printing : 0.000 s (26.808 %) +Total time : 0.001 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.169451 -0.684946 -0.080056 + O -0.195062 0.542276 -0.009546 + O 0.729143 1.438650 -0.050196 + H -0.722240 -1.158136 0.136090 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.320216 -1.294361 -0.151283 + 1 O 8.0000 0 15.999 -0.368614 1.024753 -0.018040 + 2 O 8.0000 0 15.999 1.377881 2.718655 -0.094857 + 3 H 1.0000 0 1.008 -1.364836 -2.188560 0.257173 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.282152910809 0.00000000 0.00000000 + O 2 1 0 1.288136046137 117.40935698 0.00000000 + H 1 2 3 1.032347199272 100.46582373 170.76923088 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.422917863239 0.00000000 0.00000000 + O 2 1 0 2.434224350430 117.40935698 0.00000000 + H 1 2 3 1.950853481745 100.46582373 170.76923088 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1680 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.275438739097 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.634e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22304 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5576 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.2754387391 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.5 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5698609576776050 0.00e+00 1.01e-05 1.21e-04 2.65e-05 0.0 + *** Restarting incremental Fock matrix formation *** + 2 -205.5698610327595190 -7.51e-08 1.54e-05 2.33e-04 1.03e-04 0.0 + 3 -205.5698605639803134 4.69e-07 1.33e-05 2.29e-04 2.98e-04 0.0 + 4 -205.5698610235048989 -4.60e-07 1.83e-05 3.02e-04 1.16e-04 0.0 + 5 -205.5698602326073967 7.91e-07 1.43e-05 2.23e-04 3.89e-04 0.0 + 6 -205.5698610904754844 -8.58e-07 1.89e-07 3.09e-06 1.14e-06 0.0 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 6 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.56986109047548 Eh -5593.84031 eV + +Components: +Nuclear Repulsion : 70.27543873909664 Eh 1912.29191 eV +Electronic Energy : -275.84529982957213 Eh -7506.13221 eV +One Electron Energy: -420.23654539771672 Eh -11435.21776 eV +Two Electron Energy: 144.39124556814457 Eh 3929.08554 eV + +Virial components: +Potential Energy : -410.43975894312985 Eh -11168.63364 eV +Kinetic Energy : 204.86989785265436 Eh 5574.79334 eV +Virial Ratio : 2.00341662316015 + +DFT components: +N(Alpha) : 12.000000648572 electrons +N(Beta) : 12.000000648572 electrons +N(Total) : 24.000001297144 electrons +E(X) : -23.358416795307 Eh +E(C) : -0.805248453699 Eh +E(XC) : -24.163665249006 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 8.5787e-07 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.0943e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.8938e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.8545e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.1420e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.4797e-06 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.192966 -522.2671 + 1 2.0000 -19.017330 -517.4878 + 2 2.0000 -14.269324 -388.2881 + 3 2.0000 -1.260417 -34.2977 + 4 2.0000 -0.977200 -26.5910 + 5 2.0000 -0.696099 -18.9418 + 6 2.0000 -0.569858 -15.5066 + 7 2.0000 -0.524552 -14.2738 + 8 2.0000 -0.507438 -13.8081 + 9 2.0000 -0.329335 -8.9617 + 10 2.0000 -0.287753 -7.8302 + 11 2.0000 -0.258332 -7.0296 + 12 0.0000 -0.176300 -4.7974 + 13 0.0000 0.057671 1.5693 + 14 0.0000 0.080889 2.2011 + 15 0.0000 0.150664 4.0998 + 16 0.0000 0.220933 6.0119 + 17 0.0000 0.276005 7.5105 + 18 0.0000 0.295885 8.0514 + 19 0.0000 0.327526 8.9124 + 20 0.0000 0.365260 9.9392 + 21 0.0000 0.380502 10.3540 + 22 0.0000 0.397879 10.8268 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.286283 + 1 O : 0.228763 + 2 O : -0.207631 + 3 H : 0.265150 +Sum of atomic charges: 0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.886129 s : 3.886129 + pz : 1.096617 p : 3.338028 + px : 1.402538 + py : 0.838873 + dz2 : 0.008122 d : 0.062126 + dxz : 0.009916 + dyz : 0.013667 + dx2y2 : 0.015030 + dxy : 0.015391 + + 1 O s : 3.738779 s : 3.738779 + pz : 1.383072 p : 3.887148 + px : 1.459571 + py : 1.044505 + dz2 : 0.004737 d : 0.145309 + dxz : 0.012168 + dyz : 0.046781 + dx2y2 : 0.057074 + dxy : 0.024549 + + 2 O s : 3.945579 s : 3.945579 + pz : 1.424379 p : 4.234678 + px : 1.438068 + py : 1.372231 + dz2 : 0.002076 d : 0.027374 + dxz : 0.008151 + dyz : 0.005910 + dx2y2 : 0.003775 + dxy : 0.007462 + + 3 H s : 0.705203 s : 0.705203 + pz : 0.006955 p : 0.029647 + px : 0.015138 + py : 0.007554 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.055956 + 1 O : -0.197058 + 2 O : -0.027280 + 3 H : 0.280294 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.354792 s : 3.354792 + pz : 1.019456 p : 3.380677 + px : 1.376675 + py : 0.984546 + dz2 : 0.038697 d : 0.320487 + dxz : 0.010547 + dyz : 0.063302 + dx2y2 : 0.074782 + dxy : 0.133159 + + 1 O s : 3.356497 s : 3.356497 + pz : 1.276467 p : 4.041124 + px : 1.489918 + py : 1.274739 + dz2 : 0.062788 d : 0.799437 + dxz : 0.028998 + dyz : 0.199536 + dx2y2 : 0.241094 + dxy : 0.267021 + + 2 O s : 3.593421 s : 3.593421 + pz : 1.341402 p : 4.177011 + px : 1.436410 + py : 1.399199 + dz2 : 0.029951 d : 0.256848 + dxz : 0.029946 + dyz : 0.035878 + dx2y2 : 0.081793 + dxy : 0.079280 + + 3 H s : 0.645833 s : 0.645833 + pz : 0.015684 p : 0.073873 + px : 0.042645 + py : 0.015544 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2863 7.0000 -0.2863 2.7266 2.7266 0.0000 + 1 O 7.7712 8.0000 0.2288 2.6642 2.6642 0.0000 + 2 O 8.2076 8.0000 -0.2076 1.7438 1.7438 0.0000 + 3 H 0.7348 1.0000 0.2652 0.9167 0.9167 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3918 B( 0-N , 2-O ) : 0.4557 B( 0-N , 3-H ) : 0.8790 +B( 1-O , 2-O ) : 1.2614 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 4 sec + +Total time .... 4.721 sec +Sum of individual times .... 4.706 sec ( 99.7%) + +SCF preparation .... 1.606 sec ( 34.0%) +Fock matrix formation .... 0.146 sec ( 3.1%) + Startup .... 0.008 sec ( 5.3% of F) + Split-RI-J .... 0.020 sec ( 13.6% of F) + XC integration .... 0.097 sec ( 66.5% of F) + Basis function eval. .... 0.006 sec ( 6.1% of XC) + Density eval. .... 0.008 sec ( 7.9% of XC) + XC-Functional eval. .... 0.005 sec ( 5.1% of XC) + XC-Potential eval. .... 0.007 sec ( 7.0% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.009 sec ( 0.2%) +Total Energy calculation .... 0.012 sec ( 0.2%) +Population analysis .... 2.888 sec ( 61.2%) +Orbital Transformation .... 0.006 sec ( 0.1%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.009 sec ( 0.2%) +SOSCF solution .... 0.032 sec ( 0.7%) +Finished LeanSCF after 7.7 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 50.7 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360238 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007173743 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.563047585071 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.039.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.039.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.409605 0.841355 -0.077979 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5698610904754844 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.033352776 0.783703845 -0.035315915 +Nuclear contribution : -0.879714983 -1.494332318 0.166513617 + ----------------------------------------- +Total Dipole Moment : -0.846362206 -0.710628473 0.131197702 + ----------------------------------------- +Magnitude (a.u.) : 1.112894715 +Magnitude (Debye) : 2.828753562 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.452010 0.427146 0.380504 +Rotational constants in MHz : 103488.669262 12805.529169 11407.229969 + +Dipole components along the rotational axes: +x,y,z [a.u.] : -0.928533 0.609024 0.073831 +x,y,z [Debye]: -2.360143 1.548016 0.187664 + + + +Dipole moment calculation done in 1.0 sec + +Maximum memory used throughout the entire PROP-calculation: 26.3 MB + + ************************************************************* + * RELAXED SURFACE SCAN STEP 40 * + * * + * Dihedral ( 2, 1, 0, 3) : 180.00000000 * + ************************************************************* + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 100 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 0 +The number of degrees of freedom .... 6 +Storing new coordinates .... done + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(O 1,N 0) 1.2823 0.744862 + 2. B(O 2,O 1) 1.2914 0.728668 + 3. B(H 3,N 0) 1.0353 0.398604 + 4. A(O 1,N 0,H 3) 100.4965 0.362612 + 5. A(N 0,O 1,O 2) 117.2658 0.449840 + 6. D(O 2,O 1,N 0,H 3) 180.0000 0.043969 C + ----------------------------------------------------------------- + +Number of atoms .... 4 +Number of degrees of freedom .... 6 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.175887 -0.684339 -0.047658 + O -0.189219 0.541632 0.041551 + O 0.726470 1.442671 -0.089862 + H -0.731845 -1.162121 0.092261 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.332378 -1.293214 -0.090060 + 1 O 8.0000 0 15.999 -0.357573 1.023537 0.078520 + 2 O 8.0000 0 15.999 1.372828 2.726254 -0.169815 + 3 H 1.0000 0 1.008 -1.382987 -2.196090 0.174347 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.282152910809 0.00000000 0.00000000 + O 2 1 0 1.288136046137 117.40935698 0.00000000 + H 1 2 3 1.032347199272 100.46582373 170.76923088 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.422917863239 0.00000000 0.00000000 + O 2 1 0 2.434224350430 117.40935698 0.00000000 + H 1 2 3 1.950853481745 100.46582373 170.76923088 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.181380497591 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.645e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22298 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.2 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.1813804976 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.5 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -205.5660375698768121 0.00e+00 3.82e-04 3.94e-03 2.82e-02 0.700 0.1 +Warning: op=0 Small HOMO/LUMO gap ( 0.082) - skipping pre-diagonalization + Will do a full diagonalization + 2 -205.5673482655143971 -1.31e-03 4.44e-04 4.83e-03 2.15e-02 0.700 0.0 + ***Turning on AO-DIIS*** + 3 -205.5684233583966716 -1.08e-03 3.37e-04 3.73e-03 1.53e-02 0.700 0.0 + 4 -205.5691756345505610 -7.52e-04 8.39e-04 9.42e-03 1.08e-02 0.000 0.0 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -205.5709255925393109 -1.75e-03 6.69e-05 7.50e-04 6.96e-04 0.0 + *** Restarting incremental Fock matrix formation *** + 6 -205.5709286950611840 -3.10e-06 2.20e-04 3.08e-03 8.81e-04 0.0 + 7 -205.5708527264559962 7.60e-05 1.64e-04 2.91e-03 5.18e-03 0.0 + 8 -205.5709366445003070 -8.39e-05 2.68e-05 2.11e-04 1.14e-04 0.0 + 9 -205.5709367359784210 -9.15e-08 8.43e-06 1.41e-04 1.49e-04 0.0 + 10 -205.5709368008143656 -6.48e-08 1.15e-05 9.69e-05 1.26e-04 0.0 + 11 -205.5709368536415695 -5.28e-08 5.54e-06 4.55e-05 4.12e-05 0.0 + 12 -205.5709368806012094 -2.70e-08 1.20e-06 1.72e-05 7.54e-06 0.0 + 13 -205.5709368817035170 -1.10e-09 5.97e-07 6.65e-06 3.89e-06 0.0 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 13 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57093688170352 Eh -5593.86958 eV + +Components: +Nuclear Repulsion : 70.18138049759131 Eh 1909.73245 eV +Electronic Energy : -275.75231737929482 Eh -7503.60203 eV +One Electron Energy: -420.05977607058622 Eh -11430.40762 eV +Two Electron Energy: 144.30745869129143 Eh 3926.80559 eV + +Virial components: +Potential Energy : -410.42760761336092 Eh -11168.30299 eV +Kinetic Energy : 204.85667073165737 Eh 5574.43341 eV +Virial Ratio : 2.00348666288237 + +DFT components: +N(Alpha) : 11.999997760353 electrons +N(Beta) : 11.999997760353 electrons +N(Total) : 23.999995520705 electrons +E(X) : -23.355199371873 Eh +E(C) : -0.805037463100 Eh +E(XC) : -24.160236834973 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.1023e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.6536e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 5.9725e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 6.9612e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.8875e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.4483e-05 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.192960 -522.2670 + 1 2.0000 -19.016652 -517.4694 + 2 2.0000 -14.270525 -388.3207 + 3 2.0000 -1.258829 -34.2545 + 4 2.0000 -0.976064 -26.5600 + 5 2.0000 -0.696146 -18.9431 + 6 2.0000 -0.569307 -15.4916 + 7 2.0000 -0.524004 -14.2589 + 8 2.0000 -0.507007 -13.7964 + 9 2.0000 -0.328954 -8.9513 + 10 2.0000 -0.288347 -7.8463 + 11 2.0000 -0.258220 -7.0265 + 12 0.0000 -0.176029 -4.7900 + 13 0.0000 0.055354 1.5063 + 14 0.0000 0.079659 2.1676 + 15 0.0000 0.149362 4.0643 + 16 0.0000 0.220450 5.9988 + 17 0.0000 0.276809 7.5324 + 18 0.0000 0.294730 8.0200 + 19 0.0000 0.327235 8.9045 + 20 0.0000 0.367311 9.9951 + 21 0.0000 0.381364 10.3775 + 22 0.0000 0.396596 10.7919 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.283109 + 1 O : 0.227945 + 2 O : -0.210114 + 3 H : 0.265278 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.886300 s : 3.886300 + pz : 1.100446 p : 3.334267 + px : 1.394028 + py : 0.839792 + dz2 : 0.008330 d : 0.062543 + dxz : 0.009428 + dyz : 0.013560 + dx2y2 : 0.015465 + dxy : 0.015760 + + 1 O s : 3.739835 s : 3.739835 + pz : 1.383442 p : 3.886835 + px : 1.459969 + py : 1.043424 + dz2 : 0.005170 d : 0.145384 + dxz : 0.012415 + dyz : 0.046388 + dx2y2 : 0.056246 + dxy : 0.025165 + + 2 O s : 3.946315 s : 3.946315 + pz : 1.429388 p : 4.236465 + px : 1.439225 + py : 1.367853 + dz2 : 0.002464 d : 0.027334 + dxz : 0.007490 + dyz : 0.006057 + dx2y2 : 0.003999 + dxy : 0.007325 + + 3 H s : 0.705330 s : 0.705330 + pz : 0.006508 p : 0.029392 + px : 0.015356 + py : 0.007527 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.055442 + 1 O : -0.196565 + 2 O : -0.029386 + 3 H : 0.281393 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.356427 s : 3.356427 + pz : 1.021547 p : 3.377824 + px : 1.371401 + py : 0.984875 + dz2 : 0.039240 d : 0.321191 + dxz : 0.009501 + dyz : 0.062930 + dx2y2 : 0.075242 + dxy : 0.134278 + + 1 O s : 3.358097 s : 3.358097 + pz : 1.279460 p : 4.040844 + px : 1.487148 + py : 1.274236 + dz2 : 0.062158 d : 0.797624 + dxz : 0.030799 + dyz : 0.200437 + dx2y2 : 0.238178 + dxy : 0.266052 + + 2 O s : 3.595428 s : 3.595428 + pz : 1.348180 p : 4.178241 + px : 1.435015 + py : 1.395046 + dz2 : 0.029830 d : 0.255716 + dxz : 0.030712 + dyz : 0.036829 + dx2y2 : 0.079974 + dxy : 0.078372 + + 3 H s : 0.645415 s : 0.645415 + pz : 0.014438 p : 0.073192 + px : 0.043253 + py : 0.015500 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2831 7.0000 -0.2831 2.7296 2.7296 -0.0000 + 1 O 7.7721 8.0000 0.2279 2.6670 2.6670 -0.0000 + 2 O 8.2101 8.0000 -0.2101 1.7450 1.7450 -0.0000 + 3 H 0.7347 1.0000 0.2653 0.9166 0.9166 -0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3941 B( 0-N , 2-O ) : 0.4564 B( 0-N , 3-H ) : 0.8790 +B( 1-O , 2-O ) : 1.2620 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 4 sec + +Total time .... 4.962 sec +Sum of individual times .... 4.944 sec ( 99.6%) + +SCF preparation .... 1.411 sec ( 28.4%) +Fock matrix formation .... 0.322 sec ( 6.5%) + Startup .... 0.015 sec ( 4.5% of F) + Split-RI-J .... 0.053 sec ( 16.4% of F) + XC integration .... 0.199 sec ( 61.9% of F) + Basis function eval. .... 0.015 sec ( 7.6% of XC) + Density eval. .... 0.018 sec ( 9.2% of XC) + XC-Functional eval. .... 0.011 sec ( 5.4% of XC) + XC-Potential eval. .... 0.015 sec ( 7.5% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.027 sec ( 0.5%) +Total Energy calculation .... 0.028 sec ( 0.6%) +Population analysis .... 3.025 sec ( 61.0%) +Orbital Transformation .... 0.014 sec ( 0.3%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.070 sec ( 1.4%) +SOSCF solution .... 0.048 sec ( 1.0%) +Finished LeanSCF after 8.1 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 51.0 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360145 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007180973 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.564116053990 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003844 -0.000005987 0.000000501 + 2 O : -0.000000401 0.000000546 0.000000079 + 3 O : 0.000003871 0.000008709 -0.000000442 + 4 H : 0.000000374 -0.000003269 -0.000000138 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000123776 +RMS gradient ... 0.0000035731 +MAX gradient ... 0.0000087092 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.002217971 0.000035602 -0.000351042 + 2 O : -0.002460485 -0.000430950 0.000390343 + 3 O : 0.002029551 0.001619910 -0.000304732 + 4 H : -0.001787037 -0.001224562 0.000265431 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000345564 -0.0000074746 0.0000124846 + +Norm of the Cartesian gradient ... 0.0047995326 +RMS gradient ... 0.0013855057 +MAX gradient ... 0.0024604847 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.301 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.005 sec ( 1.6%) +RI-J Coulomb gradient .... 0.058 sec ( 19.4%) +XC gradient .... 0.021 sec ( 7.0%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 26.4 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.564116054 Eh +Current gradient norm .... 0.004799533 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999974891 +Lowest eigenvalues of augmented Hessian: + -0.000025123 0.361912753 0.394326640 0.448832333 0.720081947 +Length of the computed step .... 0.007086620 +The final length of the internal step .... 0.007086620 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0028931005 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0021596417 RMS(Int)= 0.0028922018 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0015138954 0.0001000000 NO + MAX gradient 0.0026007468 0.0003000000 NO + RMS step 0.0028931005 0.0020000000 NO + MAX step 0.0054986649 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0029 Max(Angles) 0.08 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2823 0.001265 -0.0009 1.2814 + 2. B(O 2,O 1) 1.2914 0.002601 -0.0019 1.2895 + 3. B(H 3,N 0) 1.0353 0.002168 -0.0029 1.0324 + 4. A(O 1,N 0,H 3) 100.50 0.000493 -0.08 100.42 + 5. A(N 0,O 1,O 2) 117.27 -0.000666 0.08 117.35 + 6. D(O 2,O 1,N 0,H 3) 180.00 0.000005 0.00 180.00 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 1.933 %) +Internal coordinates : 0.000 s ( 0.665 %) +B/P matrices and projection : 0.000 s ( 2.757 %) +Hessian update/contruction : 0.001 s (17.744 %) +Making the step : 0.000 s ( 1.141 %) +Converting the step to Cartesian: 0.000 s ( 0.887 %) +Storing new data : 0.000 s ( 0.729 %) +Checking convergence : 0.000 s ( 0.000 %) +Final printing : 0.002 s (74.081 %) +Total time : 0.003 s + +Time for energy+gradient : 13.897 s +Time for complete geometry iter : 14.828 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.175510 -0.684680 -0.047603 + O -0.188596 0.540662 0.041425 + O 0.724969 1.441169 -0.089647 + H -0.730591 -1.159308 0.092117 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.331666 -1.293858 -0.089957 + 1 O 8.0000 0 15.999 -0.356395 1.021704 0.078282 + 2 O 8.0000 0 15.999 1.369993 2.723415 -0.169409 + 3 H 1.0000 0 1.008 -1.380618 -2.190774 0.174077 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.281391126833 0.00000000 0.00000000 + O 2 1 0 1.289455027789 117.35076658 0.00000000 + H 1 2 3 1.032382339832 100.41844286 180.00000000 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.421478300152 0.00000000 0.00000000 + O 2 1 0 2.436716864529 117.35076658 0.00000000 + H 1 2 3 1.950919887780 100.41844286 180.00000000 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1678 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.262658093701 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.625e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22296 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.9 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5709414689642358 0.00e+00 7.10e-05 8.70e-04 1.17e-04 0.7 + *** Restarting incremental Fock matrix formation *** + 2 -205.5709473443899356 -5.88e-06 4.61e-05 7.41e-04 1.62e-04 0.2 + 3 -205.5709449132497184 2.43e-06 3.42e-05 6.12e-04 9.45e-04 0.2 + 4 -205.5709476067360697 -2.69e-06 3.13e-05 5.71e-04 1.10e-04 0.2 + 5 -205.5709475305847604 7.62e-08 1.53e-05 2.69e-04 1.42e-04 0.1 + 6 -205.5709478125993428 -2.82e-07 8.30e-06 1.39e-04 7.02e-05 0.2 + 7 -205.5709477478662279 6.47e-08 6.09e-06 1.09e-04 1.17e-04 0.2 + 8 -205.5709478336713687 -8.58e-08 3.58e-07 4.21e-06 2.59e-06 0.2 + 9 -205.5709478337556675 -8.43e-11 1.46e-07 1.47e-06 1.49e-06 0.2 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57094783375567 Eh -5593.86988 eV + +Components: +Nuclear Repulsion : 70.26265809370058 Eh 1911.94413 eV +Electronic Energy : -275.83360592745623 Eh -7505.81401 eV +One Electron Energy: -420.21330113548112 Eh -11434.58525 eV +Two Electron Energy: 144.37969520802491 Eh 3928.77124 eV + +Virial components: +Potential Energy : -410.43851400618104 Eh -11168.59977 eV +Kinetic Energy : 204.86756617242537 Eh 5574.72989 eV +Virial Ratio : 2.00343334806222 + +DFT components: +N(Alpha) : 11.999997756332 electrons +N(Beta) : 11.999997756332 electrons +N(Total) : 23.999995512664 electrons +E(X) : -23.358173326978 Eh +E(C) : -0.805208187744 Eh +E(XC) : -24.163381514721 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 8.4299e-11 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.4671e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.4589e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.0529e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.4867e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.2359e-06 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 3 sec +Finished LeanSCF after 7.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 51.2 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360192 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007177099 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.564130926544 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003845 -0.000005975 0.000000501 + 2 O : -0.000000400 0.000000543 0.000000079 + 3 O : 0.000003849 0.000008674 -0.000000439 + 4 H : 0.000000395 -0.000003242 -0.000000141 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Norm of the Dispersion gradient ... 0.0000123339 +RMS gradient ... 0.0000035605 +MAX gradient ... 0.0000086740 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : 0.000281718 -0.000043245 -0.000029981 + 2 O : -0.001099448 -0.000584664 0.000160720 + 3 O : 0.000862754 0.000597512 -0.000135641 + 4 H : -0.000045024 0.000030397 0.000004902 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : -0.0000393372 -0.0000055862 0.0000101873 + +Norm of the Cartesian gradient ... 0.0016677296 +RMS gradient ... 0.0004814321 +MAX gradient ... 0.0010994482 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.429 sec + +Densities .... 0.000 sec ( 0.1%) +One electron gradient .... 0.004 sec ( 1.0%) +RI-J Coulomb gradient .... 0.052 sec ( 12.1%) +XC gradient .... 0.023 sec ( 5.2%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 26.4 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.564130927 Eh +Current gradient norm .... 0.001667730 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999996934 +Lowest eigenvalues of augmented Hessian: + -0.000002745 0.358773934 0.371147157 0.467271764 0.592882537 +Length of the computed step .... 0.002476227 +The final length of the internal step .... 0.002476227 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0010109153 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0005790905 RMS(Int)= 0.0010108308 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000001372 +Previously predicted energy change .... -0.000012562 +Actually observed energy change .... -0.000014873 +Ratio of predicted to observed change .... 1.183907686 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000148726 0.0000050000 NO + RMS gradient 0.0004657982 0.0001000000 NO + MAX gradient 0.0010425026 0.0003000000 NO + RMS step 0.0010109153 0.0020000000 YES + MAX step 0.0020183653 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0011 Max(Angles) 0.08 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2814 0.000081 -0.0001 1.2813 + 2. B(O 2,O 1) 1.2895 0.001043 -0.0011 1.2884 + 3. B(H 3,N 0) 1.0324 0.000026 -0.0002 1.0321 + 4. A(O 1,N 0,H 3) 100.42 -0.000094 0.01 100.43 + 5. A(N 0,O 1,O 2) 117.35 -0.000446 0.08 117.43 + 6. D(O 2,O 1,N 0,H 3) 180.00 0.000006 0.00 180.00 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.042 %) +Internal coordinates : 0.000 s ( 0.022 %) +B/P matrices and projection : 0.000 s ( 0.065 %) +Hessian update/contruction : 0.132 s (98.339 %) +Making the step : 0.000 s ( 0.040 %) +Converting the step to Cartesian: 0.000 s ( 0.026 %) +Storing new data : 0.000 s ( 0.022 %) +Checking convergence : 0.000 s ( 0.007 %) +Final printing : 0.002 s ( 1.432 %) +Total time : 0.135 s + +Time for energy+gradient : 13.946 s +Time for complete geometry iter : 15.045 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.175439 -0.684829 -0.047595 + O -0.187857 0.540626 0.041301 + O 0.724351 1.441012 -0.089548 + H -0.730642 -1.158965 0.092134 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.331532 -1.294139 -0.089941 + 1 O 8.0000 0 15.999 -0.354998 1.021635 0.078048 + 2 O 8.0000 0 15.999 1.368826 2.723118 -0.169222 + 3 H 1.0000 0 1.008 -1.380713 -2.190126 0.174107 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.281259166444 0.00000000 0.00000000 + O 2 1 0 1.288386954858 117.42622808 0.00000000 + H 1 2 3 1.032139361053 100.43128764 180.00000000 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.421228931156 0.00000000 0.00000000 + O 2 1 0 2.434698499198 117.42622808 0.00000000 + H 1 2 3 1.950460724430 100.43128764 180.00000000 + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1680 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.289056213811 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.615e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22295 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.5 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Occupation numbers will be reassigned to an Aufbau configuration + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 1.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5709444707506179 0.00e+00 3.29e-05 3.72e-04 6.95e-05 0.5 + *** Restarting incremental Fock matrix formation *** + 2 -205.5709459341847207 -1.46e-06 2.53e-05 4.38e-04 1.09e-04 0.3 + 3 -205.5709449278722616 1.01e-06 1.92e-05 3.30e-04 5.97e-04 0.2 + 4 -205.5709460449762958 -1.12e-06 8.33e-06 1.48e-04 2.93e-05 0.1 + 5 -205.5709460427527517 2.22e-09 3.48e-06 5.94e-05 3.50e-05 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57094604275275 Eh -5593.86983 eV + +Components: +Nuclear Repulsion : 70.28905621381111 Eh 1912.66246 eV +Electronic Energy : -275.86000225656392 Eh -7506.53229 eV +One Electron Energy: -420.26450039052395 Eh -11435.97845 eV +Two Electron Energy: 144.40449813396006 Eh 3929.44616 eV + +Virial components: +Potential Energy : -410.44155305279651 Eh -11168.68246 eV +Kinetic Energy : 204.87060701004376 Eh 5574.81263 eV +Virial Ratio : 2.00341844563713 + +DFT components: +N(Alpha) : 11.999997742342 electrons +N(Beta) : 11.999997742342 electrons +N(Total) : 23.999995484683 electrons +E(X) : -23.359146052474 Eh +E(C) : -0.805270819156 Eh +E(XC) : -24.164416871631 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -2.2235e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 5.9417e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.4832e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.1749e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.5000e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 3.8457e-05 Tolerance : 1.0000e-05 + + +Total SCF time: 0 days 0 hours 0 min 3 sec +Finished LeanSCF after 6.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 51.4 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +------------------------- ---------------- +Dispersion correction -0.000360200 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007173767 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.564132475741 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +XC gradient ... done ( 0.0 sec) +Dispersion correction ... done ( 0.0 sec) + +------------------- +DISPERSION GRADIENT +------------------- + + 1 N : -0.000003845 -0.000005973 0.000000501 + 2 O : -0.000000397 0.000000544 0.000000079 + 3 O : 0.000003844 0.000008669 -0.000000438 + 4 H : 0.000000398 -0.000003240 -0.000000141 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Norm of the Dispersion gradient ... 0.0000123273 +RMS gradient ... 0.0000035586 +MAX gradient ... 0.0000086687 +gCP correction ... done + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 N : -0.000144387 0.000078787 0.000043924 + 2 O : -0.000133967 -0.000312588 0.000007071 + 3 O : 0.000172826 0.000173660 -0.000031559 + 4 H : 0.000105528 0.000060140 -0.000019437 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000425893 -0.0000040328 0.0000022656 + +Norm of the Cartesian gradient ... 0.0004699425 +RMS gradient ... 0.0001356607 +MAX gradient ... 0.0003125878 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.297 sec + +Densities .... 0.001 sec ( 0.2%) +One electron gradient .... 0.007 sec ( 2.3%) +RI-J Coulomb gradient .... 0.059 sec ( 19.9%) +XC gradient .... 0.017 sec ( 5.9%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 26.5 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 4 +Number of internal coordinates .... 6 +Current Energy .... -205.564132476 Eh +Current gradient norm .... 0.000469942 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999999796 +Lowest eigenvalues of augmented Hessian: + -0.000000194 0.365363692 0.369420908 0.447522664 0.514914376 +Length of the computed step .... 0.000639322 +The final length of the internal step .... 0.000639322 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0002610020 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0001266840 RMS(Int)= 0.0002610027 +Imposing constraints: + Iter 0: RMS(Cart)= 0.0000000000 RMS(Int)= 0.0000000000 +CONVERGED +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000097 +Previously predicted energy change .... -0.000001372 +Actually observed energy change .... -0.000001549 +Ratio of predicted to observed change .... 1.128751743 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000015492 0.0000050000 YES + RMS gradient 0.0001272609 0.0001000000 NO + MAX gradient 0.0002467031 0.0003000000 YES + RMS step 0.0002610020 0.0020000000 YES + MAX step 0.0005584582 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0003 Max(Angles) 0.00 + Max(Dihed) 0.00 Max(Improp) 0.00 + --------------------------------------------------------------------- + + The step convergence is overachieved with + reasonable convergence on the gradient + Convergence will therefore be signaled now + + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(O 1,N 0) 1.2813 -0.000145 0.0001 1.2814 + 2. B(O 2,O 1) 1.2884 0.000247 -0.0003 1.2881 + 3. B(H 3,N 0) 1.0321 -0.000123 0.0001 1.0323 + 4. A(O 1,N 0,H 3) 100.43 -0.000007 0.00 100.43 + 5. A(N 0,O 1,O 2) 117.43 0.000005 0.00 117.43 + 6. D(O 2,O 1,N 0,H 3) 180.00 0.000007 -0.00 180.00 C + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 0.085 %) +Internal coordinates : 0.000 s ( 0.025 %) +B/P matrices and projection : 0.000 s ( 0.162 %) +Hessian update/contruction : 0.011 s (12.469 %) +Making the step : 0.000 s ( 0.052 %) +Converting the step to Cartesian: 0.000 s ( 0.035 %) +Storing new data : 0.000 s ( 0.029 %) +Checking convergence : 0.000 s ( 0.012 %) +Final printing : 0.077 s (87.129 %) +Total time : 0.088 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 3 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + N 0.175507 -0.684836 -0.047606 + O -0.187746 0.540734 0.041285 + O 0.724240 1.440928 -0.089532 + H -0.730709 -1.158982 0.092144 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 N 7.0000 0 14.007 0.331661 -1.294152 -0.089963 + 1 O 8.0000 0 15.999 -0.354788 1.021839 0.078018 + 2 O 8.0000 0 15.999 1.368614 2.722959 -0.169190 + 3 H 1.0000 0 1.008 -1.380840 -2.190159 0.174128 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.281356806057 0.00000000 0.00000000 + O 2 1 0 1.288091431519 117.43041262 0.00000000 + H 1 2 3 1.032266194983 100.43160574 180.00000000 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + N 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.421413443284 0.00000000 0.00000000 + O 2 1 0 2.434140041022 117.43041262 0.00000000 + H 1 2 3 1.950700405822 100.43160574 180.00000000 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 2 Type O : 11s6p2d contracted to 5s3p2d pattern {62111/411/11} + Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 3 groups of distinct atoms + + Group 1 Type N : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 2 Type O : 8s3p3d contracted to 6s3p3d pattern {311111/111/111} + Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0N basis set group => 1 +Atom 1O basis set group => 2 +Atom 2O basis set group => 2 +Atom 3H basis set group => 3 + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 4 +Number of basis functions ... 77 +Number of shells ... 33 +Maximum angular momentum ... 2 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 101 + # of shells in Aux-J ... 41 + Maximum angular momentum in Aux-J ... 2 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 33 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 561 +Shell pairs after pre-screening ... 554 +Total number of primitive shell pairs ... 2022 +Primitive shell pairs kept ... 1680 + la=0 lb=0: 147 shell pairs + la=1 lb=0: 169 shell pairs + la=1 lb=1: 55 shell pairs + la=2 lb=0: 102 shell pairs + la=2 lb=1: 60 shell pairs + la=2 lb=2: 21 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 70.293432484355 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 3.613e-04 +Time for diagonalization ... 0.001 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.002 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit +Diffuse basis detected: some atoms will have their outermost + angular grid increased by 1. + +Total number of grid points ... 22295 +Total number of batches ... 350 +Average number of points per batch ... 63 +Average number of grid points per atom ... 5574 +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 7.7 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Functional kind .... Exchange + Functional name .... Re-regularized SCAN exchange by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 6 + Parameter 0 _c1 = 6.670000e-01 : c1 parameter + Parameter 1 _c2 = 8.000000e-01 : c2 parameter + Parameter 2 _d = 1.240000e+00 : d parameter + Parameter 3 _k1 = 6.500000e-02 : k1 parameter + Parameter 4 _eta = 1.000000e-03 : eta parameter + Parameter 5 _dp2 = 3.610000e-01 : dp2 parameter + Functional kind .... Correlation + Functional name .... Re-regularized SCAN correlation by Furness et al + Functional family .... MGGA + Functional refs + [ 0] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 8208-8215 (2020), doi: 10.1021/acs.jpclett.0c02405 + [ 1] J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun., J. Phys. Chem. Lett. 11, 9248-9248 (2020), doi: 10.1021/acs.jpclett.0c03077 + Functional external parameters .... 1 + Parameter 0 _eta = 1.000000e-03 : Regularization parameter + Gradients option PostSCFGGA .... off + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 101 + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... RHF + Total Charge Charge .... 0 + Multiplicity Mult .... 1 + Number of Electrons NEL .... 24 + Basis Dimension Dim .... 77 + Nuclear Repulsion ENuc .... 70.2934324844 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + COSX micro iterations for RIJONX calc.... off + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 1500 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +Occupation numbers will be reassigned to an Aufbau configuration +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.1 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.7 sec +Maximum memory used throughout the entire GUESS-calculation: 4.1 MB + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -205.5709460521573533 0.00e+00 7.83e-06 6.94e-05 1.86e-05 0.9 + *** Restarting incremental Fock matrix formation *** + 2 -205.5709461380160974 -8.59e-08 1.20e-05 2.26e-04 5.47e-05 0.9 + 3 -205.5709458274884014 3.11e-07 1.02e-05 1.86e-04 3.04e-04 0.3 + 4 -205.5709461482651363 -3.21e-07 5.29e-06 9.90e-05 4.50e-05 0.2 + 5 -205.5709460874711567 6.08e-08 3.90e-06 7.41e-05 1.35e-04 0.5 + 6 -205.5709461569200585 -6.94e-08 7.70e-08 1.31e-06 6.34e-07 0.6 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 6 CYCLES * + ***************************************************** + + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -205.57094615692006 Eh -5593.86983 eV + +Components: +Nuclear Repulsion : 70.29343248435528 Eh 1912.78154 eV +Electronic Energy : -275.86437864127532 Eh -7506.65137 eV +One Electron Energy: -420.27158363333967 Eh -11436.17119 eV +Two Electron Energy: 144.40720499206435 Eh 3929.51982 eV + +Virial components: +Potential Energy : -410.44155077965183 Eh -11168.68240 eV +Kinetic Energy : 204.87060462273178 Eh 5574.81257 eV +Virial Ratio : 2.00341845788701 + +DFT components: +N(Alpha) : 11.999997736609 electrons +N(Beta) : 11.999997736609 electrons +N(Total) : 23.999995473217 electrons +E(X) : -23.359048642343 Eh +E(C) : -0.805277450727 Eh +E(XC) : -24.164326093070 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 6.9449e-08 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.3109e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 7.7008e-08 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.3745e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 6.3403e-07 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 5.4053e-07 Tolerance : 1.0000e-05 + + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -19.193187 -522.2732 + 1 2.0000 -19.016758 -517.4723 + 2 2.0000 -14.269773 -388.3003 + 3 2.0000 -1.260732 -34.3063 + 4 2.0000 -0.977517 -26.5996 + 5 2.0000 -0.695836 -18.9347 + 6 2.0000 -0.570108 -15.5134 + 7 2.0000 -0.524991 -14.2857 + 8 2.0000 -0.507368 -13.8062 + 9 2.0000 -0.329083 -8.9548 + 10 2.0000 -0.288558 -7.8521 + 11 2.0000 -0.258053 -7.0220 + 12 0.0000 -0.175417 -4.7733 + 13 0.0000 0.057780 1.5723 + 14 0.0000 0.080794 2.1985 + 15 0.0000 0.150955 4.1077 + 16 0.0000 0.220736 6.0065 + 17 0.0000 0.276739 7.5305 + 18 0.0000 0.294736 8.0202 + 19 0.0000 0.327502 8.9118 + 20 0.0000 0.367348 9.9961 + 21 0.0000 0.381294 10.3755 + 22 0.0000 0.396435 10.7875 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +----------------------- +MULLIKEN ATOMIC CHARGES +----------------------- + 0 N : -0.283605 + 1 O : 0.229386 + 2 O : -0.210226 + 3 H : 0.264445 +Sum of atomic charges: -0.0000000 + +-------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES +-------------------------------- + 0 N s : 3.885323 s : 3.885323 + pz : 1.101877 p : 3.335783 + px : 1.394325 + py : 0.839581 + dz2 : 0.008322 d : 0.062499 + dxz : 0.009410 + dyz : 0.013572 + dx2y2 : 0.015512 + dxy : 0.015682 + + 1 O s : 3.737945 s : 3.737945 + pz : 1.382795 p : 3.886267 + px : 1.460700 + py : 1.042772 + dz2 : 0.005207 d : 0.146402 + dxz : 0.012458 + dyz : 0.046766 + dx2y2 : 0.056601 + dxy : 0.025369 + + 2 O s : 3.945903 s : 3.945903 + pz : 1.428096 p : 4.236737 + px : 1.441713 + py : 1.366928 + dz2 : 0.002502 d : 0.027585 + dxz : 0.007530 + dyz : 0.006138 + dx2y2 : 0.004033 + dxy : 0.007381 + + 3 H s : 0.705926 s : 0.705926 + pz : 0.006585 p : 0.029629 + px : 0.015477 + py : 0.007567 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +---------------------- +LOEWDIN ATOMIC CHARGES +---------------------- + 0 N : -0.054747 + 1 O : -0.197248 + 2 O : -0.028229 + 3 H : 0.280224 + +------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES +------------------------------- + 0 N s : 3.354619 s : 3.354619 + pz : 1.022407 p : 3.379274 + px : 1.371808 + py : 0.985059 + dz2 : 0.039175 d : 0.320854 + dxz : 0.009455 + dyz : 0.062917 + dx2y2 : 0.075386 + dxy : 0.133921 + + 1 O s : 3.356101 s : 3.356101 + pz : 1.278758 p : 4.040935 + px : 1.487933 + py : 1.274244 + dz2 : 0.062262 d : 0.800211 + dxz : 0.030872 + dyz : 0.201420 + dx2y2 : 0.239122 + dxy : 0.266535 + + 2 O s : 3.593275 s : 3.593275 + pz : 1.346617 p : 4.178210 + px : 1.437018 + py : 1.394576 + dz2 : 0.029884 d : 0.256745 + dxz : 0.030752 + dyz : 0.037096 + dx2y2 : 0.080376 + dxy : 0.078637 + + 3 H s : 0.645992 s : 0.645992 + pz : 0.014643 p : 0.073784 + px : 0.043563 + py : 0.015578 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 N 7.2836 7.0000 -0.2836 2.7298 2.7298 -0.0000 + 1 O 7.7706 8.0000 0.2294 2.6678 2.6678 0.0000 + 2 O 8.2102 8.0000 -0.2102 1.7458 1.7458 0.0000 + 3 H 0.7356 1.0000 0.2644 0.9172 0.9172 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-N , 1-O ) : 1.3937 B( 0-N , 2-O ) : 0.4565 B( 0-N , 3-H ) : 0.8797 +B( 1-O , 2-O ) : 1.2630 + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 8 sec + +Total time .... 8.619 sec +Sum of individual times .... 8.079 sec ( 93.7%) + +SCF preparation .... 1.570 sec ( 18.2%) +Fock matrix formation .... 2.222 sec ( 25.8%) + Startup .... 0.402 sec ( 18.1% of F) + Split-RI-J .... 0.030 sec ( 1.3% of F) + XC integration .... 0.459 sec ( 20.7% of F) + Basis function eval. .... 0.007 sec ( 1.5% of XC) + Density eval. .... 0.008 sec ( 1.7% of XC) + XC-Functional eval. .... 0.006 sec ( 1.3% of XC) + XC-Potential eval. .... 0.009 sec ( 2.0% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.290 sec ( 3.4%) +Total Energy calculation .... 0.015 sec ( 0.2%) +Population analysis .... 3.239 sec ( 37.6%) +Orbital Transformation .... 0.175 sec ( 2.0%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.147 sec ( 1.7%) +SOSCF solution .... 0.421 sec ( 4.9%) +Finished LeanSCF after 12.1 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 51.7 MB + + +------------------------------------------------------------------------------- + DFT DISPERSION CORRECTION + + DFTD4 V3.4.0 +------------------------------------------------------------------------------- +The R2SCAN3C composite method is recognized +Using three-body term ABC +Active option DFTDOPT ... 5 + +------------------------- ---------------- +Dispersion correction -0.000360202 +------------------------- ---------------- + +------------------ ----------------- +gCP correction 0.007173748 +------------------ ----------------- + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -205.564132611371 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +Storing optimized geometry in input.040.xyz ... done +Storing optimized geometry and energy in input.xyzall ... done +Storing actual gbw-file in input.040.gbw ... done + + + ************************************************************ + * Program running with 50 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 4 +Number of basis functions ... 77 +Max core memory ... 5900 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... 0.414224 0.841856 -0.054097 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 1 +Irrep : 0 +Energy : -205.5709461569200585 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: 0.040080240 0.778230537 0.011413731 +Nuclear contribution : -0.889969836 -1.495372485 0.113333442 + ----------------------------------------- +Total Dipole Moment : -0.849889596 -0.717141948 0.124747173 + ----------------------------------------- +Magnitude (a.u.) : 1.119002572 +Magnitude (Debye) : 2.844278500 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 3.466074 0.427322 0.380421 +Rotational constants in MHz : 103910.296104 12810.790096 11404.734445 + +Dipole components along the rotational axes: +x,y,z [a.u.] : -0.936601 -0.612328 0.000010 +x,y,z [Debye]: -2.380650 -1.556415 0.000025 + + + +Dipole moment calculation done in 1.1 sec + +Maximum memory used throughout the entire PROP-calculation: 26.8 MB + **** RELAXED SURFACE SCAN DONE *** + + SUMMARY OF THE CALCULATED SURFACE + +---------------------------- +RELAXED SURFACE SCAN RESULTS +---------------------------- + +Column 1: NONAME + +The Calculated Surface using the 'Actual Energy' + -180.00000000 -205.56412863 + -170.76923077 -205.56304415 + -161.53846154 -205.55981277 + -152.30769231 -205.55449922 + -143.07692308 -205.54721698 + -133.84615385 -205.53811775 + -124.61538462 -205.52741740 + -115.38461538 -205.51539728 + -106.15384615 -205.50245689 + -96.92307692 -205.49000818 + -87.69230769 -205.49181718 + -78.46153846 -205.50275068 + -69.23076923 -205.51519265 + -60.00000000 -205.52710432 + -50.76923077 -205.53796901 + -41.53846154 -205.54748809 + -32.30769231 -205.55543296 + -23.07692308 -205.56160894 + -13.84615385 -205.56584894 + -4.61538462 -205.56801310 + 4.61538462 -205.56801483 + 13.84615385 -205.56585336 + 23.07692308 -205.56161212 + 32.30769231 -205.55542977 + 41.53846154 -205.54748298 + 50.76923077 -205.53796909 + 60.00000000 -205.52710778 + 69.23076923 -205.51519567 + 78.46153846 -205.50275147 + 87.69230769 -205.49181828 + 96.92307692 -205.49000878 + 106.15384615 -205.50245773 + 115.38461538 -205.51540006 + 124.61538462 -205.52742038 + 133.84615385 -205.53811826 + 143.07692308 -205.54721530 + 152.30769231 -205.55449977 + 161.53846154 -205.55981412 + 170.76923077 -205.56304759 + 180.00000000 -205.56413261 + +The Calculated Surface using the SCF energy + -180.00000000 -205.57094234 + -170.76923077 -205.56985728 + -161.53846154 -205.56662479 + -152.30769231 -205.56131061 + -143.07692308 -205.55402755 + -133.84615385 -205.54492799 + -124.61538462 -205.53422760 + -115.38461538 -205.52220513 + -106.15384615 -205.50924953 + -96.92307692 -205.49638825 + -87.69230769 -205.49808206 + -78.46153846 -205.50920682 + -69.23076923 -205.52173166 + -60.00000000 -205.53370817 + -50.76923077 -205.54463137 + -41.53846154 -205.55421496 + -32.30769231 -205.56222277 + -23.07692308 -205.56845825 + -13.84615385 -205.57274563 + -4.61538462 -205.57493635 + 4.61538462 -205.57493772 + 13.84615385 -205.57274895 + 23.07692308 -205.56845963 + 32.30769231 -205.56221746 + 41.53846154 -205.55420673 + 50.76923077 -205.54463013 + 60.00000000 -205.53370804 + 69.23076923 -205.52173350 + 78.46153846 -205.50920844 + 87.69230769 -205.49808249 + 96.92307692 -205.49638951 + 106.15384615 -205.50925117 + 115.38461538 -205.52220963 + 124.61538462 -205.53423041 + 133.84615385 -205.54492928 + 143.07692308 -205.55402638 + 152.30769231 -205.56131161 + 161.53846154 -205.56662687 + 170.76923077 -205.56986109 + 180.00000000 -205.57094616 + + +-------------------------------- +SUGGESTED CITATIONS FOR THIS RUN +-------------------------------- + +Below you find a list of papers that are relevant to this ORCA run +We neither can nor want to force you to cite these papers, but we appreciate if you do +You receive ORCA, which is the product of decades of hard work by many enthusiastic individuals, for free +The only thing we kindly ask in return is that you cite our papers, +We deeply appreciate it, if you show your appreciation for ORCA by not just citing the generic ORCA reference. + +Please note that relegating all ORCA citations to the supporting information does *not* help us. +SI sections are not indexed - citations you put there will not count into any citation statistics +But we need these citations in order to attract the funding resources that allow us to do what we are doing + +Therefore, if you are a happy ORCA user, please consider citing a few of the papers listed below in the main body of your paper + +In addition to the list printed below, the program has created the file input.bibtex that contains the list in bibtex format +You can import this file easily into all common literature databanks and citation aid programs + + +List of essential papers. We consider these as the minimum necessary citations + + 1. Neese,F. + Software update: the ORCA program system, version 5.0 + WIRES Comput. Molec. Sci., 2022 12(1)e1606 + doi.org/10.1002/wcms.1606 + 2. Grimme,S.; Hansen,A.; Ehlert,S.; Mewes,J. + r2SCAN-3c: A 'Swiss army knife' composite electronic-structure method + J. Chem. Phys., 2021 154 064103 + doi.org/10.1063/5.0040021 + +List of papers to cite with high priority. The work reported in these papers was absolutely +necessary for this run to complete. +Our perspective: the developers of density functionals and basis sets usually get cited in chemistry papers +Good! But without the algorithms to do something with them, the functionals or basis sets would not do anything. +Hence, in our opinion, the algorithm design and method developments papers are equally worthy of getting cited + + 1. Neese,F. + An improvement of the resolution of the identity approximation for the formation of the Coulomb matrix + J. Comp. Chem., 2003 24(14)1740-1747 + doi.org/10.1002/jcc.10318 + 2. Neese,F. + The SHARK Integral Generation and Digestion System + J. Comp. Chem., 2022 1-16 + doi.org/10.1002/jcc.26942 + 3. Lehtola,S.; Steigemann,C.; Oliveira,M.; Marques,M. + Recent developments in Libxc - A comprehensive library of functionals for density functional theory + Software X, 2018 7 + doi.org/10.1016/j.softx.2017.11.002 + 4. Caldeweyher,E.; Bannwarth,C.; Grimme,S. + Extension of the D3 dispersion coefficient model + J. Chem. Phys., 2017 147 034112-XXXX + doi.org/10.1063/1.4993215 + 5. Caldeweyher,E.; Ehlert,S.; Hansen,A.; Neugebauer,H.; Spicher,S.; Bannwarth,C.; Grimme,S. + A generally applicable atomic-charge dependent London dispersion correction + J. Chem. Phys., 2019 150 154122-XXXX + doi.org/10.1063/1.5090222 + 6. Caldeweyher,E.; Mewes,J.; Ehlert,S.; Grimme,S. + Extension and evaluation of the D4 London-dispersion model for periodic systems + Phys. Chem. Chem. Phys., 2020 22(16)8499-8512 + doi.org/10.1039/D0CP00502A + +List of suggested additional citations. These are papers that are important in the 'surrounding' of +of this run, or papers that preceded the highly important papers. If you like your results we are grateful for a citation. + + 1. Neese,F. + The ORCA program system + WIRES Comput. Molec. Sci., 2012 2(1)73-78 + doi.org/10.1002/wcms.81 + 2. Neese,F. + Software update: the ORCA program system, version 4.0 + WIRES Comput. Molec. Sci., 2018 8(1)1-6 + doi.org/10.1002/wcms.1327 + 3. Neese,F.; Wennmohs,F.; Becker,U.; Riplinger,C. + The ORCA quantum chemistry program package + J. Chem. Phys., 2020 152 Art. No. L224108 + doi.org/10.1063/5.0004608 + +List of optional additional citations + + 1. Neese,F. + Approximate second-order SCF convergence for spin unrestricted wavefunctions + Chem. Phys. Lett., 2000 325(1-3)93-98 + doi.org/10.1016/s0009-2614(00)00662-x + +Timings for individual modules: + +Sum of individual times ... 1442.032 sec (= 24.034 min) +Startup calculation ... 219.333 sec (= 3.656 min) 15.2 % +SCF iterations ... 933.648 sec (= 15.561 min) 64.7 % +Property calculations ... 51.165 sec (= 0.853 min) 3.5 % +SCF Gradient evaluation ... 235.115 sec (= 3.919 min) 16.3 % +Geometry relaxation ... 2.771 sec (= 0.046 min) 0.2 % + ****ORCA TERMINATED NORMALLY**** +TOTAL RUN TIME: 0 days 0 hours 28 minutes 16 seconds 986 msec